JPH09141748A - Formation of transparent optical three-dimensional shaped article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the shape characteristics and transparency of an excellent three-dimensional shaped article by using a transparent optical radical curable liquid compsn. prepared by dissolving specific pts.wt. of specific polyorganosiloxane in specific pts.wt. of an optical radical curable liquid. SOLUTION: A transparent optical radical curable liquid compsn. used in the formation of a transparent optical three-dimensional shaped article is obtained by dissolving 10-200 pts.wt. of polyorganosiloxane in 100 pts.wt. of an optical radical curable liquid. Polyorganosiloxane has a trivalent and/or tetravalent siloxane unit forming a three-dimensional structure and a siloxane unit having a hydrocarbon group having carbon atoms directly bonded to silicon atoms and substituted with an org. group containing a radical polymerizable group as its structural units.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming a transparent optical three-dimensional object. In the presence of a photopolymerization initiator, a layer of a photoradical curable liquid composition containing a photoradical curable liquid is formed, and at least a part of the layer is irradiated by activating radiation, for example, an ultraviolet laser beam. After photo-curing, a new layer of the photo-radical curable liquid composition is formed on the photo-cured product, and at least a part of it is photo-cured by irradiating this layer with actinic radiation again. Repeatedly, an optical three-dimensional object which is a three-dimensional integral photo-cured product is formed from a continuous layer of the photo-radical curable liquid composition (JP-A-62-35966, JP-A-62-10140).
8, JP-A-3-21432, European Patent Publication 250
No. 121). Such an optical three-dimensional structure is mainly used as a shape confirmation model. The present invention is not limited to the shape confirmation model as described above, and as a characteristic that can be used as a practical part, a transparent molded article having excellent shape characteristics such as shape accuracy during molding and shape retention during hot molding The present invention relates to a method for forming an optical three-dimensional model that can be obtained.

[0002]

2. Description of the Related Art Conventionally, when a three-dimensional object is formed using a photo-radical curable liquid composition, the photo-radical curable liquid composition is irradiated with energy rays to form a green state cured product, and then the molded product is machined. For the purpose of improving physical properties and thermal properties, further irradiation with energy rays or post-curing such as heat treatment is performed. The cured product thus post-cured is generally provided as a three-dimensional molded item. The three-dimensional object obtained in this manner has a low shape accuracy due to deformation and the like, or even an object having an excellent shape accuracy is further deformed under a hot state, for example, under a use condition of 110 ° C or higher. It has been pointed out that the shape retention is deteriorated. The shape accuracy of the modeled object is low.
This is mainly because the cured products in the green state have low elastic properties such as rigidity and are easily deformed by their own weight or slight external stress. Also, the shape retention property in the hot state deteriorates when hot. This is largely due to lack of elastic properties such as rigidity. As means for improving the elastic properties such as rigidity of a molded object, 1) An example using a photocurable liquid having a high concentration of a polymerizable group for the purpose of increasing the crosslinking density of the obtained three-dimensional molded object, 2) Photocuring There are examples (Japanese Patent Application Laid-Open Nos. 7-26060 and 7-26062) in which inorganic solid fine particles and reinforcing fiber whiskers are contained as a filler in the ionic liquid.
In addition, as a means to reduce strain stress between each cured layer during molding and improve the shape accuracy of the green state,
3) Disperse fine particles in the photocurable liquid for the purpose of controlling the curing reaction by refracting, reflecting, and scattering the light incident on the photocurable liquid to control the penetration depth of the light and reducing the curing shrinkage. (JP-A-3-103415, JP-A-3-114732, JP-A-3-114733, JP-A-3-15520), 4) Dissolving a latent radiation polarizing substance in a photocurable liquid for the same purpose as in 3) above. There is an example (Japanese Patent Laid-Open No. 3-41126) in which, when photocured, the phase is separated to form a separated phase having a refractive index different from that of the cured photocurable liquid phase. However, in the example of 1) above, the volumetric shrinkage due to curing is increased, and the volumetric shrinkage is further increased by the post cure, resulting in deformation such as warpage due to internal stress and structural destruction such as cracks, and the shape accuracy is reversed. descend. In addition, in the above examples 2) to 4), the obtained three-dimensional object is opaque without exception. The three-dimensional molded objects obtained by these conventional examples cannot be used for applications that require shape accuracy at the time of molding and shape characteristics such as shape retention during hot and transparency at the same time.

