JP2020121431A - Model material clear composition - Google Patents

Abstract

To provide a model material clear composition witch has a peak wavelength in the wavelength range of 360-410 nm and can be cured with LED light sources that are widely used in the conventional art, is suitable for a material jet stereolithography method, and can obtain a stereoscopic stereolithography object having high hardness even though it is a colorless or achromatic clear stereoscopic stereolithography object.SOLUTION: It is a model material clear composition used in material jet stereolithography using an LED light source with a peak wavelength in a range of 360 nm to 410 nm, the model material clear composition comprising a polymerizable compound, a photopolymerization initiator and a sensitizer, wherein a maximum value of the absorption wavelength of the photopolymerization initiator is 400 nm or less, the sensitizer is selected from a group consisting of dialkoxyanthracenes and bisalkanoyloxyanthracenes, and a molded product formed from the model material clear composition has a curing shrinkage deformation degree of 15 mm or less.SELECTED DRAWING: None

Description

The present invention relates to a model material clear composition used in a material jet stereolithography method.

A light emitting diode (LED) has been widely used as a light source for a material jet stereolithography method because it has advantages such as low power consumption and long life. However, the main photopolymerization initiators used in a model material composition of a type that is cured by using an LED light source generally absorb light in a wavelength range of more than 400 nm, and thus the obtained photofabrication product is colored yellow. However, there is a problem that it is difficult to obtain a colorless or achromatic clear stereolithographic object. In order to solve such a problem, for example, in Patent Document 1, an LED light source having an ink composition containing a photopolymerization initiator that does not exhibit light absorption in a wavelength range exceeding 400 nm and having a peak between wavelengths 275 and 310 nm is disclosed. A method for obtaining a three-dimensional model by curing with a resin is disclosed.

JP, 2017-1226, A

However, the LED light source having a peak in the wavelength range of 275 to 310 nm as described in Patent Document 1 uses short wavelength energy and has a peak wavelength in the same range as that of the LED light source in the vicinity of 360 to 410 nm. When it is used as an energy source, it is not practical as a light source for the material jet stereolithography from the viewpoints of safety and cost, since it is likely to generate heat because it requires a high voltage and consumes a large amount of power. Also, if you try to suppress heat generation and use it in a safe range, the energy will be low, and it will be difficult to secure sufficient hardness of the obtained stereolithography product.If you install a cooling device, large-scale equipment is required. It is also disadvantageous in terms of cost. Therefore, in consideration of safety and cost, it can be said that it is more practical to use an LED light source having a peak wavelength in the vicinity of 360 to 410 nm. In order to manufacture a more complicated and high-definition three-dimensional object in the material jet stereolithography method using such an LED light source, it is indispensable to improve the hardness, and the colorless and transparent three-dimensional object is excellent in appearance. However, there is a strong demand for a model material clear composition capable of obtaining a three-dimensional stereolithography object having high hardness.

Therefore, the present invention is a colorless or achromatic clear three-dimensional stereolithography object that has a peak wavelength in the range of 360 to 410 nm and can be cured by an LED light source that has been widely used in the past. It is an object of the present invention to provide a model material clear composition suitable for a material jet stereolithography method capable of obtaining a three-dimensional stereolithography object having hardness.

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides the following preferred embodiments.
[1] A model material clear composition used in a material jet stereolithography method using an LED light source having a peak wavelength in the range of 360 nm to 410 nm, comprising a polymerizable compound, a photopolymerization initiator and a sensitizer. The maximum value of the absorption wavelength of the photopolymerization initiator is 400 nm or less, the sensitizer is selected from the group consisting of dialkoxyanthracene and bisalkanoyloxyanthracene, and a molding formed from the model material clear composition. A model material clear composition having a curing shrinkage deformation of 15 mm or less.
[2] The sensitizer according to the above [1], wherein the sensitizer contains at least one selected from 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 9,10-bisoctanoyloxyanthracene. Model material clear composition.
[3] The model material clear composition according to the above [1] or [2], wherein the content of the sensitizer is 0.01 to 2% by mass based on the total mass of the model material clear composition.
[4] Any of [1] to [3] above, wherein the photopolymerization initiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. The model material clear composition described in Crab.
[5] The model material clear according to any one of the above [1] to [4], wherein the content of the photopolymerization initiator is 0.1 to 5 mass% with respect to the total mass of the model material clear composition. Composition.
[6] The model material clear composition according to any one of the above [1] to [5], which has a viscosity at 25°C of 1 mPa·s or more and less than 500 mPa·s.
[7] The model material clear composition according to any one of [1] to [6], wherein the glass transition temperature of the model material clear composition is 30 to 70°C.
[8] The model material clear composition as described in any of [1] to [7] above, which contains a monofunctional polymerizable compound or a bifunctional polymerizable compound.
[9] The model material clear composition as described in any of [1] to [8] above, which contains acryloylmorpholine as the polymerizable compound.
[10] A material jet light comprising the model material clear composition according to any one of the above [1] to [9] and a support material composition for forming a support material by a material jet optical molding method. Molding composition set.

ADVANTAGE OF THE INVENTION According to this invention, although it is a colorless or achromatic clear three-dimensional stereolithography thing which has a peak wavelength in the wavelength range of 360-410 nm and can be hardened|cured by the LED light source generally used widely conventionally, it is high. It is possible to provide a model material clear composition suitable for a material jet stereolithography method, which can obtain a three-dimensional stereolithography object having hardness.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

<Model material clear composition>
The model material clear composition of the present invention is a model material composition used in a material jet stereolithography method using an LED light source having a peak wavelength in the range of 360 to 410 nm. The model material clear composition of the present invention comprises a photopolymerization initiator and a sensitizer selected from the group consisting of dialkoxyanthracene and bisalkanoyloxyanthracene, and the absorption wavelength of the photopolymerization initiator contained therein is increased. The maximum value is 400 nm or less. By using a photopolymerization initiator having a maximum absorption wavelength of 400 nm or less in combination with a sensitizer having a specific structure, curing is performed using a general LED light source having a peak wavelength of 360 to 410 nm. Even if it is, the obtained stereolithography product is difficult to be colored, and while maintaining high transparency of colorless or achromatic color, it is possible to secure high hardness that can reduce deformation and curing shrinkage, so that it has an excellent appearance and is complicated. It is a model material clear composition suitable for obtaining a high-definition stereolithography object.

The maximum value of the absorption wavelength of the photopolymerization initiator contained in the model material clear composition of the present invention is 400 nm or less. When the photopolymerization initiator has absorption in a wavelength range exceeding 400 nm, it tends to be colored such as yellow when cured using a general LED light source having a peak wavelength in the range of 360 to 410 nm, and is colorless or non-colored. It becomes difficult to obtain a colored and highly transparent stereolithography object. The maximum value of the absorption wavelength of the photopolymerization initiator contained in the model material clear composition of the present invention is preferably 380 nm or less, more preferably 360 nm or less. From the viewpoint of suppressing coloration, the minimum value of the absorption wavelength is not particularly limited as long as it exhibits absorption in the range of 400 nm or less and the maximum value of the absorption wavelength is in the range of 400 nm or less. As long as it is a photopolymerization initiator exhibiting light absorption within the range of the above upper and lower limits, it is a general LED light source having a colorless or achromatic color and having high transparency as a stereolithography object having a peak wavelength in the range of 360 to 410 nm. Can be obtained by using. The absorption wavelength of the photopolymerization initiator can be measured, for example, in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent capable of dissolving the photopolymerization initiator, and examples thereof include acetonitrile.

In the model material clear composition of the present invention, the photopolymerization initiator is a compound that promotes a radical reaction by irradiating light, and is not particularly limited as long as the maximum absorption wavelength is 400 nm or less. Conventionally known photopolymerization initiators can be used. Specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-Methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2 Α-hydroxyalkylphenone compounds such as -methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, such as 2,2-dimethoxy-1,2-diphenylethan-1-one A benzyl methyl ketal compound and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more. Among them, a sensitizer selected from the group consisting of dialkoxyanthracene and bisalkanoyloxyanthracene which can obtain a colorless or achromatic and highly transparent stereolithography product, and which is contained in the model material clear composition of the present invention. In combination with the above, an alkylphenone-based photopolymerization initiator is preferable from the viewpoint of achieving high hardness that is unlikely to cause deformation or curing shrinkage, and 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl propane-1. It is more preferable to include at least one selected from the group consisting of-one.

A commercially available product may be used as the photopolymerization initiator. Specific examples of such commercially available products include Irgacure (registered trademark) 1173, Irgacure 184, Irgacure 907, Irgacure 127, Irgacure 2959, Irgacure 651 (above, manufactured by BASF Japan Ltd.) and the like.

