JP2016098314A - Cellulose-based material, composition set for manufacturing molded object, molded object, dialyzer, dialysis apparatus, dialysis method, and method for manufacturing molded object - Google Patents

Abstract

To provide a cellulosic material having a self-repairing function and capable of being used for the manufacture of a highly reliable shaped article, a composition set for producing a shaped article, and a highly reliable shaped article having a self-repairing function And providing a method for producing a shaped article that can efficiently produce a highly reliable shaped article having a self-repairing function.
The cellulosic material of the present invention is a cellulosic material containing a cellulose derivative, wherein the cellulose derivative has an amine structure in the molecule. It is preferable that the amine structure is introduced into a repeating unit of a polymer chain having a repeating structure introduced into the cellulose skeleton structure of the cellulose derivative. The cellulose derivative preferably has a polyallylamine structure.
[Selection figure] None

Description

The present invention is a cellulosic material, a composition set for manufacturing a molded article, a molded article, a dialyzer,
The present invention relates to a dialysis apparatus, a dialysis method, and a manufacturing method of a shaped article.

Cellulose is a renewable resource, has an enormous amount of accumulation on the earth, is excellent in biocompatibility and degradability, and is an environmentally friendly material. (For example, refer to Patent Document 1).

However, in the past, most of the applications of cellulose are paper products such as printing paper and corrugated paper, and in addition to that, it is used for fibers (cellulose fibers) etc. There was a problem that it was not fully utilized.

On the other hand, there is an attempt to provide an artificial blood vessel using cellulose produced by a microorganism (see Patent Document 1).

However, with such a technique, there is a problem in that the efficiency of manufacturing an artificial blood vessel that is a molded article using cellulose or cellulose is low, and the shape is difficult to control. Also,
In artificial blood vessels, etc., once a defect occurs, it is difficult to replace it, and higher safety is required. However, with conventional technology, it is difficult to sufficiently prevent the occurrence of defects, and safety There was a problem with reliability.

JP-A-3-272772

An object of the present invention is to provide a cellulosic material that has a self-repairing function and can be used for manufacturing a highly reliable shaped article, a composition set for producing a shaped article, and has a self-repairing function and high reliability. Providing a modeled object, providing a highly reliable dialyzer, dialysis device, dialysis method, and manufacturing a modeled object that has a self-repair function and can efficiently manufacture a highly reliable modeled object It is to provide a method.

Such an object is achieved by the present invention described below.
The cellulosic material of the present invention is a cellulosic material containing a cellulose derivative,
The cellulose derivative has an amine structure in the molecule.

Thereby, the cellulosic material which has a self-repair function and can be used for manufacture of a highly reliable molded article can be provided.

In the cellulose material of the present invention, the amine structure is preferably introduced into a repeating unit of a polymer chain having a repeating structure introduced into the cellulose skeleton structure of the cellulose derivative.

As a result, the strength of the modeled object can be improved, the self-repair function of the modeled object can be improved, and the reliability and durability of the modeled object can be improved. can do. Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article (cellulosic member).

In the cellulose material of the present invention, the cellulose derivative preferably has a primary amine or a salt thereof as the amine structure.

As a result, the strength of the modeled object can be improved, the self-repair function of the modeled object can be improved, and the reliability and durability of the modeled object can be improved. can do.

In the cellulose material of the present invention, the cellulose derivative preferably has a polyallylamine structure.

As a result, the strength of the modeled object can be improved, the self-repair function of the modeled object can be improved, and the reliability and durability of the modeled object can be improved. can do. Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article (cellulosic member).

In the cellulose-based material of the present invention, the amine structure is preferably provided in a substituent introduced into a hydroxyl group bonded to the 6-position carbon of β-glucose constituting cellulose.

As a result, the interaction between ions between the cellulose derivative and the anionic compound can be more effectively exhibited, the strength of the model can be improved, and the self-repair function of the model Can be made more excellent, and the reliability and durability of the molded article can be made more excellent. Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article (cellulosic member).

The composition set for manufacturing a molded article of the present invention includes a first composition containing the cellulosic material of the present invention,
And a second composition containing a divalent or higher anionic compound.

Thereby, the composition set for modeling thing manufacture which can be used for manufacture of a highly reliable modeling thing which has a self-repair function can be provided.

In the composition set for manufacturing a molded article of the present invention, it is preferable that the first composition includes, as the cellulose-based material, particles having at least a region including a surface composed of the cellulose derivative.

Thereby, the mechanical strength etc. of the molded article manufactured can be made more excellent.
Moreover, a shaped article with high dimensional accuracy can be manufactured more efficiently.

In the composition set for manufacturing a shaped article of the present invention, the second composition is preferably a liquid.
Thereby, a model with higher dimensional accuracy can be manufactured with more excellent productivity.

The shaped article of the present invention is manufactured using the cellulosic material of the present invention.
Thereby, a highly reliable shaped article having a self-repair function can be provided.

The shaped article of the present invention is manufactured using the composition set for producing a shaped article of the present invention.
Thereby, a highly reliable shaped article having a self-repair function can be provided.