[0003]

DISCLOSURE OF THE INVENTION The problem to be solved by the present invention is that, in the conventional method for molding a molded article using a photo-radical curable liquid composition, the shape characteristics and transparency of the obtained three-dimensional molded article are simultaneously improved. This is a point that cannot be satisfied.

[0004]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies to solve the above problems, it is correct and suitable to use a photoradical curable liquid composition in which a photoradical curable liquid and a specific polyorganosiloxane optically form a specific system. Found.

That is, according to the present invention, a layer of a photoradical-curable liquid composition containing a photoradical-curable liquid is formed in the presence of a photopolymerization initiator, and this layer is irradiated with actinic radiation to at least the layer. After photo-curing a part,
An optical three-dimensional structure in which a new layer of a photo-radical-curable liquid composition is formed on a photo-cured product, and at least a part of the composition is photo-cured by irradiating the layer with actinic radiation again. In forming a shaped article, a transparent photoradical curable liquid composition in which the following polyorganosiloxane is dissolved in the photoradical curable liquid at a ratio of 10 to 200 parts by weight per 100 parts by weight of the photoradical curable liquid is used. The present invention relates to a method for forming a transparent optical three-dimensional object characterized by the above.

Polyorganosiloxane: substituted with a trivalent and / or tetravalent siloxane unit as a constitutional unit, and a hydrocarbon group having a carbon atom directly bonded to a silicon atom and containing a radically polymerizable group. Three-dimensional structure of polyorganosiloxane having siloxane unit having a hydrocarbon group

The polyorganosiloxane used in the present invention has, as its constitutional unit, a trivalent siloxane unit and / or a tetravalent siloxane unit which forms a three-dimensional structure. Such trivalent siloxane units include siloxane units represented by the general formula [RSiO _3/2 ], and tetravalent siloxane units include [SiO 2
₂ ] is a silicic acid anhydride unit. Here, R is a substituted or unsubstituted hydrocarbon group having a carbon atom directly bonded to a silicon atom. In the present invention, the content ratio of such trivalent and / or tetravalent siloxane units in the polyorganosiloxane is not particularly limited, but it is usually 5 mol% or more, preferably 15 mol% or more. Organosiloxane is used.

Further, the polyorganosiloxane used in the present invention has, as a constitutional unit thereof, a hydrocarbon group having a carbon atom directly bonded to a silicon atom and substituted with an organic group containing a radically polymerizable group as described above. It has a siloxane unit having a hydrocarbon group (hereinafter referred to as a siloxane unit having a radically polymerizable group). Examples of the siloxane unit having a radically polymerizable group include 1) (meth) acryloxyalkylsiloxane units such as methacryloxypropylsiloxane units and acryloxyethylsiloxane units, 2) dimethacryloxypropylsiloxane units, and diacryloxyethylsiloxane. Units such as di (meth) acryloxyalkylsiloxane units, 3) methacryloxypropyl-methylsiloxane units, acryloxyethyl-ethylsiloxane units and other (meth) acryloxyalkylalkylsiloxane units, 4) vinylsiloxane units, vinyl Examples thereof include vinyl group-containing siloxane units such as a roxypropylsiloxane unit, and among them, a (meth) acryloxyalkylsiloxane unit is preferable.