The content of the photopolymerization initiator in the model material clear composition is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the model material clear composition. is there. When the content of the photopolymerization initiator is at least the above lower limit value, unreacted polymerization components can be sufficiently reduced and curability can be sufficiently enhanced. On the other hand, when the content of the photopolymerization initiator is less than or equal to the above upper limit, the amount of the photopolymerization initiator remaining unreacted in the photofabrication product can be reduced, and the unreacted photopolymerization initiator remains. By doing so, it is possible to suppress yellowing of the stereolithography object.

The model material clear composition of the present invention is used as a photopolymerization initiator in order to achieve a sufficiently high color suppressing effect when cured using a general LED light source having a peak wavelength in the range of 360 to 410 nm. It is preferable that a photopolymerization initiator exhibiting absorption in a wavelength range of more than 400 nm is not substantially contained. In the present invention, "substantially free" means that the content of the photopolymerization initiator that absorbs in a wavelength range of more than 400 nm is 0.5% by mass or less based on the total mass of the model material clear composition. It means that the content of the photopolymerization initiator exhibiting absorption in a wavelength range of more than 400 nm is more preferably 0.1% by mass or less based on the total mass of the model material clear composition, and further preferably It is 0 mass %.

The model material clear composition of the present invention contains at least one sensitizer selected from the group consisting of dialkoxyanthracenes and bisalkanoyloxyanthracenes. In the clear model material composition used to obtain a highly transparent stereolithography product without coloring, in many cases, since the coloring due to the photopolymerization initiator is prominent, a model material composition containing a colorant is often present. It is desired to reduce the amount of the photopolymerization initiator as compared with. When the content of the photopolymerization initiator is reduced, the curability of the model material composition tends to be lowered, so that it becomes necessary to supplement this. On the other hand, as compared with a model material composition containing a colorant such as a pigment or a dye having a property of generally absorbing light, a photopolymerization initiator or a polymerizable compound is contained in the case of containing the same degree of photopolymerization initiator. Light energy is likely to act and the polymerization reaction is facilitated. For this reason, there is a problem that the curing of the composition is more likely to proceed than necessary, and that the model material clear composition is more likely to exhibit the problems of deformation and curing shrinkage as compared with the model material composition containing a colorant. In addition, since a three-dimensional three-dimensional object is thicker than a two-dimensional object (printed object), even a slight color is easily recognized, and a problem of coloration and deterioration of transparency is likely to occur remarkably. .. The model material clear composition of the present invention has a specific structure selected from the group consisting of dialkoxyanthracene and bisalkanoyloxyanthracene in combination with the photopolymerization initiator having the maximum absorption wavelength of 400 nm or less. By using the sensitizer, the curing shrinkage is improved while maintaining the good curability of the clear material for model material, and the coloring is suppressed to an extent that is sufficiently permissible as a three-dimensional three-dimensional object, and transparency is improved. A high-precision stereolithography product can be obtained by using a general LED light source having a peak wavelength in the range of 360 to 410 nm.

〔式（１）中、Ｒ^１は互いに独立して、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数１〜８のアルコキシ基またはアリルオキシ基のうちいずれかを表し、Ｘ^１およびＹ^１は同一であっても異なっていてもよく、水素原子または炭素数１〜８のアルキル基のうちのいずれかを表す〕
で表されるアントラセン化合物が挙げられる。具体的には、例えば、９，１０−ジメトキシアントラセン、９，１０−ジエトキシアントラセン、９，１０−ジプロポキシアントラセン、９，１０−ジブトキシアントラセン、２−エチル−９，１０−ジエトキシアントラセン、２−エチル−９，１０−ジプロポキシアントラセン、２−エチル−９，１０−ジブトキシアントラセン、９，１０−ビス（２−エチルヘキシルオキシ）アントラセン、９，１０−ビス（２−メチルヘキシルオキシ）アントラセン、９，１０−ビス（２−プロピルヘキシルオキシ）アントラセン、９，１０−ビス（２−ブチルヘキシルオキシ）アントラセン等が挙げられる。 Examples of the dialkoxyanthracene that can be contained in the model material clear composition of the present invention include the following formula (1):

[In the formula (1), R ^1's each independently represent an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an allyloxy group. , X ¹ and Y ¹ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
An anthracene compound represented by Specifically, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(2-methylhexyloxy)anthracene , 9,10-bis(2-propylhexyloxy)anthracene, 9,10-bis(2-butylhexyloxy)anthracene and the like.

〔式（２）中、Ｒ^２は互いに独立して、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数１〜８のアルコキシ基またはアリルオキシ基のうちのいずれかを表し、Ｘ^２およびＹ^２は同一であっても異なっていてもよく、水素原子または炭素数１〜８のアルキル基のうちのいずれかを表す〕
で表されるアントラセン化合物が挙げられる。具体的には、例えば、９，１０−ビスオクタノイルオキシアントラセン、９，１０−ビスプロピオニルオキシアントラセン、９，１０−ビスブチリルオキシアントラセン、９，１０−ビスヘキサノイルオキシアントラセン、９，１０−ビスヘプタノイルオキシアントラセン、９，１０−ビスオクタノイルオキシアントラセン、９，１０−ビス（２−エチルヘキサノイルオキシ）アントラセン等が挙げられる。 In addition, as the bisalkanoyloxyanthracene that can be included in the model material clear composition of the present invention, for example, the following formula (2):

[In the formula (2), R ^2's each independently represent an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an allyloxy group. X ² and Y ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
An anthracene compound represented by Specifically, for example, 9,10-bisoctanoyloxyanthracene, 9,10-bispropionyloxyanthracene, 9,10-bisbutyryloxyanthracene, 9,10-bishexanoyloxyanthracene, 9,10- Examples thereof include bisheptanoyloxyanthracene, 9,10-bisoctanoyloxyanthracene, and 9,10-bis(2-ethylhexanoyloxy)anthracene.

The above anthracene compounds may be used alone or in combination of two or more. Above all, the model material clear composition can be prepared by using a general LED light source that can activate the photopolymerization initiator in response to a wavelength region near 400 nm and has a peak wavelength in the range of 360 to 410 nm. As the sensitizer is 9,10-diethoxyanthracene, 9,10 because the curing shrinkage is improved while maintaining good curability and a colorless or achromatic three-dimensional stereoscopically shaped product is easily obtained. -It is preferable to include at least one selected from dibutoxyanthracene and 9,10-bisoctanoyloxyanthracene.

The model material clear composition of the present invention may contain a known sensitizer other than dialkoxyanthracene and bisalkanoyloxyanthracene within a range that does not affect the effects of the present invention. Examples of such sensitizers include thioxanthone sensitizers. When a sensitizer other than dialkoxyanthracene and bisalkanoyloxyanthracene is contained, the content thereof in the model material clear composition of the present invention is 100 parts by mass of dialkoxyanthracene and bisalkanoyloxyanthracene contained in the model material clear composition. On the other hand, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and it is particularly preferable that no sensitizer other than dialkoxyanthracene and bisalkanoyloxyanthracene is contained.

The content of the sensitizer in the model material clear composition of the present invention is preferably 0.01 to 2 mass% with respect to the total mass of the model material clear composition. When the content of the sensitizer is within the above range, the photopolymerization initiator can be sufficiently activated, and the curing shrinkage can be effectively suppressed while maintaining the good curability of the model material clear composition. You can The content of the sensitizer is preferably 0.05% by mass or more, and more preferably 1.5% by mass or less, based on the total mass of the model material clear composition. When the model material clear composition contains a plurality of types of sensitizers, the content of the sensitizer means the total amount of all the sensitizers contained in the model material clear composition.

The model material clear composition of the present invention contains a polymerizable compound. The model material clear composition of the present invention preferably has a glass transition temperature of 30 to 70° C., and the polymerizable compound constituting the model material clear composition is selected so that the model material clear composition has the glass transition temperature. Preferably. As such a polymerizable compound, the model material clear composition of the present invention has at least one monofunctional or difunctional polymerizable monomer (hereinafter, referred to as “polymerized”) having a glass transition temperature (Tg) as a homopolymer of 25° C. or higher. (Also referred to as a polymerizable monomer (A))). The polymerizable monomer (A) functions as a reactive diluent, promotes curability while suppressing cure shrinkage, and contributes to improvement in modeling accuracy of the stereolithography object. In particular, by composing the model material clear composition by combining the polymerizable monomer (A) with the polymerizable monomer (B) and/or oligomer described later, it is easy to control curability and clear without coloring. It is possible to obtain a model material clear composition which is capable of suppressing curing shrinkage while providing a high hardness and brittleness resistance in a well-balanced manner, even though it is a simple stereolithography product.