The shaped article of the present invention includes a cellulose derivative having an amine structure in the molecule, and a divalent or higher anionic compound,
An ionic bond is formed between the amine structure and the anionic functional group of the anionic compound.
Thereby, a highly reliable shaped article having a self-repair function can be provided.

In the shaped article of the present invention, it is preferable that the anionic compound contains polyphosphoric acid.

Thereby, the mechanical strength etc. of a molded article can be made more excellent. In addition, the self-repair function can be exhibited more effectively. From such a thing, durability and reliability of a molded article can be made more excellent.

The shaped article of the present invention is preferably a medical device.
Thereby, the effect of the present invention that has a self-repair function and high reliability is more remarkably exhibited.

The shaped article of the present invention is preferably an artificial blood vessel.
Thereby, the effect of the present invention that has a self-repair function and high reliability is more remarkably exhibited.

The shaped article of the present invention is preferably a dialysis member.
Thereby, the effect of the present invention that has a self-repair function and high reliability is more remarkably exhibited.

The dialyzer of the present invention is characterized by including the shaped article of the present invention.
Thereby, a safe and highly reliable dialyzer can be provided.

The dialysis apparatus of the present invention is characterized by including the shaped article of the present invention.
Thereby, a highly safe and reliable dialysis apparatus can be provided.

The dialysis method of the present invention is characterized by performing dialysis using the shaped article of the present invention.
Thereby, a safe and highly reliable dialysis method can be provided.

The method for producing a shaped article of the present invention includes a layer forming step of forming a layer having a predetermined thickness using a particle-containing composition containing particles,
A binding liquid applying step of applying a binding liquid to a predetermined region of the layer;
It is a method for producing a shaped article by sequentially repeating these steps,
The particle-containing composition contains a cellulose derivative having an amine structure in the molecule,
The binding liquid contains a divalent or higher anionic compound.

Thereby, the manufacturing method of the molded article which has a self-repair function and can manufacture a highly reliable molded article efficiently can be provided.

It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the molded article of this invention. It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of the molded article of this invention. It is sectional drawing which shows typically suitable embodiment of the manufacturing apparatus used for manufacture of the molded article of this invention. It is a side view which shows typically suitable embodiment of the member for dialysis as a molded article of this invention. It is a schematic diagram which shows suitable embodiment of the dialysis apparatus of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

《Cellulosic material》
First, the cellulose material of the present invention will be described in detail.

The cellulosic material of the present invention contains a cellulose derivative.
And the said cellulose derivative has an amine structure in a molecule | numerator.

Such a cellulose derivative forms a suitable ionic bond with a divalent or higher anionic compound as described in detail later. For this reason, in the molded object comprised with the material containing a cellulose derivative and an anionic compound, the state which the cellulose derivative and the anionic compound couple | bonded suitably can be taken. In more detail, the bond between the cellulose derivative and the anionic compound is bonded by an ionic bond, which is a kind of intermolecular force, but compared with the usual intermolecular forces such as van der Waals force and hydrogen bond. The power is great. Therefore, the strength of the modeled object can be made sufficiently excellent. In addition, for example, even when a defect is generated such as a molded article is scratched or a relatively small fracture occurs due to an external force, an ionic interaction (intermolecular) between a cellulose derivative and an anionic compound occurs. The self-healing function that repairs the above-described defects is exhibited. Therefore,
The modeled object is excellent in reliability and durability.

[Cellulose derivative]
As described above, the cellulose material of the present invention includes a cellulose derivative having an amine structure in the molecule.

Cellulose is a compound in which β-glucose is polymerized by a glycosidic bond. In the present invention, the cellulose derivative may be any compound that can be derived from cellulose by a chemical reaction. For example, at least one hydroxyl group of cellulose is present. And the like (including those obtained by condensation reaction of at least part of the hydroxyl groups of cellulose with other compounds).

In addition, the said substituent may be similarly introduced about all the repeating units (glucose structure), and may be introduced only to a part of repeating unit (glucose structure). . Moreover, the site | part in which the said substituent was introduce | transduced may differ with repeating units (glucose structure).

And the cellulose derivative contained in the cellulose-type material of this invention has an amine structure in a molecule | numerator.

Examples of amine structures include primary amines, secondary amines, tertiary amines and salts thereof.
A grade ammonium etc. are mentioned. In the present invention, the amine structure may be an aromatic heterocyclic structure containing a nitrogen atom as a hetero atom (for example, a pyridine structure).

Among the above, the amine structure of the cellulose derivative is preferably a primary amine or a salt thereof.

Thereby, the bond strength between the cellulose derivative and the anionic compound can be increased, and the strength of the molded article can be further improved. In addition, the self-repair function of a shaped article composed of a material containing a cellulose derivative and an anionic compound can be made more excellent, and the reliability and durability of the shaped article can be made more excellent. it can.

The amine structure may be introduced at any site of the cellulose derivative,
It is preferably provided in a substituent introduced into a hydroxyl group bonded to the 6-position carbon of β-glucose constituting cellulose. That is, an amine structure is preferably introduced into R ³ of the following formula (2).

