JPH07329191A - Photoforming - Google Patents

Abstract

PURPOSE:To prevent a liquid crystal panel from becoming deteriorated qualitatively due to ultraviolet ray and thereby enhance a value of practical use by forming a first layer plane cured product by projecting a desired plane photoimage to the interface of a resin through a mask and repeating this step to laminate the cured product for the final formation of a three-dimensional form. CONSTITUTION:A light emitted from a visible light source with a wavelength of 400 to 1500nm as an output wavelength free from an ultraviolet wavelength is emitted to a photocurable resin containing a chemical compound with at least, one unsaturated double bond in a single molecule or/and an epoxy compound and a metallocene compound under focus adjustment and convergent degree adjustment. Further, thus the light permeates a liquid crystal panel 5 controlled by a control device 8 under a pattern control. Consequently, a first layer plane cured product is obtained by projecting a desired plane light image to the interface of the resin through a mask. For the second and following layers, a thin layer of resin is applied to the layer formed after the sequential formation of the cured products, and a three-dimensional form is obtained by repeating the above laminating procedures.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photomask system for irradiating a photocurable resin with light energy of a desired shape and laminating the obtained layered flat cured product to form a three-dimensional model. The present invention relates to an improvement of the stereolithography method.

[0002]

2. Description of the Related Art Conventionally, various stereolithography methods have been known for irradiating a photocurable resin with light energy to form a three-dimensional molding, and recently, in particular, recently published by Nikkan Kogyo Shimbun. "Stereolithography" (published on October 30, 1990, author: Yoji Marutani, Kazuo Okawa, Seiji Hayano, Naoichiro Saito, Takashi Nakai).

As a conventional stereolithography method, a particularly common one is to provide a base plate as a modeling table near a resin liquid level in an open top type resin tank in which a photocurable resin is stored. By irradiating the free liquid surface with light from above, the first cured resin layer is formed on the plate, and then the plate is lowered to the inside of the tank by the thickness of the cured resin layer. Repeating the method of irradiating the resin on the first resin cured product layer with light to form the second resin cured product layer, and successively laminating sliced resin cured product layers. Is a method for forming a desired three-dimensional shape. This method is called the free liquid surface method because the table in the tank is sequentially submerged from the free liquid surface of the resin to form the molded article while laminating the cured product.

As another method, a base plate is provided near the bottom in a resin tank whose bottom is a light transmission window, and light is emitted from below the resin tank toward the plate through the bottom transmission window. The resin between the bottom surface and the bottom surface is cured as a resin cured material layer of the first layer, and then the plate is pulled up to peel off the resin cured material layer of the first layer from the bottom surface.
The method of forming the second resin cured material layer by light from below the resin tank between the first layer resin cured material layer and the bottom surface is repeated. Since the liquid level of the resin is regulated between the plate and the existing cured product layer, it is called the regulated liquid level method.

Further, in the prior art, as an exposure method for irradiating the resin with light, a method of scanning a laser beam with data of a sectional shape to be formed and a uniform light source irradiation through a pre-fabricated photomask are performed. The method is considered, and the former is called the scanning method and the latter is called the photomask method.

However, in the scanning method using a laser light source, since the laser light itself is a beam with a fine diameter of several microns to 300 microns, it takes a lot of time to perform an operation for scanning to cover a desired cross-sectional shape. Therefore, there is a problem that the production efficiency is low.

[0007]

On the other hand, the photolithography method using the photomask method as the prior art is capable of exposing a cross section of a desired shape, so that the exposure time per laminated surface layer is short,
Although it has an advantage that the scanning method can be shortened, which is not provided by the scanning method, it has the following technical problems.

The point pointed out as the problem is that in the conventional photomask method, it is necessary to prepare in advance a huge number of photomasks corresponding to the number of layers of the sectional shape. Therefore, recently, in order to solve the problem of such a photomask method, a liquid crystal panel is used instead of preparing a physical photomask for each laminated section, and a desired sectional shape is formed on this liquid crystal panel for each laminated section. A technique of using a liquid crystal panel as a photomask has been proposed, in which drawing is performed by a control device.