In the polyorganosiloxane used in the present invention, as the siloxane units other than the silicic acid anhydride unit and the siloxane unit having a radically polymerizable group, 1) methylsiloxane unit, butylsiloxane unit, octylsiloxane unit, phenylsiloxane are used. Units such as trivalent siloxane units having a hydrocarbon group having a carbon atom directly bonded to a silicon atom, 2) ureidopropylsiloxane units, glycidoxypropylsiloxane units, N, N-dimethylaminopropylsiloxane units, Siloxane units having hydrocarbon groups having substituents other than radically polymerizable groups, 3) dimethylsiloxane units, diethylsiloxane units, ureidopropyl methylsiloxane units, glycidoxypropyl methylsiloxane units, N, N-di Such as chill aminopropyl methyl siloxane units, divalent siloxane units having a substituted or unsubstituted hydrocarbon group directly bonded to a silicon atom.

In the present invention, a polyorganosiloxane having a siloxane unit having a silanol group can be used as the constituent unit. The present invention does not particularly limit the structure of the polyorganosiloxane having a siloxane unit having a silanol group, and the structure contained in the siloxane unit as an unreacted group in a polysiloxane forming reaction based on polycondensation of a silanol group. Can be taken. For example, in the synthesis of polyorganosiloxane, the polycondensation reaction of silanol groups produced by hydrolysis of a silanol-forming compound is appropriately adjusted,
The silanol group can be introduced into the molecule of the polyorganosiloxane by a known means for leaving an unreacted group.

As the siloxane units constituting the polyorganosiloxane, other than the siloxane unit having a radical polymerizable group described above, a siloxane unit that is used to impart solubility to the photoradical curable liquid and a photoradical curable liquid used A siloxane unit having a substituent having a chemical structural affinity can be appropriately selected.

For the synthesis of the polyorganosiloxane used in the present invention, a known method by hydrolysis / polycondensation of a compound which forms a silanol by hydrolysis (hereinafter referred to as a silanol-forming compound) can be applied.

In the present invention, the silanol-forming compound that forms a siloxane unit having a radical-polymerizable group, which is an essential constituent unit of polyorganosiloxane, includes 1) methacryloxypropyltrimethoxysilane and acryloxyethyl. (Meth) acryloxyalkyltrialkoxysilanes such as triethoxysilane, 2) alkoxysilanes containing a vinyl group such as vinyltrimethoxysilane and vinyloxypropyltrimethoxysilane. As the silanol-forming compound that forms a siloxane unit other than the siloxane unit having a radical-polymerizable group, a silanol-forming compound that forms a silicic anhydride unit represented by [SiO ₂ ] is advantageous. Can be used. Examples thereof include orthoethyl silicate, tetramethoxysilane, tetrachlorosilane, trichlorohydrogensilane and the like.

In the polyorganosiloxane used in the present invention, as the silanol-forming compound used in the polyorganosiloxane-forming reaction, the proportion of the silanol-forming compound that forms a siloxane unit having a radical polymerizable group is particularly limited. It is not a thing, but it is preferable to set it as a ratio of 10 to 80 mol% in all silanol-forming compounds, and the silanol-forming compound and the silicic acid anhydride unit which will form a siloxane unit having a radically polymerizable group. It is further preferable that the total amount of the silanol-forming compounds to be formed is 50 mol% or more in the total silanol-forming compounds.

In the photoradical curable liquid composition used in the present invention, the above-mentioned polyorganosiloxane is dissolved in the photoradical curable liquid, and therefore the photoradical curable liquid composition is transparent. Here, transparent means
The polyorganosiloxane is present in the photo-radical curable liquid in a particle size at the molecular level, and due to the presence of the particles, light scattering, reflection, refraction and other phenomena can be almost ignored, that is, polyorganosiloxane exists. Means that the light transmittance is not affected. Above all, it is preferable to use an optically transparent photoradical curable liquid composition in which the polyorganosiloxane is dissolved in the photoradical curable liquid even with respect to actinic radiation to be irradiated, for example, ultraviolet rays.

In the present invention, known radical-polymerizable monomers can be used as the photo-radical curable liquid. This includes, for example, (meth) acrylic acid esters such as alkyl (meth) acrylate, alkanediol di (meth) acrylate, alkanetriol tri (meth) acrylate, polyether polyol poly (meth) acrylate, and (meth) acryloyl modified Urethane etc. are mentioned.