（式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立に、水素原子または置換
基を表す。ただし、少なくとも、分子内に少なくとも１つの前記アミン構造を含む官能基
が導入されている。）

(In Formula (2), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituent, provided that at least one amine structure is included in the molecule. Functional group has been introduced.)

Thereby, the amine structure can be efficiently exposed outside the molecule of the cellulose derivative. As a result, the interionic interaction between the cellulose derivative and the anionic compound can be more effectively exhibited, the strength of the model can be improved, and the self-repair function of the model Can be made more excellent, and the reliability and durability of the molded article can be made more excellent. Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article (cellulosic member). In addition, a method (detailed later) (
When manufacturing a model using a three-dimensional modeling method), it is possible to form a strong ionic bond between a cellulose derivative and an anionic compound in a shorter time, and a bonded part (solidified part)
Therefore, the productivity of the shaped article can be further improved.

As long as at least one amine structure is introduced into the molecule of the cellulose derivative,
It is preferable that a plurality of amine structures are introduced in the molecule of the cellulose derivative.

Thereby, the effect by having the amine structure as described above is more remarkably exhibited, the strength of the model can be improved, and the self-repair function of the model can be improved. And the reliability and durability of the modeled object can be further improved.

In particular, the plurality of amine structures are preferably those introduced into a repeating unit of a polymer chain (side chain) having a repeating structure introduced into a cellulose skeleton structure (basic skeleton).

Thereby, the effect by having the amine structure as described above is more remarkably exhibited, the strength of the model can be improved, and the self-repair function of the model can be improved. And the reliability and durability of the modeled object can be further improved. Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article (cellulosic member). Moreover, when manufacturing a modeling thing using the method (three-dimensional modeling method) explained in full detail later, formation of the strong ionic bond between a cellulose derivative and an anionic compound is formed in a short time. Since the formation efficiency of the joint part (solidified part) becomes better, the productivity of the shaped article can be made more excellent.

The cellulose derivative preferably has a polyallylamine structure as an amine structure.

Thereby, while being able to make the intensity | strength of the molded article comprised with the material containing a cellulose derivative and an anionic compound more excellent, it can make the self-repair function of a molded article more excellent, The reliability and durability of the modeled object can be further improved.
Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article (cellulosic member). Moreover, when manufacturing a modeling thing using the method (three-dimensional modeling method) explained in full detail later, formation of the strong ionic bond between a cellulose derivative and an anionic compound is formed in a short time. Since the formation efficiency of the joint part (solidified part) becomes better, the productivity of the shaped article can be made more excellent.

In addition, as a polyallylamine structure, what is represented by following formula (3) is mentioned, for example.

（式（３）中、ｎは、２以上の整数である。）

(In formula (3), n is an integer of 2 or more.)

The polyallylamine structure represented by the formula (3) is a primary amine, but may be a secondary amine, a tertiary amine, a salt thereof, or a quaternary ammonium.

Specific examples of preferable cellulose derivatives that satisfy the above conditions include the following formula (7
) And the like.

（式（７）中、ｎ、ｍは、それぞれ独立に、２以上の整数であり、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ
^５は、それぞれ独立に、水素原子（Ｈ）またはアセチル基（ＣＨ_３ＣＯ）である。）

(In the formula (7), n and m are each independently an integer of 2 or more, and R ¹ , R ² , R ⁴ , R
⁵ is each independently a hydrogen atom (H) or an acetyl group (CH ₃ CO). )

In addition, the cellulose derivative may have a functional group (reactive functional group) that bonds the molecular chains of the cellulose derivative by a covalent bond.

In this way, the cellulose-based material has inherent features (for example, for example, while effectively preventing a decrease in strength due to separation between molecules and the like by covalently bonding molecules of the cellulose derivative) High strength, light weight, biological safety, environmental safety, etc.) can be more effectively exhibited. Moreover, the mechanical strength, durability, and reliability of the finally obtained shaped article can be further improved.

Such a functional group (reactive functional group) may be one that directly bonds the molecules of the cellulose derivative, or one that binds through another atom (at least one atom). May be.

Examples of the functional group (reactive functional group) include those containing a carbon-carbon double bond, hydroxyl groups, carboxyl groups, and the like, but those containing a carbon-carbon double bond are preferred.

Thereby, the reactivity of a cellulose derivative can be made excellent and the productivity of the molded article manufactured using a cellulosic material can be made more excellent. Moreover, it can prevent effectively that the unreacted cellulose derivative is contained unintentionally much in the manufactured molded article. In addition, the chemical stability of the covalent bond formed by the reaction can be further improved. From such a thing, durability, intensity | strength, and reliability of a molded article can be made more excellent. In addition, since the range of selection of the compound that reacts with the cellulose derivative (the compound that can react with the reactive functional group of the cellulose derivative) is widened, the range of design of the shaped article is widened.

Examples of the functional group (reactive functional group) containing a carbon-carbon double bond include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

Thereby, the reactivity of a cellulose derivative can be made further excellent and the productivity of a molded article can be made further excellent. Moreover, it can prevent more effectively that unreacted cellulose derivative is contained unintentionally much in the final molded article. In addition, the chemical stability of the covalent bond formed by the reaction can be further improved.
From such a thing, durability, intensity | strength, and reliability of a molded article can be made further excellent. In addition, since the range of selection of the compound that reacts with the cellulose derivative (the compound that can react with the reactive functional group of the cellulose derivative) is widened, the range of design of the shaped article is widened.