A monofunctional polymerizable monomer having a glass transition temperature of 25° C. or higher as a homopolymer (hereinafter, also referred to as “monofunctional polymerizable monomer (A1)”) has a glass transition temperature of a homopolymer of 25° C. or higher, And the like, which is a component having a property of being polymerized and cured by irradiation with an active energy ray, such as a polymerizable monomer having one polymerizable group in the molecule. Examples of the polymerizable group contained in the monofunctional polymerizable monomer (A1) include (meth)acryloyl group, vinyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, epoxy group and oxetanyl group. Among them, the polymerizable group contained in the monofunctional polymerizable monomer (A1) is preferably a radical polymerizable group from the viewpoint of reaction efficiency and reaction rate in photocuring, and a (meth)acryloyl group, vinyl group or allyl group is preferable. Is more preferable, and an acryloyl group or a methacryloyl group is further preferable. In addition, in this specification, "(meth)acryloyl" represents acryloyl and/or methacryloyl, and the same applies to "(meth)acrylate", "(meth)acrylamide" and the like.

In the model material clear composition of the present invention, the monofunctional polymerizable monomer (A1) preferably has a glass transition temperature of 25° C. or higher as a homopolymer and has a single ethylenic double bond in the molecule. It is a functional ethylenically unsaturated monomer. Specifically, for example, an alkyl (meth)acrylate having a linear or branched alkyl group, or having a cyclic structure such as an alicyclic structure, an aromatic ring structure or a heterocyclic structure in the molecule (meth) Acrylates and monofunctional ethylenically unsaturated monomers containing a nitrogen atom such as (meth)acrylamide and N-vinyl lactams are included. In the present specification, the alicyclic structure is an aliphatic cyclic structure in which carbon atoms are cyclically bonded, the aromatic ring structure is an aromatic cyclic structure in which carbon atoms are cyclically bonded, and the heterocyclic structure is a carbon atom. And a structure in which one or more heteroatoms are cyclically bonded.

The alkyl(meth)acrylate having a linear or branched alkyl group having a glass transition temperature of 25° C. or higher as a homopolymer, for example, preferably has 5 to 25 carbon atoms, and more preferably has 5 carbon atoms. Alkyl (meth)acrylates having 5 to 10 linear or branched alkyl groups are mentioned. Specific examples include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-hydroxyethyl methacrylate, stearyl (meth)acrylate, and the like.

The (meth)acrylate having a glass transition temperature of 25° C. or higher as a homopolymer and having an alicyclic structure is, for example, preferably an alicyclic group having 8 to 30 carbon atoms, more preferably 9 to 15 carbon atoms. (Meth)acrylate which has a structure is mentioned. Specific examples include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl methacrylate, and 3,3,5-trimethylcyclohexanol (meth)acrylate.

The (meth)acrylate having a glass transition temperature of 25° C. or higher as a homopolymer and having an aromatic ring structure is, for example, preferably an aromatic ring structure having 8 to 30 carbon atoms, more preferably 9 to 15 carbon atoms. The (meth)acrylate which it has is mentioned. Specific examples include phenoxyethyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

The (meth)acrylate having a heterocyclic structure having a glass transition temperature of 25° C. or higher as a homopolymer is, for example, preferably a heterocyclic structure having 8 to 30 carbon atoms, more preferably 9 to 15 carbon atoms. The (meth)acrylate which it has is mentioned. Specific examples include cyclic trimethylolpropane formal (meth)acrylate and the like.

Examples of monofunctional ethylenically unsaturated monomers containing a nitrogen atom different from the above (meth)acrylate include (meth)acrylamide [eg, N,N-dimethylacrylamide, N,N-diethylacrylamide]. , N-isopropyl acrylamide, hydroxyethyl acrylamide, hydroxypropyl acrylamide, N,N-acryloylmorpholine, etc.], N-vinyl lactams (eg, N-vinyl pyrrolidone, N-vinyl caprolactam, etc.), N-vinyl formamide and the like. To be

Among these, the monofunctional polymerizable monomer (A1) contained in the model material clear composition is preferably a monofunctional ethylenically unsaturated monomer having a cyclic structure in the molecule. When the monofunctional polymerizable monomer (A1) has a cyclic structure in the molecule, the glass transition temperature of the obtained photofabrication product tends to be higher than that of other monomers having no cyclic structure. Therefore, the hardness and heat resistance can be improved more effectively. When the model material clear composition of the present invention contains a monofunctional polymerizable monomer (A1) as a polymerizable compound, it has a glass transition temperature of 25° C. or higher as a homopolymer and a monofunctional polymerizable compound having a cyclic structure in the molecule. The content of the monomer is preferably 10% by mass or more, and more preferably 20% by mass or more, based on the total mass of the monofunctional polymerizable monomer (A1), and all the components contained in the model material clear composition are included. The monofunctional polymerizable monomer (A1) may have a cyclic structure in the molecule. In particular, by using a polycyclic cyclic structure as the cyclic structure, and by using a monofunctional polymerizable monomer having a cross-linked cyclic structure, the resulting stereolithography product tends to have an excellent effect of improving brittle resistance. Therefore, it is preferable that the monofunctional polymerizable monomer (A1) contains a monofunctional polymerizable monomer having a polycyclic or crosslinked cyclic structure. As the monofunctional polymerizable monomer (A1), one type may be used alone, or two or more types may be mixed and used.

In a preferred embodiment of the present invention, the model material clear composition contains a (meth)acrylate-based monomer as the monofunctional polymerizable monomer (A1), and particularly preferably has a cyclic structure in the molecule (meth). Contains an acrylate-based monomer. Examples of the (meth)acrylate-based monomer having a cyclic structure in the molecule include isobornyl (meth)acrylate, dicyclopentanyl methacrylate, dicyclopentenyloxyethyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate and cyclic trimethylolpropaneformol. It is more preferable to contain at least one selected from the group consisting of mal(meth)acrylate, isobornyl(meth)acrylate or cyclic trimethylolpropane formal(meth)acrylate is further preferable, and isobornyl acrylate is particularly preferable. Among them, by including a monofunctional (meth)acrylate-based monomer having an alicyclic structure in the molecule, compared with other monomers having an aromatic ring structure or a heterocyclic structure, High transition temperature, excellent hardness and heat resistance.

In another aspect of the present invention, the model material clear composition may contain acryloylmorpholine as the monofunctional polymerizable monomer (A1). Acryloylmorpholine has a high glass transition temperature and high curability. Therefore, when the model material clear composition contains acryloylmorpholine as a polymerizable compound, high hardness can be imparted to the obtained stereoscopically shaped product. In addition, since acryloylmorpholine suitably functions as a diluent, while maintaining the viscosity of the composition in an appropriate range, a model of a component such as an oligomer that is useful for improving the brittleness resistance of the obtained photofabrication is modeled. Since a larger amount can be blended in the clear material composition, by including acryloylmorpholine, a stereolithography product having a high balance of high strength and appropriate toughness can be obtained. Furthermore, when the model material clear composition of the present invention is used in combination with a water-soluble support material composition as described below, water such as water used as a removal solvent for removing the support material is a polar monomer. Acryloylmorpholine, which is readily soluble in polar solvents, can be used in the support material composition. The model material clear composition contains acryloylmorpholine, which is used in the support material composition, so that the surface tension is high, so that the polarities of the support material and the model material are made close while preventing the mixing of the interface between the support material and the model material. Thus, the wettability between the support material and the model material can be improved. Therefore, the inclusion of acryloylmorpholine in the model material clear composition increases the effect of maintaining the boundary between the model material and the support material during the production of the stereolithography object, and thus the stereolithography object with good dimensional accuracy can be obtained. Obtainable.

When the model material clear composition of the present invention contains acryloylmorpholine, its content is preferably 10 to 70 mass% with respect to the total mass of the model material clear composition. When the content of acryloylmorpholine is at least the above lower limit value, the hardness of the obtained photofabrication product can be effectively improved. When the content of acryloylmorpholine is not more than the above upper limit value, the degree of curing shrinkage can be easily suppressed, and the stereolithography product can be obtained with high accuracy, and the brittleness resistance of the stereolithography product can be improved. In the model material clear composition of the present invention, the content of acryloylmorpholine is more preferably 15% by mass or more, and further preferably 20% by mass or more. Further, from the viewpoint of obtaining a colorless or achromatic colored stereoscopically shaped product, the content is more preferably 60% by mass or less, and further preferably 50% by mass or less.