According to the present invention, when the photo-radical curable liquid composition is photo-cured by actinic radiation, the polyorganosiloxane dissolved therein becomes insoluble or agglomerates to make the shaped object opaque. There is no conversion. The reason is that the radical-polymerizable group contained in the polyorganosiloxane and the radical-polymerizable group contained in the photo-radical curable liquid are involved in the polymerization to form an integrated polymer having substantially no bilayer interface. It depends.

Further, as described above, the present invention provides a method for forming an optical three-dimensional molded article having improved shape characteristics by improving elastic characteristics such as rigidity of a cured product. For this purpose, as the photo-radical curable liquid, a liquid containing a vinyl monomer having an amide group or an aminocarbonyl group as a specific carbonyl group in the molecule is preferable. The reason is that by using such a radically polymerizable liquid, polar groups contained in polyorganosiloxane,
For example, it becomes possible to form a strong intermolecular bond such as a hydrogen bond between the silanol group and the above-mentioned specific carbonyl group, and as a result, it is possible to improve elastic properties such as rigidity of a cured product in a green state in photocuring. It will be extremely effective at.

As the vinyl monomer having an amide group as the specific carbonyl group as described above, 1) N, N-
Vinyl monomers having a tertiary amide group such as dimethylacrylamide, N, N-dimethylmethacrylamide, acrylic acid morpholide, methacrylic acid morpholide, N-vinylpyrrolidone and N-vinylcaprolactam, 2) N,
Examples thereof include vinyl monomers having a secondary amide group such as N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide and N-vinylacetamide. Examples of vinyl monomers having an aminocarbonyl group include various (meth) acryloyl-modified urethanes. This includes, for example, 1) n-valent polyisocyanate 1
Mol and a polyol (meth) acrylic acid partial ester having one hydroxyl group in the molecule obtained by esterification of polyol and (meth) acrylic acid n mol {hereinafter,
Unsaturated urethane obtained from (meth) acrylic ester monool} (described in JP-A-4-72353), 2) 1 mol of n-valent polyol, and n mol of diisocyanate, and (meth) as described above. Unsaturated urethane obtained from n moles of acrylic ester monool (as described in JP-A-2-145616), 3) 1 mole of n polyols and isocyanatoalkyl (meth)
Unsaturated urethane obtained from nmole of acrylate (Japanese Patent Laid-Open No. 3-163116 and Japanese Patent Laid-Open No. 6-99696).
No. 2), 4) 1 mol of a polyol (meth) acrylic acid having n free hydroxyl groups in the molecule,
Unsaturated urethane obtained from n-moles of isocyanatoalkyl (meth) acrylate (described in JP-A-4-53809), 5) Unsaturated urethane having a long-chain aliphatic hydrocarbon group in the molecule (special Kaihei 4-306214, JP-A-4-314715, JP-A 5-33
9332 and JP-A-6-9729), and 6) the mixture of unsaturated urethanes described in 1) to 5) above. Among these, (meth) acryloyl-modified Urethane and vinyl monomers having a tertiary amide group are preferred, and a mixture of both is more preferred.

In the photoradical curable liquid composition used in the present invention, the content ratio of the photoradical curable liquid and the polyorganosiloxane is 10 to 200 parts by weight of polyorganosiloxane per 100 parts by weight of the photoradical curable liquid. To do.

Next, an example of the method for producing the photo-radical curable liquid composition used in the present invention will be described. This includes hydrolyzing a silanol-forming compound containing a silanol-forming compound having a radical-polymerizable group in an aqueous medium in which a photo-radical-curable liquid is dissolved to form a silanol group, and contracting the silanol group produced. A so-called known polyorganosiloxane-forming reaction of forming a polyorganosiloxane by a polymerization reaction can be applied. The polyorganosiloxane obtained here is obtained in a state of being dissolved or dispersed in a solution in which the photoradical curable liquid is dissolved in an aqueous medium.