The reactive functional group may be introduced into any part of the cellulose derivative, but is introduced into a side chain of the cellulose derivative different from the cellulose skeleton structure (basic skeleton structure). preferable.

As a result, the characteristics inherent in cellulose (for example, high strength, light weight, biosafety,
The effect of having a reactive functional group can be exhibited while exhibiting environmental safety and the like more effectively. In addition, since the side chain of the cellulose derivative is generally more reactive than the cellulose skeleton structure (basic skeleton structure), the reaction involving the reactive functional group can proceed more efficiently.

In particular, the reactive functional group is preferably introduced by a chemical reaction into a hydroxyl group bonded to the 6-position carbon of β-glucose constituting cellulose. That is, the above formula (2
It is preferable that the reactive functional group is introduced into R ³ of).

Thereby, from making the steric hindrance of the reactive functional group small, the reactivity of the cellulose derivative can be made excellent, and the productivity of the shaped article can be made more excellent. . Moreover, it can prevent that unreacted cellulose derivative is contained unintentionally much in the final molded article. From such a thing, durability, intensity | strength, and reliability of a molded article can be made more excellent. Moreover, the synthesis | combination of the cellulose derivative as a structural component of a cellulosic material can be performed efficiently. As a result, it can also contribute to the reduction of the production cost of a molded article.

Moreover, it is preferable that the said reactive functional group is introduce | transduced into the cellulose frame | skeleton via the at least 1 carbon-carbon single bond in the basic cellulose structure.

Thereby, the reactivity of the said reactive functional group can be made more excellent, and the productivity etc. of a molded article can be made more excellent.

The reaction for bonding the molecular chains of the cellulose derivative by covalent bonds is preferably progressed by irradiation with ultraviolet rays.

Thereby, the productivity of a molded article can be made more excellent while preventing unintentional modification | denaturation, deterioration, etc. of material more effectively. Moreover, complication of the structure of the manufacturing apparatus of a molded article can be prevented, and the production cost of a molded article can be suppressed.

The cellulose derivative (in particular, the cellulose derivative in which the reactive functional group contains a carbon-carbon double bond) is preferably one that reacts with a siloxane compound having two or more SH bonds in the molecule.

Thereby, the formation efficiency of the said covalent bond can be made more excellent, and the productivity of a molded article can be made more excellent. Moreover, it can prevent effectively that unreacted cellulose derivative is contained unintentionally much in a molded article. In addition, the chemical stability of the covalent bond formed by the reaction can be further improved. From such a thing, durability, intensity | strength, and reliability of a molded article can be made more excellent. Moreover, the chemical reaction which forms the said covalent bond can be performed suitably by heating.

The siloxane compound with which the cellulose derivative reacts preferably has two or more SH bonds in the molecule, but more preferably has three or more SH bonds in the molecule. .

Thereby, a more complicated network structure can be formed by the chemical reaction that forms the covalent bond, and the durability, strength, and the like of the molded article can be further improved.

The siloxane compound with which the cellulose derivative reacts may be a chain compound, but is preferably a cyclic compound.
Thereby, durability, intensity | strength, etc. of a molded article can be made more excellent.

Examples of the siloxane compound that satisfies such conditions (siloxane compound that reacts with a cellulose derivative) include those represented by the following formula (4).

In addition, the cellulose derivative (particularly, the cellulose derivative in which the reactive functional group includes a carbon-carbon double bond) may react with a crosslinking agent.

Thereby, for example, a more complicated network structure can be formed by a chemical reaction that forms the covalent bond, and the durability, strength, and the like of the shaped article can be further improved.
Further, for example, the chemical reaction for forming the covalent bond can be suitably performed by irradiation with light such as ultraviolet rays.

As a crosslinking agent, the compound etc. which have polymerizable functional groups, such as a vinyl group and a (meth) acryloyl group, are mentioned, for example.

Among them, as the crosslinking agent, a compound having a plurality of polymerizable functional groups in the molecule is preferable,
A compound in which both ends of the alkyl chain are modified with a polymerizable functional group is more preferable.
As such a crosslinking agent, the compound etc. which are represented by following formula (5) are mentioned, for example.

（式（５）中、ｎは、１以上の整数である。）

(In formula (5), n is an integer of 1 or more.)

The weight average molecular weight of the cellulose derivative contained in the cellulosic material is not particularly limited, but is preferably from 5,000 to 10,000,000, and preferably from 10,000 to 7,000.
More preferably, it is 000 or less.

Thereby, durability, intensity | strength, and reliability of the molded article manufactured can be made more excellent.

Although the content rate of the cellulose derivative in a cellulosic material is not specifically limited, 50
It is preferably at least mass%, more preferably at least 70 mass%, and even more preferably at least 80 mass%.

Thereby, the effect by including a cellulose derivative as mentioned above is exhibited more notably.