In the model material clear composition of the present invention, the bifunctional polymerizable monomer having a glass transition temperature of 25° C. or higher as a homopolymer (hereinafter, also referred to as “bifunctional polymerizable monomer (A2)”) is a homopolymer glass. It is a component having a transition temperature of 25° C. or higher and having a property of being polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and is a polymerizable monomer having two polymerizable groups in the molecule. Examples of the polymerizable group contained in the bifunctional polymerizable monomer (A2) include (meth)acryloyl group, vinyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, epoxy group and oxetanyl group. Among them, the polymerizable group contained in the bifunctional polymerizable monomer (A2) is preferably a radical polymerizable group from the viewpoint of reaction efficiency and reaction rate in photocuring, and a (meth)acryloyl group, vinyl group or allyl group is preferable. Is more preferable, and an acryloyl group or a methacryloyl group is further preferable.

In the model material clear composition of the present invention, the bifunctional polymerizable monomer (A2) preferably has a glass transition temperature of 25° C. or higher as a homopolymer and has two ethylenic double bonds in the molecule. It is a functional ethylenically unsaturated monomer. Specific examples thereof include linear or branched alkylene glycol di(meth)acrylates and cyclic structure-containing di(meth)acrylates. The bifunctional polymerizable monomer (A2) may be used alone or in combination of two or more.

The linear or branched alkylene glycol di(meth)acrylate is preferably a linear or branched alkylene glycol di(meth)acrylate having 10 to 20 carbon atoms, for example, 1,3-butylene glycol di(meth)acrylate. Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate , Triethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, allyl methacrylate and the like.

The cyclic structure-containing di(meth)acrylate is preferably a cyclic structure-containing di(meth)acrylate having 15 to 30 carbon atoms, and examples thereof include ethoxylated (EO3 mol) bisphenol A di(meth)acrylate and tricyclodecane dimethanol dimethacrylate. (Meth)acrylate etc. are mentioned.

Among these, from the viewpoint of dilutability and reactivity, (meth)acrylate-based monomers are preferable, and 1,3-butylene glycol di(meth)acrylate and 1,4-butanediol di(meth) are preferred. Acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and polyethylene glycol More preferably, at least one selected from the group consisting of #200 di(meth)acrylate is included, and 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate or neopentyl glycol di( (Meth)acrylate is more preferable, and tripropylene glycol di(meth)acrylate is particularly preferable.

In the present invention, the polymerizable monomer (A) has a glass transition temperature of 25° C. or higher when it is made into a homopolymer, and the glass transition temperature is preferably 40° C. or higher, more preferably 60° C. or higher, further preferably It is 65°C or higher. When the glass transition temperature is 25° C. or higher, high hardness can be imparted to the stereolithography product obtained by photocuring the model material clear composition. The upper limit of the glass transition temperature of the polymerizable monomer (A) is not particularly limited, but is usually 200° C. or lower, preferably 150° C. or lower. The glass transition temperature is the same for the monofunctional polymerizable monomer (A1) and the bifunctional polymerizable monomer (A2).

In the model material clear composition of the present invention, the polymerizable monomer (A) may be composed of only the monofunctional polymerizable monomer (A1), or may be composed of only the difunctional polymerizable monomer (A2). It may be composed of the polymerizable monomer (A1) and the bifunctional polymerizable monomer (A2). Usually, as the amount of the bifunctional polymerizable monomer (A2) increases, the curing rate of the model material clear composition tends to increase, and the hardness of the obtained model material tends to increase, and the monofunctional polymerizable monomer (A1) and the bifunctional polymerizable monomer (A1) By using in combination with the polymerizable monomer (A2), curability, mechanical strength and hardness can be easily controlled, and a model material clear composition excellent in these balances can be obtained.

The content of the monofunctional or difunctional polymerizable monomer (A) having a glass transition temperature as a homopolymer of 25° C. or more in the model material clear composition of the present invention is relative to the total mass of the model material clear composition. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 80% by mass. % Or less, more preferably 70% by mass or less, and further preferably 60% by mass or less. When the content of the polymerizable compound (A) is within the above range, appropriate dilutability and reactivity can be imparted. When two or more kinds of polymerizable monomers (A) are included, the above range means the range with respect to the total content.

The model material clear composition of the present invention comprises, as a polymerizable compound, at least one monofunctional or difunctional polymerizable monomer (hereinafter, referred to as “polymerizable monomer (Tg) as a homopolymer”, which is less than 25° C.). B)” is also included). The polymerizable monomer (B) functions as a reactive diluent, promotes curability while suppressing cure shrinkage, and contributes to improvement in modeling accuracy of the optically molded product. In particular, by forming the model material clear composition by combining the above-mentioned polymerizable monomer (A) and preferably the oligomer described below, the curability is easily controlled, and the obtained photofabrication while suppressing the curing shrinkage. It is possible to obtain a model material clear composition capable of imparting high hardness and brittle resistance in a well-balanced manner.

A monofunctional polymerizable monomer having a glass transition temperature of less than 25° C. as a homopolymer (hereinafter, also referred to as “monofunctional polymerizable monomer (B1)”) has a glass transition temperature of a homopolymer of less than 25° C. And the like, which is a component having a property of being polymerized and cured by irradiation with an active energy ray, such as a polymerizable monomer having one polymerizable group in the molecule. Examples of the polymerizable group contained in the monofunctional polymerizable monomer (B1) include (meth)acryloyl group, vinyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, epoxy group and oxetanyl group. Among them, the polymerizable group contained in the monofunctional polymerizable monomer (B1) is preferably a radical polymerizable group from the viewpoint of reaction efficiency and reaction rate in photocuring, and a (meth)acryloyl group, vinyl group or allyl group is preferable. Is more preferable, and an acryloyl group or a methacryloyl group is further preferable.

Examples of the alkyl(meth)acrylate having a glass transition temperature of less than 25° C. as a homopolymer and having a linear or branched alkyl group include, for example, preferably 5 to 30 carbon atoms, and more preferably carbon atoms. Alkyl (meth)acrylates having 9 to 20 linear or branched alkyl groups are mentioned. Specific examples include ethyl acrylate, butyl acrylate, lauryl acrylate, lauryl methacrylate, isodecyl acrylate, isodecyl methacrylate, isooctyl acrylate, tridecyl acrylate, tridecyl methacrylate, caprolactone acrylate, and alkoxylated lauryl acrylate. ..

The (meth)acrylate having a glass transition temperature of less than 25° C. as a homopolymer and having an alicyclic structure is, for example, preferably an alicyclic group having 8 to 30 carbon atoms, and more preferably 8 to 20 carbon atoms. (Meth)acrylate which has a structure is mentioned. Specific examples include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, and alkoxylated tetrahydrofurfuryl acrylate.

The (meth)acrylate having a glass transition temperature of less than 25° C. as a homopolymer and an aromatic ring structure is, for example, preferably an aromatic ring structure having 8 to 30 carbon atoms, more preferably 8 to 20 carbon atoms. The (meth)acrylate which it has is mentioned. Specific examples include 2-phenoxyethyl acrylate, ethoxylated (4) nonylphenol acrylate, and alkoxylated phenol acrylate.

Among these, the monofunctional polymerizable monomer (B1) contained in the model material clear composition is preferably a monofunctional ethylenically unsaturated monomer having a cyclic structure in the molecule. The monofunctional ethylenically unsaturated monomer having a cyclic structure in the molecule tends to contribute to the improvement of the adhesion force of the model material as compared with other monomers having no cyclic structure in the molecule. For example, since the adhesion between the model material obtained by curing at the time of modeling and the printing stage, the molding base medium, etc. can be improved, the monofunctional ethylenic polymer having a cyclic structure in the molecule as the monofunctional polymerizable monomer (B1). By containing the unsaturated monomer, the effect of suppressing warpage during modeling and the effect of suppressing modeling failure such as peeling of the model material from the modeling base due to curing shrinkage during modeling can be expected. When the model material clear composition of the present invention contains a monofunctional polymerizable monomer (B1) as a polymerizable compound, it has a glass transition temperature of less than 25° C. as a homopolymer and a monofunctional polymerizable compound having a cyclic structure in the molecule. The content of the monomer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the monofunctional polymerizable monomer (B1), and all of the components contained in the model material clear composition are included. The monofunctional polymerizable monomer (B1) may have a cyclic structure in the molecule. As the monofunctional polymerizable monomer (B1), one type may be used alone, or two or more types may be mixed and used.

In a preferred embodiment of the present invention, the model material clear composition contains a (meth)acrylate-based monomer as the monofunctional polymerizable monomer (B1), and particularly preferably has a cyclic structure in the molecule (meth). Contains an acrylate-based monomer.