From the solution in which the polyorganosiloxane thus obtained is dissolved or dispersed, the aqueous medium contained therein is distilled off to obtain a transparent photoradical-curable liquid composition.

In the production of the above photo-radical curable liquid composition, a mixed solvent of water and a lower alcohol is usually used as an aqueous medium, but in order to obtain compatibility with the photo-radical curable liquid to be used, The type can be appropriately selected.

In the present invention, a photopolymerization initiator is used when the photoradical-curable liquid composition is subjected to optical three-dimensional modeling. The present invention does not particularly limit the kind of the photopolymerization initiator, but as the photopolymerization initiator, 1) benzoin,
Carbonyl compounds such as α-methylbenzoin, anthraquinone, 1-hydroxycyclohexylphenyl ketone and acetophenone, 2) sulfur compounds such as diphenylsulfide, diphenyldisulfide and dithiocarbamate, 3) polycyclic aromatic compounds such as α-chloromethylnaphthalene and anthracene A compound etc. are mentioned. The amount of the photopolymerization initiator used is usually 0.1 to 5 parts by weight, preferably 1 to 5 parts by weight, dissolved in advance in the photoradical curable liquid per 100 parts by weight of the photoradical curable liquid. It is preferable to use a new one. A photosensitizer such as n-butylamine, triethanolamine, or N, N-dimethylaminoethyl methacrylate may be used together with the photopolymerization initiator.

In the present invention, a desired three-dimensional object can be obtained by using a known optical three-dimensional object forming method. That is,
After supplying the photo-radical curable liquid composition with an appropriate thickness that the energy ray can reach, irradiating this with the energy ray to form the first hardened layer, a new photo-radical hardened layer is formed on the hardened layer. A desired three-dimensional structure can be formed by sequentially supplying the volatile liquid composition and irradiating the composition with an energy ray to form the next cured layer. Examples of energy rays used for optically forming a three-dimensional molded object include visible rays, ultraviolet rays, and electron rays, and ultraviolet rays are preferable.

The optical three-dimensional molded article obtained by applying the method of the present invention has excellent shape characteristics, that is, excellent shape accuracy at the time of molding and shape retention at the time of hot and having transparency. By having such characteristics, the obtained optical three-dimensional molded article can be used as a practical part that requires shape characteristics and transparency.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the method for forming a transparent optical three-dimensional object according to the present invention are as follows. 1) 40 parts by weight of acrylic acid morpholide and glycerin monoacrylate monomethacrylate / 2,4-tolylene diisocyanate / hydroxyethyl acrylate = 1
100 parts by weight of a photo-radical curable liquid consisting of 60 parts by weight of (meth) acryloyl-modified urethane which is a reaction product of 1/1 / molar ratio, γ-methacryloxypropyltrimethoxysilane / orthoethyl silicate = 4 / 100 parts by weight of polyorganosiloxane a, which is a three-dimensional structure having a methacryloxypropyl group as a radically polymerizable group in the molecule, which is obtained by hydrolyzing 1 (molar ratio) of a silane mixture and further polycondensation, was dissolved. A method of subjecting a transparent photo-radical-curable liquid composition to the above-described optical three-dimensional modeling method in the presence of a photopolymerization initiator.

2) N, N-dimethylacrylamide 30
Parts by weight and glycerin monoacrylate monomethacrylate / isophorone diisocyanate = 2/1 (molar ratio)
(Meth) acryloyl-modified urethane 70 which is a reaction product of
100 parts by weight of a photo-radical curable liquid consisting of 1 part by weight and γ-methacryloxypropyltrimethoxysilane /
Three-dimensional having a methacryloxypropyl group as a radically polymerizable group in the molecule obtained by hydrolyzing a silane mixture of ureidopropylmethyldimethoxysilane / orthoethylsilicate = 2/1/1 (molar ratio) and further polycondensation A method of subjecting a transparent photo-radical-curable liquid composition in which 150 parts by weight of a polyorganosiloxane b which is a structure is dissolved to the above-mentioned optical three-dimensional modeling method in the presence of a photopolymerization initiator.