[Other ingredients]
In addition, the cellulose-based material may contain components (other components) other than the above-described cellulose derivative (cellulose derivative having an amine structure in the molecule).

Examples of such components include cellulose derivatives that do not have an amine structure as described above (other cellulose derivatives) and cellulose that has not been chemically modified. Such components may be left as unreacted components at the time of synthesizing the cellulose derivative (cellulose derivative having an amine structure in the molecule), or may be caused by a side reaction, for example. Also good.

In addition, the cellulosic material includes a plurality of particles, and the particles are provided on the surface of the core composed of a material other than the cellulose derivative having an amine structure in the molecule, and have an amine structure in the molecule. The surface layer comprised with the material containing the cellulose derivative which has may be provided.

The cellulose-based material of the present invention may contain a raw material-derived subcomponent (for example, lignin, hemicellulose, etc.).

In addition, the cellulosic material may include a carrier that holds the above-described cellulose derivative. For example, when the cellulosic material includes a plurality of particles, the particles may have mother particles (base) for holding the cellulose derivative near the outer surface of the particles. In other words, the cellulosic material is composed of base particles as a carrier,
It may include a plurality of particles having a surface layer composed of a cellulose derivative having an amine structure in the molecule.
Thereby, the mechanical strength etc. of the molded article manufactured can be made more excellent.

In this case, the constituent material of the carrier is not particularly limited. For example, silica, alumina,
Various metal oxides such as titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide and potassium titanate; various metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; silicon nitride, titanium nitride, Various metal nitrides such as aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; carbonates of various metals such as calcium carbonate and magnesium carbonate; various kinds such as calcium sulfate and magnesium sulfate Metal sulfates; silicates of various metals such as calcium silicate and magnesium silicate; phosphates of various metals such as calcium phosphate; borates of various metals such as aluminum borate and magnesium borate, and these Inorganic materials such as composites, polyethylene resin; polypropylene; polyethylene oxide; polypropylene Polystyrene; Polyurethane; Polyester; Silicone resin; Acrylic silicone resin; Polymers containing (meth) acrylic acid esters such as polymethyl methacrylate; ) Crosspolymers containing acrylic acid esters as constituent monomers (ethylene acrylic acid copolymer resins, etc.); polyamide resins such as nylon 12, nylon 6, copolymer nylon; polyimide; gelatin; starch; chitin; Of these, composite materials containing two or more of them may be mentioned.

《Method for manufacturing shaped objects》
Next, the manufacturing method of the molded article of this invention is demonstrated.

The shaped article of the present invention is not particularly limited as long as it is manufactured using the cellulose-based material of the present invention as described above.

Examples of the production method for producing the shaped article of the present invention include various molding methods such as compression molding, extrusion molding, and injection molding, and methods for subjecting bulk materials to machining such as cutting, grinding, and polishing.

Moreover, as a manufacturing method of the molded article of the present invention, a three-dimensional modeling method as described below (a layer forming step of forming a layer using the composition is performed a plurality of times, the layers are stacked, and the molded article (tertiary The method of producing the original shaped object) can be used.

Thereby, even a modeled object requiring high dimensional accuracy or a modeled object with a complicated shape can be efficiently manufactured with sufficient dimensional accuracy. Moreover, it can respond suitably also to manufacture of the multiple types of molded article from which shape and magnitude | size differ.

In particular, in the three-dimensional modeling method, the stability of the shape of the layer can be further improved by forming the layer using the above-described cellulose-based material of the present invention. Moreover, when the composition containing the anionic compound (second composition) is applied, the composition can be quickly absorbed, and the unintentional wetting and spreading of the composition can be effectively prevented. be able to.
As a result, the dimensional accuracy of the finally obtained shaped article can be further improved. In addition, the amount of volatile components as constituent components of the material used for manufacturing the modeled object can be reduced as a whole, the productivity of the modeled object can be further improved, and resource saving and environment can be reduced. It is also preferable from the viewpoint of low load.

Hereinafter, a specific example of a manufacturing method of a model when a three-dimensional modeling method is applied will be described.
1 and 2 are cross-sectional views schematically showing each step in a preferred embodiment of the method for manufacturing a shaped article of the present invention.

As shown in FIG. 1 and FIG. 2, the manufacturing method of the present embodiment uses a particle-containing composition (first composition) P1 ′ containing the cellulosic material of the present invention as particles, and a side support (frame). Liquid) containing an anionic compound having a valence of 2 or more with respect to the layer P1 by the layer formation step (1a, 1d) for forming the layer P1 having a predetermined thickness in the region surrounded by the body 45 and the ink jet method. Composition(
2nd composition) The liquid composition provision process (1b, 1) which provides P12 and forms the coupling | bond part P13.
c, 1e, 1f), and sequentially repeating these steps (1g), and then, among the particles constituting each layer P1, those not bound by a binder (anionic compound, etc.) The unbonded particle removing step (1h) is removed.

Hereinafter, each step will be described.
<Layer formation process>
In the layer formation step, a layer P1 having a predetermined thickness is formed using a particle-containing composition (first composition) P1 ′ containing particles composed of a cellulosic material (1a, 1d).