In the model material clear composition of the present invention, the bifunctional polymerizable monomer having a glass transition temperature as a homopolymer of less than 25° C. (hereinafter, also referred to as “bifunctional polymerizable monomer (B2)”) is a homopolymer glass. It is a polymerizable monomer having a transition temperature of less than 25° C. and having a property of being polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and having two polymerizable groups in the molecule. Examples of the polymerizable group contained in the bifunctional polymerizable monomer (B2) include (meth)acryloyl group, vinyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, epoxy group and oxetanyl group. Among them, the polymerizable group contained in the bifunctional polymerizable monomer (B2) is preferably a radical polymerizable group from the viewpoint of reaction efficiency and reaction rate in photocuring, and a (meth)acryloyl group, vinyl group or allyl group is preferable. Is more preferable, and an acryloyl group or a methacryloyl group is further preferable.

In the model material clear composition of the present invention, the bifunctional polymerizable monomer (B2) preferably has a glass transition temperature of less than 25° C. as a homopolymer and has two ethylenic double bonds in the molecule. It is a functional ethylenically unsaturated monomer. Specific examples thereof include linear or branched alkylene glycol di(meth)acrylates and cyclic structure-containing di(meth)acrylates. The bifunctional polymerizable monomer (B2) may be used alone or in combination of two or more.

Examples of the bifunctional polymerizable monomer (B2) used in the model material clear composition of the present invention include polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol ( 600) diacrylate, polyethylene glycol (600) dimethacrylate, cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, ethoxylated (2) bisphenol A dimethacrylate, ethoxylated (10) bisphenol A diacrylate, ethoxylated (10 ) Bisphenol A dimethacrylate, ethoxylated (30) bisphenol A diacrylate, ethoxylated (30) bisphenol A dimethacrylate, alkoxylated neopentyl glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,12- Dodecanediol dimethacrylate and the like can be mentioned.

In the present invention, the polymerizable monomer (B) has a glass transition temperature of less than 25° C. when it is a homopolymer, and the glass transition temperature is preferably 20° C. or lower, more preferably 15° C. or lower. When the glass transition temperature is less than 25°C, the curing shrinkage can be reduced, and by combining it with a polymerizable monomer having a glass transition temperature of 25°C or more, the curing shrinkage of the shaped article can be optimized. The lower limit of the glass transition temperature of the polymerizable monomer (B) is not particularly limited, but is usually −70° C. or higher, preferably −20° C. or higher. The glass transition temperature is the same for the monofunctional polymerizable monomer (B1), the bifunctional polymerizable monomer (B2), and the polyfunctional polymerizable monomer (B3) described later.

In the model material clear composition of the present invention, the polymerizable monomer (B) may be composed of only the monofunctional polymerizable monomer (B1) or may be composed of only the difunctional polymerizable monomer (B2). It may be composed of the polymerizable monomer (B1) and the bifunctional polymerizable monomer (B2). Usually, as the amount of the bifunctional polymerizable monomer (B2) increases, the curing rate of the model material clear composition tends to increase, and the hardness of the obtained model material tends to increase, and the monofunctional polymerizable monomer (B1) and the bifunctional polymerizable monomer (B1) tend to increase. By using the polymerizable monomer (B2) in combination, it is possible to easily control curability, mechanical strength and hardness, and to obtain a model material clear composition having an excellent balance of these.

The content of the monofunctional or difunctional polymerizable monomer (B) having a glass transition temperature as a homopolymer of less than 25° C. in the model material clear composition of the present invention is relative to the total mass of the model material clear composition. It is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, still more preferably 30% by mass or more, preferably 80% by mass or less. , More preferably 75% by mass or less, further preferably 70% by mass or less. When the content of the polymerizable compound (B) is within the above range, appropriate dilutability and reactivity can be imparted. When two or more kinds of polymerizable monomers (B) are contained, the above range means the range with respect to the total content.

Furthermore, the model material clear composition of the present invention is a trifunctional or higher polyfunctional polymerizable monomer having a glass transition temperature of less than 25° C. as a homopolymer (hereinafter, also referred to as “polyfunctional polymerizable monomer (B3)”). May be included. The polyfunctional polymerizable monomer (B3) is a component having a glass transition temperature of a homopolymer of less than 25° C. and having a property of being polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and has a polymerizable property in a molecule. It is a polymerizable monomer having three or more groups. Generally, the hardness of the photofabricated product obtained by blending the polyfunctional polymerizable compound tends to be high, but on the other hand, curing shrinkage tends to occur. However, the polyfunctional polymerizable compound (B3) is used as the polyfunctional polymerizable compound. By using it, it is possible to moderately increase the hardness of the stereolithography object while suppressing curing shrinkage. When the model material clear composition of the present invention contains a polyfunctional polymerizable compound, it is preferable to use the polyfunctional polymerizable monomer (B3) as the polyfunctional polymerizable compound, and the polyfunctional polymerizable compound is the polyfunctional polymerizable monomer ( More preferably, it is only B3). The hardness of the stereolithography product obtained by containing the polyfunctional polymerizable monomer tends to increase, and when the content of the polyfunctional polymerizable monomer increases, curing shrinkage easily occurs. By using the polyfunctional polymerizable monomer (B3) having a glass transition temperature of less than 25° C. as a polymer, curing shrinkage can be softened as compared with the case of using the polyfunctional polymerizable monomer having a glass transition temperature of 25° C. or higher. it can. Examples of the polymerizable group contained in the polyfunctional polymerizable monomer (B3) include (meth)acryloyl group, vinyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, epoxy group and oxetanyl group. Among them, the polymerizable group contained in the polyfunctional polymerizable monomer (B3) is preferably a radical polymerizable group from the viewpoint of reaction efficiency and reaction rate in photocuring, and a (meth)acryloyl group, vinyl group or allyl group is preferable. Is more preferable, and an acryloyl group or a methacryloyl group is further preferable.

In the model material clear composition of the present invention, the polyfunctional polymerizable monomer (B3) preferably has a glass transition temperature as a homopolymer of less than 25° C. and has three or more ethylenic double bonds in the molecule. It is a polyfunctional ethylenically unsaturated monomer. Specifically, for example, ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, ethoxylated (15) trimethylolpropane triacrylate , Propoxylated (3) trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, ethoxylated (4) pentaerythritol tetraacrylate and the like. As the polyfunctional polymerizable monomer (B3), one type may be used alone, or two or more types may be mixed and used.

When the model material clear composition of the present invention contains a polyfunctional polymerizable monomer (B3), its content is preferably 30% by mass or less, and more preferably 20 mass% with respect to the total mass of the model material clear composition. % Or less. When the content of the polyfunctional polymerizable monomer (B3) is at most the above upper limit, it is possible to obtain a model material clear composition capable of effectively suppressing curing shrinkage without excessively increasing the hardness of the obtained stereolithography product. it can. The lower limit of the content of the polyfunctional polymerizable monomer (B3) is not particularly limited, and the model material clear composition of the present invention may not contain the polyfunctional polymerizable monomer (B3) at all (that is, 0 mass%).

The model material clear composition of the present invention preferably contains an oligomer as a polymerizable compound. The oligomer is a component having the property of being polymerized and cured by irradiation with active energy rays. By blending the oligomer, it is possible to obtain a stereolithography product that has an increased fracture strength of the obtained stereolithography product, has appropriate toughness, and is hard to break even when bent.
Here, in the present specification, the “oligomer” refers to one having a weight average molecular weight Mw of 500 to 10,000. The preferred weight average molecular weight Mw of the oligomer is 800 or more, more preferably more than 1,000. The weight average molecular weight Mw means a polystyrene equivalent weight average molecular weight measured by GPC (Gel Permeation Chromatography). As the oligomer, only one kind may be used, or two or more kinds may be used in combination.

Examples of the oligomer include epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, urethane (meth)acrylate oligomer, and polyether (meth)acrylate oligomer. As the oligomer, a bifunctional or higher polyfunctional oligomer is preferable, and a bifunctional oligomer is more preferable. Further, from the viewpoint of wide selection of materials and selection of materials having various characteristics, an oligomer having a urethane group is preferable, a urethane (meth)acrylate oligomer is more preferable, and a urethane acrylate oligomer is further preferable. is there.

The glass transition temperature of the oligomer is preferably 0°C or higher, more preferably 5°C or higher, preferably 250°C or lower, more preferably 200°C or lower. When the glass transition temperature of the oligomer is within the above range, a tenacious stereolithography product can be produced while maintaining the hardness.