3) 25 parts by weight of N-vinylcaprolactam, and (meth) acryloyl-modified urethane 75 from 2) above.
100 parts by weight of a photo-radical curable liquid consisting of 1 part by weight and γ-methacryloxypropyltrimethoxysilane /
N, N-dimethylaminopropyltrimethoxysilane /
Tertiary having a methacryloxypropyl group as a radically polymerizable group in the molecule obtained by hydrolyzing a silane mixture of orthoethyl silicate / octamethyltetrasiloxane = 16/4/16/1 (molar ratio) and further polycondensation A method of subjecting a transparent photoradical-curable liquid composition in which 60 parts by weight of polyorganosiloxane c, which is the original structure, is dissolved to the above-described optical three-dimensional modeling method in the presence of a photopolymerization initiator.

[0030]

EXAMPLES Examples will be given below to make the constitution and effects of the present invention more specific, but the present invention is not limited to the examples. In the following Examples and the like, parts indicate parts by weight, and% indicates% by weight.

Test Category 1 (Synthesis of polyorganosiloxane etc.)-Synthesis of polyorganosiloxane a 300 parts of methanol, 62 parts of acrylic acid morpholide and 0.5 * 10 ³ mol / m ³ of hydrochloric acid aqueous solution 30 in a flask
Parts were charged and stirred to obtain a uniform solution. At room temperature, γ-methacryloxypropyltrimethoxysilane 1
98 parts (0.8 mol) and orthoethyl silicate 42
Part (0.2 mol) of the mixture was added dropwise over 1 hour to carry out hydrolysis and polycondensation reaction. Then, the mixture was stirred at room temperature for 2 hours, further at 60 ° C. for 3 hours, and then cooled to room temperature to obtain a transparent solution containing polyorganosiloxane a.
The concentrations of polyorganosiloxane and acrylic acid morpholide in the solution obtained here were 24.5% and 9.8%, respectively.

Synthesis of polyorganosiloxane b As in the case of polyorganosiloxane a, 300 parts of methanol, 29 parts of N, N-dimethylacrylamide,
30 parts of 0.5 × 10 ³ mol / m ³ aqueous hydrochloric acid solution, 124 parts of γ-methacryloxypropyltrimethoxysilane (0.5 mol), 52 parts of ureidopropyl methyldimethoxysilane (0.25 mol) and orthoethyl. Hydrolysis and polycondensation reaction was carried out using 52 parts (0.25 mol) of silicate to give 24.
An almost transparent colloidal solution containing 7% and N, N-dimethylacrylamide in a ratio of 4.9% was obtained.

Synthesis of polyorganosiloxane c As in the case of polyorganosiloxane a, 300 parts of methanol, 49 parts of N-vinylcaprolactam, 1.5 ×
30 parts of 10 ³ mol / m ³ ammonia water, 99 parts (0.4 mol) of γ-methacryloxypropyltrimethoxysilane, 21 parts (0.1 mol) of N, N-dimethylaminopropyltrimethoxysilane, orthoethyl. Silicate 8
Using 3 parts (0.4 mol) and 7 parts (0.025 mol) of octamethyltetrasiloxane, a hydrolysis and polycondensation reaction was carried out to give a polyorganosiloxane c of 19.9%.
And a clear solution containing N-vinylcaprolactam in a proportion of 8.3% was obtained.

Synthesis of polyorganosiloxane r-1 As in the case of polyorganosiloxane a, 27 parts of acrylic acid morpholide, 300 parts of methanol, 0.5 × 10 5.
30 parts of a ³ mol / m ³ aqueous hydrochloric acid solution, 46 parts (0.2 mol) of γ-methacryloxypropyl methyldimethoxysilane and 30 parts of octamethyltetrasiloxane (0.1
Mol) is used to carry out hydrolysis and polycondensation reaction, and the proportion of polyorganosiloxane r-1 having a linear structure having a radical polymerizable group in the molecule is 15.5% and acrylic acid morpholide is 6.2%. To obtain a transparent solution.