Thus, by using the first composition P1 ′ containing the cellulose-based material as particles, the dimensional accuracy of the finally obtained shaped article (three-dimensional shaped article) P10 can be improved. Moreover, the heat resistance, mechanical strength, etc. of the molded article P10 can be made more excellent.

The particle-containing composition (first composition) P1 ′ will be described in detail later.
In this step, the layer P1 is formed with a flattened surface using a flattening means.

In the first layer formation step, the layer P1 is formed on the surface of the stage 41 with a predetermined thickness (1a).
). At this time, the side surface of the stage 41 and the side surface support portion 45 are in close contact (contact), and the first composition P1 ′ may fall from between the stage 41 and the side surface support portion 45. It is prevented.

In the second and subsequent layer formation steps, a new layer P1 (second layer) is formed on the surface of the layer P1 (first layer) formed in the previous step (1d). At this time, the side surface of the layer P1 of the stage 41 (at least the uppermost layer P1 when there are a plurality of layers P1 on the stage 41) and the side surface support portion 45 are in close contact (contact). Stage 41 and stage 41
The first composition P1 ′ is prevented from falling from between the upper layer P1.

In this step, the first composition P1 ′ may be heated. Thus, for example, the first
In the case where the composition P1 ′ includes a molten component, the first composition P1 ′ can be more preferably pasty.

The viscosity of the first composition P1 ′ in this step is 500 mPa · s or more and 1000000 m.
It is preferably Pa · s or less. Thereby, generation | occurrence | production of the unintentional dispersion | variation in the film thickness in the layer P1 formed can be prevented more effectively.

In this specification, the viscosity is an E-type viscometer (for example, VISC manufactured by Tokyo Keiki Co., Ltd.).
The value measured at 25 ° C. using ONIC ELD).

The thickness of the layer P1 formed in this step is not particularly limited, but is, for example, 20 μm or more and 500
It is preferably not more than μm, more preferably not less than 30 μm and not more than 150 μm. Thereby, while making productivity of modeling thing P10 sufficiently excellent, modeling thing P10 manufactured
It is possible to more effectively prevent the occurrence of unintentional irregularities and the like, and to improve the dimensional accuracy of the shaped article P10.

<Liquid composition application process (binding liquid application process)>
After forming the layer P1 in the layer forming step, a liquid composition (second composition) P12 containing a divalent or higher anionic compound is applied as a binding liquid to the layer P1 by an ink jet method (1b). 1e).

Since the anionic compound contained in the second composition P12 forms a suitable ionic bond with the cellulose derivative (cellulose derivative having an amine structure in the molecule) constituting the layer P1, In the part to which the second composition P12 is applied in the layer P1,
A cellulose derivative and an anionic compound couple | bond together and the coupling | bond part P13 is formed. This coupling | bond part P13 comprises a solid part in the molded article P10.
The liquid composition (second composition) P12 will be described in detail later.

In this step, the liquid composition P12 is selectively applied only to a portion of the layer P1 corresponding to the real part (substantial portion) of the shaped article P10 to be manufactured.

Thereby, the cellulose derivative which comprises the layer P1, and the anionic compound which comprises the liquid composition P12 couple | bond together, and can form the coupling | bond part (substance part) P13 of a desired shape.

In this step, since the liquid composition P12 is applied by the ink jet method, the liquid composition P
Even if the application pattern of 12 has a finer shape, the liquid composition P has higher reproducibility.
12 can be given. As a result, the dimensional accuracy of the shaped article P10 finally obtained can be made higher.

In addition, when the anionic compound contained in the second composition P12 comes into contact with a cellulose derivative having an amine structure in the molecule, it forms an ionic bond as described above in a short time (1
c, 1f). For this reason, when the 2nd composition P12 is provided to the layer P1, the coupling | bond part P13 excellent in shape stability will be formed rapidly. Therefore, the productivity of the shaped article P10 can be made excellent, and the dimensional accuracy of the finally obtained shaped article P10 can be made excellent.

As described above, by providing the second composition P12, the coupling portion P1 can be easily and reliably performed.
3 may be formed, but other treatments may be performed, for example, in order to make the coupling force of the coupling part P13 (strength of the shaped article P10 finally obtained, etc.) and the like better. For example,
When the cellulose derivative has a reactive functional group, or when the second composition P12 ′ contains a curable resin, a treatment for advancing these chemical reactions may be performed. When performing such a chemical reaction (for example, a reaction that forms a covalent bond), the chemical reaction can be performed by, for example, heating or energy rays (for example, light rays such as ultraviolet rays, electron beams, positron beams, neutron beams, α rays). , Ion beam, etc.).

In particular, when the chemical reaction proceeds by heating, the configuration of the manufacturing apparatus for the shaped article P10 can be simplified. Moreover, even if the raw material of the shaped object P10 is a material with low light transmittance,
The target reaction can be suitably advanced.

When the chemical reaction proceeds by heating, the heating temperature is preferably 50 ° C. or higher and 180 ° C. or lower, and more preferably 60 ° C. or higher and 150 ° C. or lower.