When the model material clear composition of the present invention contains an oligomer, its content is preferably 1 to 40% by mass, and more preferably 5% by mass or more, based on the total mass of the model material clear composition. %, more preferably 10% by mass or more, further preferably 30% by mass or less, and further preferably 20% by mass or less. When the content of the oligomer is within the range of the above upper and lower limits, while maintaining the viscosity of the model material clear composition in an appropriate range, the breaking strength of the obtained stereolithography product is increased, the toughness is moderate, and the bending is achieved. Even if it is hard to crack, it is possible to obtain a stereolithography product.

The model material clear composition of the present invention preferably contains at least one monofunctional polymerizable compound or difunctional polymerizable compound as the polymerizable compound. The monofunctional polymerizable compound and/or the bifunctional polymerizable compound constituting the model material clear composition of the present invention are conventionally known in the art so that the glass transition temperature of the obtained model material clear composition becomes a desired temperature. From the polymerizable compounds of, for example, the polymerizable monomers (A) and (B) exemplified above, oligomers and the like can be appropriately selected.

The content of the monofunctional polymerizable compound and the bifunctional polymerizable compound in the model material clear composition of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass of the polymerizable compounds. It is more preferably 95% by mass or more, particularly preferably 98% by mass or more, and all the polymerizable compounds constituting the model material clear composition may be monofunctional polymerizable compounds and/or difunctional polymerizable compounds. When the content of the monofunctional polymerizable compound and the bifunctional polymerizable compound in the model material clear composition is at least the above lower limit, it is easy to control the hardness of the obtained photofabrication, and cure shrinkage while imparting an appropriate hardness. It is possible to obtain a model material clear composition capable of effectively suppressing the above.

In other words, when the model material clear composition of the present invention contains a polyfunctional polymerizable compound, the content of the monofunctional polymerizable compound and the content of the difunctional polymerizable compound are preferably larger than the content of the polyfunctional polymerizable compound. Specifically, the content of the polyfunctional polymerizable compound contained in the model material clear composition of the present invention is preferably less than 20% by mass, more preferably less than 15% by mass, based on the total mass of the polymerizable compounds. %, more preferably less than 10% by mass, particularly preferably less than 5% by mass. Moreover, in one aspect of the present invention, the model material clear composition may not include any polyfunctional polymerizable compound.

The glass transition temperature of the model material clear composition of the present invention is preferably 30 to 70°C. When the glass transition temperature of the model material clear composition is within the above range, it is possible to obtain a stereolithographic product with high accuracy and appropriate hardness while effectively suppressing curing shrinkage. The glass transition temperature of the model material clear composition can be controlled by, for example, the type and amount of the polymerizable compounds constituting the composition, the combination, and the like. For example, by including the polymerizable monomer (A) and the polymerizable monomer (B) in combination, the glass transition temperature of the model material clear composition can be easily controlled, and a stereolithographic object having a desired hardness can be easily obtained. At the same time, by further containing an oligomer as required, the toughness of the obtained photofabrication product can be easily controlled. The glass transition temperature of the model material clear composition of the present invention is more preferably 35° C. or higher, and more preferably 65° C. or lower.
The glass transition temperatures of the polymerizable compound and the model material clear composition can be measured by the method described in Examples below.

The content of the polymerizable compound in the model material clear composition of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, with respect to the total mass of the model material clear composition. It is preferably 99.9% by mass or less, and more preferably 99.5% by mass or less.

The model material clear composition is a storage stabilizer, a surface modifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, a chain transfer agent, a filler, if necessary, within a range that does not impair the effects of the present invention. , Diluent solvents, thickeners, and other additives.

The surface conditioner is a component that adjusts the surface tension of the model material clear composition to an appropriate range, and the type thereof is not particularly limited. By setting the surface tension of the model material clear composition to an appropriate range, it is possible to stabilize the dischargeability and suppress interfacial mixing between the model material clear composition and the support material composition. As a result, it is possible to obtain a modeled article with good dimensional accuracy.

Examples of the surface modifier include silicone compounds. Examples of the silicone-based compound include silicone-based compounds having a polydimethylsiloxane structure. Specific examples include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyaralkyl-modified polydimethylsiloxane. As these, by name, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, manufactured by Big Chemie), TEGO-Rad2100. , TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700 (manufactured by Degussa), Granol 100, Granol 115, Granol 400, Granol 410, Granol 435, Granol 440,. Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by Kyoeisha Chemical Co., Ltd.) or the like may be used. Further, a surface conditioner other than the silicone-based compound (for example, a fluorine-based surface conditioner or the like) may be used. These may be used alone or in combination of two or more.

When the model material clear composition contains a surface conditioner, its content is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, based on the total mass of the model material clear composition. %, preferably 3.0 mass% or less, more preferably 1.5 mass% or less. When the content of the surface modifier is within the above range, it is easy to adjust the surface tension of the model material clear composition to an appropriate range.

The storage stabilizer is a component capable of increasing the storage stability of the model material clear composition. Further, it is possible to prevent head clogging caused by polymerization of the polymerizable compound by heat energy. Examples of the storage stabilizer include hindered amine compounds (HALS), phenolic antioxidants, phosphorus antioxidants, nitrosamine compounds, and the like. Specifically, hydroquinone, methoquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, cuperon Al, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST-. 1 (manufactured by ALBEMARLE), t-butylcatechol, pyrogallol, BASF manufactured TINUVIN 111 FDL, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, TINUVIN 400 and the like. These may be used alone or in combination of two or more.

When the model material clear composition contains a storage stabilizer, the content thereof is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the model material clear composition, from the viewpoint of easily obtaining the above effect. It is more preferably 0.1 to 2 parts by mass.

The model material clear composition of the present invention is a clear composition having high transparency, which does not contain a colorant or contains only a small amount of a pigment and/or a dye such as a bluing agent. The content of the colorant in the model material clear composition is usually 0.1 mass% or less, more preferably 0.05 mass% or less, based on the total mass of the model material clear composition, and the lower limit is 0 mass. % Or more.

The model material clear composition of the present invention is formed from the model material clear composition of the present invention because it imparts high transparency and transparency to the photofabrication product obtained by photocuring and has an excellent effect of suppressing curing shrinkage. The degree of cure shrinkage deformation of the shaped article is 15 mm or less, preferably 10 mm or less, and more preferably 5 mm or less. The model material clear composition of the present invention is less likely to be colored and is less likely to undergo curing shrinkage deformation, so that it can be suitably used for producing a complicated and dense three-dimensional molded article that requires excellent appearance and high modeling accuracy. Note that the lower the curing shrinkage deformation degree, the more accurately the three-dimensional stereolithography object can be obtained, so the lower limit value of the curing shrinkage deformation degree is ideally 0 mm.

In the present invention, the curing shrinkage deformation degree means a value measured according to the following procedure.
A model material clear composition is poured into a 100 mm×100 mm×1 mm frame provided on a PET film, and a cured product obtained by curing the composition by light irradiation is deformed by curing shrinkage as compared with that before curing, The height warped upward from the PET film surface is measured. The degree of cure shrinkage deformation is calculated as the amount of displacement of the warped height. The detailed measuring method will be described in Examples below.

Since the model material clear composition of the present invention is used in the material jet stereolithography, it preferably has a viscosity of 1 mPa·s or more and less than 500 mPa·s at 25°C. From the viewpoint of improving dischargeability from the material jet nozzle, the viscosity at 25° C. is preferably 20 to 400 mPa·s, and more preferably 20 to 300 mPa·s. The above-mentioned viscosity can be measured using an R100 viscometer in accordance with JIS Z8803. The viscosity of the model material clear composition can be controlled by adjusting the type of the polymerizable compound and the compounding ratio thereof, the type of the diluent solvent and the thickener, and the addition amount thereof.

The surface tension of the model material clear composition of the present invention is preferably 24 to 34 mN/m, more preferably 28 to 30 mN/m. When the surface tension is within the above range, the droplets ejected from the nozzle can be formed normally even when the material jet is ejected at high speed, and it is possible to ensure an appropriate droplet amount and landing accuracy and to prevent satellite generation. It is possible to suppress, and it becomes easy to improve modeling accuracy. In the present invention, the surface tension of the model material clear composition can be controlled by adjusting the type of the surface modifier and the compounding amount thereof.

The method for producing the model material clear composition of the present invention is not particularly limited. For example, it can be manufactured by uniformly mixing the components constituting the model material clear composition using a mixing and stirring device or the like.