However, the technique of using this liquid crystal panel as a photomask still has the following unsolved problems in reality. That is, since the photo-curable resin used in the stereolithography method is an ultraviolet-curable resin,
It is necessary to mainly irradiate light from a light source containing ultraviolet rays, but on the other hand, liquid crystal has a property that it is very weak to ultraviolet rays systematically, so that it is severely deteriorated by being irradiated with ultraviolet rays. . For these reasons, many technologies that use liquid crystal panels as photomasks have been disclosed, but as a practical problem, none of these technologies have practical utility and are still fatal. Has become a technical defect.

[0010]

The present invention was developed for the purpose of solving the above-mentioned problems of the conventional stereolithography method, and one or more unsaturated diamines in one molecule. A photocurable resin containing a compound A or (and) an epoxy compound B having a heavy bond and a metallocene compound C is irradiated with light emitted from a visible light source having an output wavelength of 400 to 1500 nm excluding the ultraviolet wavelength. The desired planar light image is mask-projected on the resin interface by passing through the liquid crystal panel whose pattern is adjusted by the optical system and the pattern is controlled by the control device to obtain the first layer of the cured product. The second and subsequent layers are characterized in that the layers after the cured product is sequentially filled with a thin layer of resin and this operation is repeated to form a three-dimensional model.

[0011]

In the present invention, a visible light curable photocurable resin, that is, a compound A having one or more unsaturated double bonds in one molecule and / or an epoxy compound B and a metallocene compound C are contained. Since the photocurable resin to be irradiated is irradiated with visible light having an output wavelength of 400 to 1500 nm excluding the ultraviolet wavelength, it is possible to cure the resin while appropriately protecting the liquid crystal panel. It is possible to sufficiently realize the stereolithography method used as a photomask.

[0012]

EXAMPLE Next, the stereolithography method according to the present invention will be described with reference to the modeling apparatus according to the free liquid level method shown in FIG. 1. Reference numeral 12 is a resin molding tank for storing the photocurable resin 11. A base plate 9 a that moves up and down in the tank by an elevator device 9 is provided in the tank 12, and a light irradiation device 1 is arranged above the resin modeling tank 12.

The light irradiation device 1 is capable of irradiating visible light having an output wavelength of 400 to 1500 nm excluding the ultraviolet wavelength, and specifically, a halogen lamp, a mercury lamp, a xenon lamp, a metal halide lamp. Are preferably used. However, even these light irradiation devices 1 may sometimes contain a small amount of ultraviolet rays. Therefore, in order to eliminate the obstacle in such a case, an ultraviolet cut filter 2 is arranged below the light irradiation device 1. Further, below the ultraviolet cut filter 2, a shutter device 3 for projecting or blocking the light energy emitted from the light irradiating device 1 is provided.

The shutter device 3 is operated by a shutter controller 6 controlled by a computer unit 8. Further, below the shutter device 3,
Optical lens groups 4a, 4 for performing focus adjustment and focus adjustment of light energy emitted from the light irradiation device 1.
b and a liquid crystal panel 5 as a photomask are arranged. In this embodiment, the liquid crystal panel 5 is arranged between the optical lens 4a on the light irradiation device 1 side and the optical lens group 4b on the photocurable resin 11 side, but the optical lens group is the light irradiation device 1 '. May be provided on the side or on the side of the photocurable resin 11 which is the irradiated body.

The liquid crystal panel 5 includes a liquid crystal panel controller 7 controlled by the computer unit 8.
Operated by this computer unit 8
Controls not only the liquid crystal panel controller 7 and the shutter controller 6, but also the light irradiation device 1, the molding elevator 9, the resin supply device 10 attached to the resin molding tank 12, and the like.

The computer unit 8 arithmetically controls the plane shape for three-dimensional additive manufacturing, and this is drawn as an image serving as a photomask on the liquid crystal panel 5, from which the light irradiation device 1 and the ultraviolet cut filter 2 and The light energy adjusted by the optical lens groups 4a and 4b is transmitted, and the light image drawn by the liquid crystal panel is projected on the photocurable resin 11 in the resin modeling tank 12.

In a photomask type optical molding technique using a liquid crystal that has been conventionally proposed, an ultraviolet curable resin is used as a photocurable resin used for molding, and light energy including ultraviolet rays or near ultraviolet rays is applied to the resin. It was necessary to irradiate. However, electromagnetic waves having a short wavelength such as ultraviolet rays have a drawback that they cannot be put into practical use because they have a property of destroying the structure of liquid crystal. Therefore, in the present invention, as the photocurable resin 11 to which the light energy is applied,
A special resin that can be cured by visible light having an output wavelength of 400 to 1500 nm in which ultraviolet rays are actively excluded is used.