Moreover, when a chemical reaction is advanced by light irradiation, the productivity of the shaped article P10 can be further improved while more effectively preventing unintentional modification / deterioration of the material.

When the chemical reaction proceeds by irradiation with light, as the light, for example, ultraviolet rays, infrared rays, visible rays, X-rays, microwaves, radio waves and the like can be used, but ultraviolet rays are preferable.

Thereby, while being able to make the productivity of the molded article P10 more excellent, complication of the structure of the manufacturing apparatus of the molded article P10 can be prevented, and the production cost of the molded article P10 can be suppressed.

When the chemical reaction is advanced by irradiation with ultraviolet rays, the peak wavelength of ultraviolet rays is 250
It is preferable that it is not less than nm and not more than 400 nm. Moreover, it is preferable that the irradiation time of the ultraviolet rays to each part where the chemical reaction should proceed is 30 seconds or more and 60 seconds or less.

For example, when the liquid composition P12 contains a volatile component (volatile solvent),
In this step, heat treatment or pressure reduction treatment for volatilizing volatile components can be performed.

<Unbound particle removal step>
And after performing repeatedly the above processes, as a post-processing process, the particle | grains which are not couple | bonded by the liquid composition P12 (anionic compound) among the particles which comprise each layer P1 (unbonded particle) are removed. An unbound particle removal step (1h) is performed. Thereby, the molded article P10 is taken out.

As a specific method of this step, for example, a method of removing unbound particles with a brush, a method of removing unbound particles by suction, a method of blowing a gas such as air, a method of applying a liquid such as water ( Examples thereof include a method of immersing the laminate obtained as described above in a liquid, a method of spraying a liquid, and a method of applying vibration such as ultrasonic vibration. Moreover, it can carry out combining 2 or more types of methods selected from these. More specifically, there are a method of immersing in a liquid such as water after blowing a gas such as air, a method of applying ultrasonic vibration in a state of immersing in a liquid such as water, and the like. Especially, it is preferable to employ | adopt the method (especially the method of immersing in the liquid containing water) which provides the liquid containing water with respect to the laminated body obtained as mentioned above.

<Modeling equipment>
Next, a manufacturing apparatus (modeled object manufacturing apparatus) that can be used for manufacturing a modeled object (three-dimensional modeled object) of the present invention will be described.

FIG. 3 is a cross-sectional view schematically showing a preferred embodiment of a manufacturing apparatus used for manufacturing a shaped article of the present invention.

The shaped article manufacturing apparatus 100 shown in FIG. 3 is shaped by repeatedly forming and laminating the layer P1 using the particle-containing composition (first composition) P1 ′ containing the cellulose-based material of the present invention as particles. The product P10 is manufactured.

As shown in FIG. 3, the molded article manufacturing apparatus 100 includes a control unit 2, a composition supply unit (particle-containing composition supply unit) 3 that supplies a particle-containing composition (first composition) P <b> 1 ′, A layer forming unit 4 that forms the layer P1 using the particle-containing composition (first composition) P1 ′ supplied from the composition supply unit 3, and a liquid composition (second composition) P12 in the layer P1. A liquid composition discharging unit (liquid composition applying unit) 5 for discharging the energy, and an energy beam irradiating unit 6 for irradiating an energy beam for advancing a chemical reaction for bonding a covalent bond.

The control unit 2 includes a computer 21 and a drive control unit 22.
The computer 21 is a general desktop computer configured with a CPU, a memory, and the like inside. The computer 21 converts the shape of the modeled object (three-dimensional modeled object) P10 into model data, and slices the modeled data into a plurality of parallel thin cross-sections (slice data) to the drive control unit 22. Output.

The drive control unit 22 functions as a control unit that drives the layer forming unit 4, the liquid composition discharge unit 5, and the energy beam irradiation unit 6. Specifically, for example, the discharge pattern and discharge amount of the liquid composition P12 by the liquid composition discharge unit 5, and the particle-containing composition P1 from the composition supply unit 3
The supply amount of ', the lowering amount of the stage 41, and the like are controlled.

The composition supply unit 3 is moved by a command from the drive control unit 22, and the particle-containing composition P <b> 1 ′ accommodated therein is supplied to the composition temporary placement unit (particle-containing composition temporary placement unit) 44. It is configured as follows.

The layer forming unit 4 includes a composition temporary placement unit 44 that temporarily holds the particle-containing composition P1 ′ supplied from the composition supply unit 3, and a particle-containing composition P1 that is held in the composition temporary placement unit 44. Squeegee (flattening means) 42 that forms the layer P1 while flattening, a guide rail 43 that regulates the operation of the squeegee 42, a stage 41 that supports the formed layer P1, and a side support that surrounds the stage 41 (Frame body) 45.

When forming a new layer P 1 on the previously formed layer P 1, the previously formed layer P 1 is moved downward relative to the side support portion 45. This defines the thickness of the newly formed layer P1.