<Composition set for material jet stereolithography>
In order to form a complicated shape or a dense shape with high accuracy, the model material clear composition of the present invention is preferably used in combination with a support material for supporting the model material during three-dimensional modeling. Therefore, the present invention is also directed to a material jet stereolithography composition set comprising the model material clear composition of the present invention and a support material composition for shaping a support material by the material jet stereolithography method. ..

<Support material composition>
The support material composition is a photocurable composition for a support material, which gives a support material by photocuring. After creating the model material, it can be removed from the model material by physically separating the support material from the model material (stereolithography) or by dissolving the support material in an organic solvent or water. A stereolithography object formed from the material clear composition is obtained. The model material clear composition of the present invention can be used in combination with various conventionally known compositions as a support material composition, but the model material is not damaged when the support material is removed, and the model material clear composition The support material composition constituting the stereolithography composition set of the present invention is preferably water-soluble because the support material can be removed gently and finely and easily.

Examples of such a water-soluble support material composition include those containing acryloylmorpholine and polyalkylene glycol.

When the support material composition contains acryloylmorpholine, a support material having excellent water solubility can be obtained. In addition, for example, when the model material clear composition and the support material composition both contain acryloylmorpholine, the model material (stereolithography) obtained has a high hardness but tends to warp easily. Since the material clear composition is strongly supported by the support material having high hardness, warping is unlikely to occur, and a stereolithographic object can be obtained with good dimensional accuracy.

The content of acryloylmorpholine contained in the support material composition is preferably 20 to 90 parts by mass, more preferably 30 parts by mass or more, and further preferably 40 parts by mass with respect to 100 parts by mass of the support material composition. The amount is not less than 70 parts by mass, more preferably not more than 80 parts by mass, further preferably not more than 70 parts by mass. When the content of acryloylmorpholine is within the above range, it is possible to improve the removability of the support material with water without lowering the support power of the support material.

In the present invention, the support material composition may contain a water-soluble monofunctional ethylenically unsaturated monomer in addition to acryloylmorpholine. Examples of the water-soluble monofunctional ethylenically unsaturated monomer include, for example, hydroxyl group-containing (meth)acrylates having 5 to 15 carbon atoms [eg, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl). (Meth)acrylate, etc., a hydroxyl group-containing (meth)acrylate having a number average molecular weight (Mn) of 200 to 1,000 [eg, polyethylene glycol mono(meth)acrylate, monoalkoxy (having 1 to 4 carbon atoms) polyethylene glycol mono(meth)] Acrylate, polypropylene glycol mono(meth)acrylate, monoalkoxy (C1-4) polypropylene glycol mono(meth)acrylate, PEG-PPG block polymer mono(meth)acrylate, etc.], C3-15 (meth) Acrylamide derivative [eg (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-butyl(meth)acrylamide, N,N'-dimethyl(meth)) Acrylamide, N,N′-diethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, N-hydroxybutyl(meth)acrylamide, etc.] and the like. These may be used alone or in combination of two or more.

When the support material composition contains a water-soluble monofunctional ethylenically unsaturated monomer, the content thereof is preferably 1 to 50 parts by mass, and more preferably 100 parts by mass of the support material composition. Is 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 50 parts by mass or less, and further preferably 30 parts by mass or less. When the content of the water-soluble monofunctional ethylenically unsaturated monomer is within the above range, the removability of the support material with water can be improved without lowering the support power of the support material.

Examples of the polyalkylene glycol contained in the support material composition include linear and multi-chain compounds having an oxyethylene group and/or an oxypropylene group. By including the polyalkylene glycol containing an oxyethylene group and/or an oxypropylene group, it is possible to further improve the water removability without lowering the support force of the support material. Further, as long as it is soluble in water, it may contain an alkyl group at the terminal, for example, preferably an alkyl chain having 6 or less carbon atoms.

Specific examples of the polyalkylene glycol containing such an oxyethylene group and/or oxypropylene group include, for example, polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene glycol mono. Examples include butyl ether and polyoxypropylene glyceryl ether. These may be used alone or in combination of two or more.

The number average molecular weight ( _Mn ) of the polyalkylene glycol containing an oxyethylene group and/or an oxypropylene group is preferably 100 to 5,000, more preferably 200 to 3,000. When the number average molecular weight of the polyalkylene glycol is within the above range, it becomes easily compatible with acryloylmorpholine or a water-soluble monofunctional ethylenically unsaturated monomer in the composition before curing, while acryloylmorpholine after light irradiation. It becomes difficult to be compatible with the cured product of the water-soluble monofunctional ethylenically unsaturated monomer, and the support material can be easily removed with water or a water-soluble solvent.

The content of the polyalkylene glycol containing an oxyethylene group and/or an oxypropylene group in the support material composition may be, for example, 20 to 95 parts by mass, preferably 20 parts by mass with respect to 100 parts by mass of the support material composition. It is more than or equal to parts by mass, preferably less than or equal to 49 parts by mass. When the content of the polyalkylene glycol containing an oxyethylene group and/or an oxypropylene group is within the above range, the support material can be removed with water or a water-soluble solvent without lowering the support ability of the support material. be able to.

Furthermore, the support material composition preferably contains a water-soluble organic solvent. The water-soluble organic solvent is a component that improves the solubility in water of the support material obtained by photocuring the support material composition. It also has the function of adjusting the viscosity of the support material composition to a low level.

As the water-soluble organic solvent, it is preferable to use a glycol-based solvent, and specifically, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate, and triethylene glycol monoacetate. Glycol ester solvents such as propylene glycol monoacetate, tetraethylene glycol monoacetate, tetrapropylene glycol monoacetate, ethylene glycol diacetate, propylene glycol diacetate; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl Glycol ether solvents such as ether, propylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Glycols such as dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate Examples include monoether acetate-based solvents. These may be used alone or in combination of two or more.

Among them, it is easy to prepare a low-viscosity support material composition, and since the support material obtained by curing is excellent in water solubility, as the water-soluble organic solvent, triethylene glycol monomethyl ether, diethylene glycol diethyl ether and di-ethylene glycol are used. Propylene glycol monomethyl ether acetate is preferred.

The content of the water-soluble organic solvent in the support material composition is preferably 35 parts by mass or less, more preferably 5 parts by mass or more, and further preferably 10 parts by mass with respect to 100 parts by mass of the support material composition. Or more, and more preferably 30 parts by mass or less. When the content of the water-soluble organic solvent is within the above range, the removability of the support material with water or the water-soluble solvent can be improved without lowering the support power of the support material.

Further, the support material composition preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that accelerates a radical reaction when irradiated with light having a wavelength in the ultraviolet ray, near ultraviolet ray or visible light region. Examples of the photopolymerization initiator include benzoin compounds having 14 to 18 carbon atoms [for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.], acetophenone compounds having 8 to 18 carbon atoms [for example, , Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc.], anthraquinone compound having 14 to 19 carbon atoms [eg, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.], a thioxanthone compound having 13 to 17 carbon atoms [for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.], carbon A ketal compound having a number of 16 to 17 [eg, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.], a benzophenone compound having a carbon number of 13 to 21 [eg, benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bis Methylaminobenzophenone, etc.], an acylphosphine oxide compound having 22 to 28 carbon atoms [eg, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4, 4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide], a mixture of these compounds, and the like. These may be used alone or in combination of two or more. A commercially available product may be used as the photopolymerization initiator, and examples thereof include IRGACURE TPO manufactured by BASF.

The content of the photopolymerization initiator in the support material composition is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the support material composition. When the content of the photopolymerization initiator is within the above range, unreacted polymerization components can be sufficiently reduced, and the curability of the support material can be easily enhanced sufficiently.

The viscosity of the support material composition in the present invention is preferably 1 to 500 mPa·s at 25° C., and more preferably 20 to 400 mPa·s, from the viewpoint of improving the dischargeability from the material jet nozzle. .. The above-mentioned viscosity can be measured using an R100 viscometer in accordance with JIS Z8803.

In the present invention, the surface tension of the support material composition is preferably 24 to 30 mN/m, more preferably 24.5 to 29.5 mN/m, and further preferably 25 to 29 mN/m. When the surface tension is within the above range, droplets ejected from the nozzle can be normally formed, and it is possible to secure an appropriate droplet amount and landing accuracy and suppress the occurrence of satellites. It becomes easy to secure high modeling accuracy. The surface tension of the support material composition can be measured according to the same method as the method for measuring the surface tension of the model material clear composition.

In the present invention, the method for producing the support material composition is not particularly limited, and for example, it can be produced by uniformly mixing the components constituting the support material composition using a mixing and stirring device or the like.