In the stereolithography method of the present invention, a photocurable resin containing compound A or (and) epoxy compound B having one or more unsaturated double bonds in one molecule and metallocene compound C is used. . The compound A having one or more unsaturated double bonds in one molecule in this resin is, for example, a compound having one or more acryloyl group and methacryloyl group, vinyl group, allyl group or vinylene group in one molecule. And unsaturated polyester compounds.

Specific examples of the compound A include epoxy (meth) acrylates obtained by reacting an epoxy resin such as a bisphenol type or novolak type aromatic epoxy resin or an aliphatic epoxy resin with (meth) acrylic acid. And polyester (meth) acrylates obtained by the reaction of polyester polyols obtained by the reaction of polyhydric alcohols and polybasic acids with (meth) acrylic acid, or polyether polyols, polyester polyols, caprolactone polyols, polycarbonate polyols, etc. Examples thereof include urethane (meth) acrylate obtained by reacting an organic polyisocyanate and the like with hydroxyl (meth) acrylate.

Further, a (meth) acrylate oligomer such as a reaction product of a compound having one or more hydroxyl group and (meth) acryloyl group in one molecule and a compound having one or more non-hydroxyl group in one molecule, , (Meth) acrylamide, N-methylol (meth) acrylamide, N-
Methoxymethyl (meth) acrylic amide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2.2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2.2-bis (4- (meth) acryloyloxyethoxyphenyl) methane, neopentyl glycol di (meth) acrylate, hydroxypipanoic acid neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate , Dioxane glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipen Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, diethylene glycol divinyl ether, trimethylol Propane trivinyl ether,
Allyl compounds such as cyclohexyldivinyl ether, N-vinylcarbazole, divinylbenzene, styrenes, triallyl isocyanurate, trimethylolpropane di (tri) allyl ether, pentaerythritol tri (tetra) allyl ether, diallyl phthalate can be mentioned. .

The unsaturated polyester is obtained, for example, by reacting a diol such as ethylene glycol, diethylene glycol, an ethylene oxide or propylene oxide adduct of bisphenol A with a dibasic acid containing an unsaturated acid such as maleic anhydride. A compound etc. are mentioned.

Examples of the epoxy compound B include bisphenol type epoxy such as bisphenol F type, bisphenol A type and bisphenol S type and novolac type epoxy such as phenol novolac and cresol novolac type, vinylcyclohexenedioxide, limonene (mono) diepoxide, 1 , 2-epoxy-5-hydroxy-4,7-methano-perhydroindene, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, bis (3,4-epoxycyclohexyl)
Adipate, alicyclic epoxy such as methacrylic acid- (3,4-epoxycyclohexyl) methyl, adipic acid diglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidyl (meth) acrylate and vinyl Examples thereof include aliphatic epoxies such as copolymers with system monomers. An alicyclic epoxy is mentioned as a particularly preferable epoxy compound.

The compound A or the epoxy compound B having one or more unsaturated double bonds in one molecule may be used alone or in admixture of two or more, if desired. it can.

On the other hand, as the metallocene compound C used in the present invention, a compound represented by the following general formula (1) is used.

[0025]

[Equation 1]

In the above general formula (1), a is a number of 1 or 2, n and q are each independently an integer of 1 to 3, and M is 1B group, 4A group to 7A of the periodic table. Tribe or 8
A monovalent to trivalent metal cation of the group, m is an integer corresponding to the valence of L + q, Q is a halogen atom,
L is a divalent to 7-valent metal or nonmetal, and R ¹ is π-
Arene, R ² is a π-arene or a π-arene anion.

Further, as the compound C consisting of the above general formula (1), particularly (η6-benzene) (η5-cyclopentadienyl) iron (divalent) hexafluorophosphate,
(Η6-cumene) (η5-cyclopentadienyl) iron (divalent) hexafluorophosphate, (η6-isopropylbenzene) (η5-cyclopentadienyl) iron (2
Ferrocene compounds such as (valent) hexafluoroantimonate and (η6-naphthalene) (η5-cyclopentadienyl) iron (divalent) hexafluoroantimonate are preferable. The above metallocene compound may be used in an amount of 1
It is possible to use one kind or a mixture of two or more kinds at any ratio.