Synthesis of polyorganosiloxane r-2 Similar to polyorganosiloxane b, methanol 300
Part, N, N-dimethylacrylamide 30 parts, 0.5 ×
30 parts of 10 ³ mol / m ³ aqueous solution, 117 parts (0.5 mol) of γ-butanoyloxypropyltrimethoxysilane, ureidopropyl methyldimethoxysilane 52
Part (0.25 mol) and 52 parts (0.25 mol) of orthoethyl silicate to carry out hydrolysis and polycondensation, and a polyorganosiloxane having a three-dimensional structure containing no radically polymerizable group in the molecule. An almost transparent colloidal solution containing 25.6% r-2 and 5.2% N, N-dimethylacrylamide was obtained.

Synthesis of silica r-3 As in the case of polyorganosiloxane a, 300 parts of methanol, 30 parts of 0.5 × 10 ³ mol / m ³ aqueous solution,
The hydrolysis and polycondensation reaction was carried out using 312 parts (1.5 mol) of orthoethyl silicate. Next, lower alcohol such as methanol and ethanol and water were distilled off from the contents under reduced pressure to obtain 30% silica r-3 as a solid content.
A milky white colloidal suspension was obtained.

Test Category 2 (Preparation of Photoradical Curable Liquid Composition) Preparation of Photoradical Curable Liquid Composition P-1 408 parts of the transparent solution containing the polyorganosiloxane a obtained in Test Category 1 was added to glycerin. Monoacrylate monomethacrylate / 2,4-tolylene diisocyanate /
Hydroxyethyl acrylate = 1/1/1 (molar ratio)
(Meth) acryloyl-modified urethane 60 which is a reaction product of
After adding and dissolving the components, the mixture was heated under reduced pressure to completely distill off lower alcohols such as methanol and ethanol and water,
A transparent photo-radical curable liquid composition P-1 comprising 40 parts of acrylic acid morpholide, 60 parts of the (meth) acryloyl-modified urethane and 100 parts by weight of polyorganosiloxane a was obtained.

Photo radical curable liquid composition P-2, P
-3 and R-1 to R-4, as in the case of the photo-radical curable liquid composition P-1, using the polyorganosiloxane or silica synthesized in Test Category 1, a photo-radical curable liquid composition. P-2 and P-
3 and photo-radical curable composition R-1 for comparison
R-4 was prepared. The compositions of these are summarized in Table 1.

The photoradical curable liquid compositions P-1 to P-3 and R-1 to R-4 obtained above and the photoradical curable liquid R- used in the photoradical curable liquid composition.
For 5 to R-7, these states were visually observed, and the light transmittance was also measured by the method described below. These results are also shown in Table 1. Light transmittance: The sample was placed in a quartz cell having a sample layer having a thickness of 1 mm, and the transmittance for ultraviolet rays having a wavelength of 3250 angstrom was measured using an absorptiometer.

[0040]

[Table 1]

In Table 1, A-1 is a (meth) acryloyl-modified urethane A which is a reaction product of glycerin monoacrylate monomethacrylate / 2,4-tolylene diisocyanate / hydroxyethyl acrylate = 1/1/1 (molar ratio). -2: (meth) acryloyl-modified urethane which is a reaction product of glycerin monoacrylate monomethacrylate / isophorone diisocyanate = 2/1 (molar ratio) B-1: acrylic acid morpholide B-2: N, N-dimethylacrylamide B-3 : N-vinylcaprolactam polyorganosiloxane a, b, c, r-1, r-2 and silica r-3: those synthesized in Test Category 1