<Manufacturing method for stereolithography>
A three-dimensional object can be manufactured from the model material clear composition of the present invention by a stereolithography method using a material jet method. In particular, the model material clear composition of the present invention is suitable for a material jet stereolithography method using an LED light source, which has a peak wavelength in the wavelength range of 360 to 410 nm and is widely used in the past. The method for producing a stereolithography product by the model material clear composition of the present invention is not particularly limited as long as it is a method for producing a three-dimensional fabrication product by the stereolithography method by the material jet method, but the model material clear composition is photocured. It is preferable that the method includes a step of obtaining a support material composition by photocuring the support material composition, and a step of removing the support material from the model material.

Specifically, for example, based on the three-dimensional CAD data of the object to be manufactured, the data of the model material clear composition which is laminated by the material jet method to form the three-dimensional object, and the three-dimensional object under manufacturing Data for the supporting material composition to be supported is prepared, and slice data for ejecting each composition is prepared with a material jet type 3D printer. Based on the prepared slice data, the model material clear composition and the supporting material composition are respectively prepared. After the ejection, the photo-curing treatment is repeated for each layer, so that a modeled product composed of a cured product of the model material clear composition (model material) and a cured product of the support material composition (support material) can be produced.

Examples of the light that cures the model material clear composition and the support material composition include active energy rays such as far infrared rays, infrared rays, visible rays, near ultraviolet rays, ultraviolet rays, electron beams, α rays, γ rays, and X rays. .. Among these, near-ultraviolet rays or ultraviolet rays are preferable from the viewpoint of easiness and efficiency of curing work.

Although a conventionally known high-pressure mercury lamp or metal halide lamp may be used as the light source, the LED method is preferable from the viewpoints of downsizing the equipment and low power consumption. In particular, the model material clear composition of the present invention has an excellent coloring suppression effect and curing shrinkage suppression effect when cured using an LED light source having a peak wavelength in the range of 360 nm to 410 nm, and thus has a peak wavelength of 360 nm to 410 nm. It is preferable to use an LED in the range of 1) as a light source, and it is possible to use a UV-LED having a central wavelength of 385 to 410 nm because light can easily reach a deep layer and hardness and dimensional accuracy of a modeled object can be improved. preferable. The amount of light is preferably 200 to 500 mJ/cm ² from the viewpoint of hardness and dimensional accuracy of the molded product.

The thickness of each layer constituting the three-dimensional model is preferably thin from the viewpoint of modeling accuracy, but is preferably 5 to 30 μm from the viewpoint of balance with the modeling speed.

The support material can be removed from the modeled object in which the model material and the support material are combined to obtain a stereolithography product made of the model material. The removal of the support material is preferably performed, for example, by immersing the obtained molded article in a removal solvent that dissolves the support material to soften the support material and then removing the support material from the surface of the model material with a brush or the like. .. Water or a water-soluble solvent such as a glycol solvent or an alcohol solvent may be used as the solvent for removing the support material. These may be used alone or in combination.

Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "parts" in the examples are% by mass and parts by mass.

1. Model material clear composition Table 1 shows the details and abbreviations of the components constituting the model material clear composition used in the examples.

(1) Preparation of Model Material Clear Composition According to each composition shown in Table 2, the components constituting each model material clear composition are uniformly mixed using a mixing and stirring device, and after stirring, a glass filter (Kiriyama (Manufactured by Seisakusho), the mixture was suction-filtered to prepare the model material clear compositions of Examples 1 to 3 and Comparative Examples 1 to 7.

(2) Physical Properties of Model Material Clear Composition The viscosity and glass transition temperature of each model material clear composition prepared in the above Examples and Comparative Examples were measured according to the following methods. The results are shown in Table 2.

<Measurement of viscosity>
The viscosity of each model material clear composition was measured using an R100 viscometer (manufactured by Toki Sangyo Co., Ltd.) under conditions of 25° C. and a cone rotation speed of 5 rpm.

<Measurement of glass transition temperature>
The glass transition temperature of each model material clear composition was measured using TG-DTA2000S Thermo Plus Evo II, DSC8230 (manufactured by Rigaku Corporation). The measurement was performed at a temperature rise temperature of 10° C./min and a measurement temperature range of −60° C. to 200° C.

(3) Evaluation of Physical Properties and Properties of Cured Product of Model Material Clear Composition A cured product was prepared from the model material clear composition prepared in the above Examples and Comparative Examples, and the physical properties and properties of each cured product are shown below. It evaluated according to the method. The results are shown in Table 2.

<Production of cured product of model material clear composition>
A silicone rubber sheet (thickness 1 mm, rubber sheet for food industry made by Togawa Rubber Co., Ltd. (K-125<50>) is cut into a rectangle of 120 mm×120 mm, and a 100 mm×100 mm square is cut out from the center of the rectangle. Then, a square frame was produced, and then the square frame was pressure-bonded and pasted onto a PET film (Lumirror S-10#25, thickness 23 μm) manufactured by Toray Industries, Inc. to produce a mold. 10 g of the model material clear compositions of Examples and Comparative Examples were poured into the frame of the mold and irradiated with an ultraviolet irradiation device (LED lamp, 385 nm, irradiation light amount: 500 mJ/cm ² ). By taking out from the sheet (square frame), evaluation samples of Examples and Comparative Examples were produced, and the evaluation samples were used to evaluate curability, coloration evaluation, and curing shrinkage.

<Curability>
The curability of the cured product of the model material clear composition produced by the above method was evaluated according to the following criteria.
◯: Hardened to become solid.
×: It remained liquid, or a tackiness remained on the surface (fingerprints were formed when touched).

<Evaluation of coloring>
The prepared cured product is placed on a white PET film (Teijin Tetron film U292W manufactured by Teijin Ltd.), and a spectrocolorimeter X-Rite 939 (manufactured by X-Rite) is used from the upper surface of the cured product on the film. Conditions: light source D65, viewing angle The value of hue L*a*b* was measured at 10°. The value b*, which is a numerical value indicating the yellowish tint, was confirmed, and if b*<2, it was determined that the yellow coloring was small (evaluation: ◯).

<Measurement of curing shrinkage deformation degree>
A cured product was prepared from the model material clear composition according to the above method, and the cured product obtained by comparison with that before curing had a maximum height from the installation surface (from the PET film surface to the upper surface of the cured product). The height was measured, and the value obtained by subtracting the thickness of the cured product (1 mm) was calculated as the displacement amount (mm), which was defined as the curing shrinkage deformation degree. It is evaluated that the larger the value is, the larger the curing shrinkage is.

As is clear from the results of Table 2, in the model material clear composition of the present invention containing a sensitizer selected from dialkoxyanthracene and bisalkanoyloxyanthracene (Examples 1 to 4), curing was performed with an LED light source of 385 nm. A colored stereolithography product was obtained while suppressing shrinkage. On the other hand, the model material clear composition containing no sensitizer (Comparative Example 3) or using a sensitizer other than dialkoxyanthracene and bisalkanoyloxyanthracene (Comparative Example 7) was modeled by an LED light source of 385 nm. The clear material composition did not cure.

Claims (10)

A model material clear composition used in a material jet stereolithography method using an LED light source having a peak wavelength in the range of 360 nm to 410 nm, comprising a polymerizable compound, a photopolymerization initiator and a sensitizer, The maximum value of the absorption wavelength of the photopolymerization initiator is 400 nm or less, the sensitizer is selected from the group consisting of dialkoxyanthracene and bisalkanoyloxyanthracene, and the curing of the shaped article formed from the model material clear composition. A model material clear composition having a shrinkage deformation degree of 15 mm or less. The model material clear composition according to claim 1, wherein the sensitizer contains at least one selected from 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-bisoctanoyloxyanthracene. Stuff. The model material clear composition according to claim 1 or 2, wherein the content of the sensitizer is 0.01 to 2 mass% with respect to the total mass of the model material clear composition. The model material according to claim 1, wherein the photopolymerization initiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Clear composition. The model material clear composition according to any one of claims 1 to 4, wherein the content of the photopolymerization initiator is 0.1 to 5 mass% with respect to the total mass of the model material clear composition. The model material clear composition according to claim 1, which has a viscosity at 25° C. of 1 mPa·s or more and less than 500 mPa·s. The model material clear composition according to any one of claims 1 to 6, wherein the model material clear composition has a glass transition temperature of 30 to 70°C. The model material clear composition according to any one of claims 1 to 7, which comprises a monofunctional polymerizable compound or a bifunctional polymerizable compound. The model material clear composition according to any one of claims 1 to 8, comprising acryloylmorpholine as the polymerizable compound. A composition set for material jet stereolithography, comprising the model material clear composition according to any one of claims 1 to 9 and a support material composition for shaping a support material by a material jet stereolithography method.