Further, the amount of the compound A or the epoxy compound B having one or more ethylenically unsaturated double bonds in one molecule used in the present invention or the amount of the compound A and the compound B used in combination is 5.0 to 9 of the total amount of the resin composition
9.9% by weight is preferable, and particularly preferably 10.0 to 9
The amount of the metallocene compound C used is 9.5% by weight.
0.1 to 10.0% by weight is preferable, and 0.5 to 8.0% by weight is particularly preferable.

In the photocurable resin composition of the present invention, the compound A or (and) the epoxy compound B having one or more unsaturated double bonds in one molecule and the metallocene compound C are mixed by a means such as stirring. Obtained by

In the photocurable resin composition of the present invention, if necessary, a photoradical polymerization inhibitor, a photocationic polymerization inhibitor,
Coloring of non-reactive polymers, crosslinking agents, extender pigments, polymerization inhibitors, thickeners, flow improvers, defoamers, leveling agents, matting agents, plasticizers, solvents, fillers, pigments or dyes Agents and auxiliaries can be used in combination.

The computer unit 8 for controlling the light irradiation device 1, the shutter controller 6, the liquid crystal panel controller 7 and the like with respect to the above-mentioned photocurable resin 11 is C
One that has built-in AD and controls additive manufacturing data from CAD input of three-dimensional model, or one that designs the three-dimensional model by another computer, or three-dimensional by CT scanner, MRI, three-dimensional shape measuring instrument Various combinations are conceivable, such as those for controlling the additive manufacturing of the device by exchanging data with the device for recognizing a three-dimensional shape.

The computer unit 8 described above is shown in FIG.
2, the desired shape of the three-dimensional layered product 14 is converted into slice data 15 for layered modeling that forms each layer of the modeled object 14 as shown in FIG. Then, an image serving as a photomask is drawn on the liquid crystal panel 5. The image at this time is the optical lens group 4a,
The negative image is selectively used by the combination of 4b.

When the liquid crystal panel 5 is structurally smaller than the desired cross-sectional shape, the desired shape can be formed by dividing the cross-sectional shape and exposing and projecting. At this time, modeling can be efficiently realized by additionally providing a mechanism for moving the light irradiation member, the modeling elevator section, and the resin modeling tank in the X direction or the Y direction.

As an example, the modeling process of the optical molding method using the free liquid surface method shown in FIG. 1 will be described. First, the base plate 9a of the modeling elevator 9 is three-dimensionally laminated by the thickness corresponding to the slice data. The computer unit 8 causes each of the desired planar shapes of the three-dimensional layered product to be submerged by causing the computer unit 8 to sink the liquid surface of the photocurable resin 11 by an amount of movement corresponding to the thickness of the first-layer modeled product layer 13 in the modeled object 14. The liquid crystal panel 5 is arithmetically controlled to draw an image of the first-layer modeled object layer 13 serving as a photomask.

In this state, the computer unit 8
The light energy adjusted by the light irradiation device 1, the ultraviolet ray cut filter 2, the shutter 3, and the optical lens groups 4a and 4b is directed to the liquid crystal panel 5 on which the image of the first-layer modeling object layer 13 is drawn. A predetermined light image drawn on the liquid crystal panel 5 is projected and projected on the liquid surface of the photo-curable resin on the base plate 9a, and the first shaped object layer 1 is formed.
Get 3. And after that, repeat the same operation one after another,
The target predetermined shaped article is constructed by stacking the following layered article layers.

As the modeling apparatus, as in the free liquid level method described in the present embodiment, a molding object to be molded on the base plate is submerged in a resin tank, and a new molding object is sequentially formed on the existing laminated molding object layer. In addition to the work subsidence method in which the modeling layers are laminated, the modeling layer is formed on the base plate fixed to the lower part of the resin modeling tank by the same free liquid level method, and the first modeling layer is After solidification, a liquid level rising method in which a photocurable resin is injected onto the solidified layer and a new model layer is laminated on the solidified layer, or a known light level method such as the above-mentioned regulated liquid level method is used. Although there are molding means, it is sufficiently possible to apply the improvement shown in the present invention to these various molding methods.