Test Category 3 (Formation of optical three-dimensional model and evaluation of model) 1) Formation of optical three-dimensional model Three-dimensional NC table equipped with a container and helium / cadmium laser light (output 25 mW, wavelength 3250 angstrom) ) An optical three-dimensional modeling apparatus mainly composed of a control system was used. The above container was filled with 100 parts of the composition prepared in Test Category 2 dissolved in 3 parts of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (hereinafter, simply referred to as mixed solution), 0.10 mm of the mixed solution from the container to a horizontal plane (XY plane)
Helium-cadmium laser beam focused from the vertical direction (Z-axis direction) to the surface (X-Y axis plane) was scanned to cure a predetermined portion. A new mixed solution with a thickness of 0.10 mm is supplied on the cured product,
It was similarly cured. Thereafter, in the same manner, a total of 30 layers were laminated and a 80 mm × 20 mm × 3 mm flat plate-shaped test piece was stereolithographically formed. The obtained shaped article was washed with isopropyl alcohol to obtain a green shaped article. By the same operation, 10 green shaped objects were obtained for each sample. Five of them were further irradiated with an ultraviolet lamp of 3 kW for 30 minutes, and then heated at 120 ° C. for 30 minutes to perform post-curing to obtain a post-curing shaped article.

2) Measurement of mechanical properties Stiffness of the obtained molded article was measured according to ASTM D747-70 as an index of the degree of easiness of deformation under constant stress. Five measurements were made for each sample, and the average value is shown in Table 2.

3) Evaluation of Thermal Physical Properties In the same manner as in 1), post-curing was further performed after optical three-dimensional modeling to prepare a 120 mm × 10 mm × 4 mm flat plate type test piece. About this test piece JIS K7
According to 207, the deflection temperature under load was measured as an index of the shape retention during hot under a load of 1.81 MPa. The results are shown in Table 2.

3) Evaluation of Hardened Product Transparency In the same manner as in 1), post-curing was further performed after optical three-dimensional modeling to prepare a 120 mm × 60 mm × 5 mm flat plate type test piece. This test piece was evaluated by the method shown below. The results are shown in Table 2. 1 test piece
It was installed parallel to the paper surface at a distance of 10 cm from the paper surface on which 0.5-point type was printed, and the transparency of characters by the naked eye was evaluated according to the following criteria, which was used as an index of transparency. ◯: It is transparent and the characters can be clearly read. Δ: Semi-transparent, and it is difficult to read characters. X: Opaque, and characters cannot be seen through at all.

[0046]

[Table 2]

[0047]

As is apparent from the above, according to the present invention described above, it is difficult for an optical three-dimensional object to be deformed in the green state, the shape-retaining property during post-curing hot is excellent, and the transparency is high. There is an effect that an excellent optical three-dimensional molded article can be obtained.

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Claims (3)

[Claims] 1. A layer of a photoradical curable liquid composition containing a photoradical curable liquid is formed in the presence of a photopolymerization initiator, and at least a part of the layer is irradiated by activating radiation. After photo-curing, a new layer of the photo-radical curable liquid composition is formed on the photo-cured product, and at least a part of it is photo-cured by irradiating this layer with actinic radiation again. In the repeated formation of an optical three-dimensional molded object, a transparent photoradical curing in which the following polyorganosiloxane is dissolved in the photoradical curable liquid at a ratio of 10 to 200 parts by weight per 100 parts by weight of the photoradical curable liquid. A method for forming a transparent optical three-dimensional object, which comprises using a liquid composition. Polyorganosiloxane: As a constitutional unit, trivalent and / or
Or a polyorganosiloxane tertiary having a tetravalent siloxane unit and a siloxane unit having a hydrocarbon group having a carbon atom directly bonded to a silicon atom and having a hydrocarbon group substituted with an organic group containing a radically polymerizable group Original structure 2. The method for forming a transparent optical three-dimensional structure according to claim 1, wherein the radical photopolymerizable liquid and the polyorganosiloxane are subjected to radical copolymerization by irradiating with actinic radiation. 3. A transparent optical three-dimensional structure according to claim 1 or 2, wherein a photoradical-curable liquid composition in which polyorganosiloxane is present in a state of being optically transparent and dissolved in the active radiation to be irradiated. Forming method.