[0037]

INDUSTRIAL APPLICABILITY As described above, in the present invention, a photocurable resin containing compound A or (and) epoxy compound B having one or more unsaturated double bonds in one molecule and metallocene compound C is used. Wavelength 400 excluding ultraviolet wavelength from resin
A light emitted from a visible light source having an output wavelength of ˜1500 nm is focused and focused by an optical system,
Since this light is transmitted to the liquid crystal panel on which the image of the target modeling layer is drawn by the pattern control by the control device, the deterioration of the liquid crystal panel due to the ultraviolet ray, which is a fatal defect in the conventional stereolithography method, can be surely performed. It is possible to provide a stereolithography method using visible light that is highly stable and can be prevented.

Further, in the conventional method of using a liquid crystal as a photomask, the liquid crystal panel is deteriorated by ultraviolet rays. Therefore, when irradiating light energy, a huge amount of liquid crystal does not depend on the number of layers of the cross-sectional shape. It was necessary to prepare a number of photomasks in advance, but in the present invention, since the liquid crystal panel is properly protected by positively excluding the ultraviolet rays in the light energy, a photomask using liquid crystals can be put into practical use. It eliminates the need to prepare a troublesome photomask, simplifies the physical effort, and enables an efficient modeling method.

Further, according to the present invention, since a photomask made of liquid crystal can be put into practical use, it has an advantage that exposure can be performed more efficiently and a molding time can be greatly shortened as compared with the laser scanning method.

[Brief description of drawings]

FIG. 1 is a front perspective view showing a configuration of an optical modeling apparatus using a visible light source, a photocurable resin, and a liquid crystal photomask according to an embodiment of the present invention.

FIG. 2 is a conceptual diagram of a layered three-dimensional model according to the stereolithography method of the present invention. Show.

[Explanation of symbols]

 1 Light Irradiation Device 2 Ultraviolet Cut Filter 3 Shutter 4 Optical Lens Group 5 Liquid Crystal Panel 6 Shutter Controller 7 Liquid Crystal Panel Controller 8 Computer Unit 9 Modeling Elevator 9a Base Plate 10 Resin Supply Device 11 Photocurable Resin 12 Resin Modeling Tank 13 First Layer Model layer stack 14 3D stack model 15 Slice data of 3D stack model

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication B29K 105: 24 (72) Inventor Koji Isobe 1-20-10 Nikura, Wako-shi, Saitama Prefecture (72) Inventor Masanori Sasahara 11-15-401 Chofu Innai Town, Shimonoseki City, Yamaguchi Prefecture

Claims (5)

[Claims] 1. A photocurable resin containing a compound A or (and) an epoxy compound B having one or more unsaturated double bonds in one molecule and a metallocene compound C, and a wavelength 400 excluding an ultraviolet wavelength. Light emitted from a visible light source having an output wavelength of ˜1500 nm is subjected to focus adjustment and focus adjustment by an optical system, and is transmitted through a liquid crystal panel whose pattern is controlled by a control device, so that a desired planar light image can be obtained on a resin interface. A plane cured product of the first layer is obtained by projecting a mask on the second layer, and the second and subsequent layers are sequentially filled with a thin layer of resin after the cured product is formed, and this operation is repeated to form a three-dimensional modeled product. The stereolithography method characterized by that. 2. A compound having at least one acryloyl group and methacryloyl group, a vinyl group, an allyl group and a vinylene group as a compound A having one or more unsaturated double bonds in one molecule, The stereolithography method according to claim 1, wherein an unsaturated polyester compound is used. 3. The stereolithography method according to claim 1, wherein an alicyclic epoxy compound is used as the epoxy compound B. 4. An unsaturated polyester compound obtained by reacting ethylene glycol, diethylene glycol, ethylene oxide of bisphenol A or a diol such as a propylene oxide adduct with a dibasic acid containing an unsaturated acid such as maleic anhydride. The stereolithography method according to claim 2, wherein a compound is used. 5. The amount of compound A or epoxy compound B having one or more ethylenically unsaturated double bonds in one molecule, or the amount of compound A and compound B used in combination is the total amount of the resin composition. The stereolithography method according to claim 1, wherein the amount is 5.0 to 99.9% by weight, and the amount of the metallocene compound C used is 0.1 to 10.0% by weight.