In particular, in this embodiment, the stage 41 has a new layer P1 on the previously formed layer P1.
Is formed, it is lowered by a predetermined amount sequentially according to a command from the drive control unit 22. As described above, since the stage 41 is configured to be movable in the Z direction (vertical direction), when forming a new layer P1, the number of members to be moved to adjust the thickness of the layer P1 is reduced. Therefore, the configuration of the molded article manufacturing apparatus 100 can be made simpler.

The stage 41 has a flat surface (part to which the particle-containing composition P1 ′ is applied).

Thereby, the layer P1 with high uniformity of thickness can be formed easily and reliably. Moreover, in the manufactured molded article P10, it is possible to effectively prevent unintentional deformation or the like from occurring.

The stage 41 is preferably composed of a high-strength material. Examples of the constituent material of the stage 41 include various metal materials such as stainless steel.

Further, the surface of the stage 41 (part to which the particle-containing composition P1 ′ is applied) may be subjected to surface treatment. Thereby, for example, more effectively preventing the constituent material of the particle-containing composition P1 ′ and the constituent material of the liquid composition P12 from adhering to the stage 41,
The durability of the stage 41 can be made more excellent, and the shaped product P10 can be produced stably over a longer period of time. Examples of the material used for the surface treatment of the surface of the stage 41 include fluorine-based resins such as polytetrafluoroethylene.

The squeegee 42 has a longitudinal shape extending in the Y direction, and includes a blade having a blade-like shape with a pointed lower end.

The length of the blade in the Y direction is greater than or equal to the width of the stage 41 (modeling region) (the length in the Y direction).

The model manufacturing apparatus 100 may include a vibration mechanism (not shown) that applies minute vibrations to the blade so that the squeegee 42 can smoothly diffuse the particle-containing composition P1 ′.

The side surface support portion 45 has a function of supporting the side surface of the layer P1 formed on the stage 41. In addition, when the layer P1 is formed, it also has a function of defining the area of the layer P1.

Moreover, surface treatment may be performed on the surface of the side surface support portion 45 (site that can come into contact with the particle-containing composition P1 ′). Thereby, for example, the constituent material of the particle-containing composition P1 ′ and the constituent material of the liquid composition P12 can be more effectively prevented from adhering to the side surface support portion 45, or the durability of the side surface support portion 45 can be improved. It can be made more excellent and stable production of the shaped article P10 over a longer period can be achieved. Further, the previously formed layer P1 is attached to the side support portion 4.
When moving downward relative to 5, unintentional disturbance can be effectively prevented from occurring in the layer P1. As a result, the dimensional accuracy and reliability of the finally obtained shaped article P10 can be further improved. As a material used for the surface treatment of the surface of the side support part 45, for example, a fluorine-based resin such as polytetrafluoroethylene can be cited.

The liquid composition application unit (liquid composition discharge unit) 5 applies the liquid composition P12 to the layer P1.

By providing such a liquid composition provision means 5, the mechanical strength of the molded article P10 can be easily and reliably improved.

In particular, in the present embodiment, the liquid composition application unit 5 is a liquid composition discharge unit that discharges the liquid composition P12 by an inkjet method.

Thereby, the liquid composition P12 can be applied in a fine pattern, and even the shaped article P10 having a fine structure can be manufactured with higher productivity.

Examples of the droplet discharge method (inkjet method) include a piezo method and a liquid composition P12.
A method of discharging the liquid composition P12 by bubbles generated by heating the liquid can be used, but the piezo method is preferable from the viewpoint of difficulty in altering the components of the liquid composition P12.

The liquid composition discharge unit (liquid composition application unit) 5 controls the pattern to be formed in each layer P1 and the amount of the liquid composition P12 applied in each part of the layer P1 according to a command from the drive control unit 22. . Liquid composition P1 by the liquid composition discharge part (liquid composition applying means) 5
The second ejection pattern, the ejection amount, and the like are determined based on slice data.

The energy ray irradiating means 6 irradiates the layer P1 to which the liquid composition P12 has been applied with an energy ray to advance a chemical reaction that bonds a covalent bond.

In particular, in the configuration shown in the figure, energy beam irradiation means 6 are provided before and after the liquid composition discharge section (liquid composition application means) 5 in the scanning direction (main scanning direction).

Thereby, since the joining formation by the energy beam irradiation means 6 can be performed in both the outward path and the return path, the productivity of the shaped article P10 can be further improved.

In addition, when it is not necessary to advance the above-described chemical reaction (for example, when the cellulose derivative does not have the above-described reactive functional group, the second composition P12 ′ does not include a curable resin, etc.). The energy beam irradiation means 6 may not be provided.

<< Composition set for molding production >>
Next, the composition set for manufacturing a shaped article of the present invention will be described.

The composition set for manufacturing a shaped article of the present invention is a first containing the cellulose-based material of the present invention described above.
And a second composition containing a divalent or higher anionic compound.

Such a composition set for manufacturing a modeled article can be suitably used for manufacturing a modeled article having high strength, a self-repairing function, and excellent reliability and durability.

Hereinafter, the particle-containing composition P1 ′ and the liquid composition (ink) P12 used in the method for manufacturing a modeled object and the modeled product manufacturing apparatus according to the above-described embodiments are provided as the first composition and the second composition, respectively. The composition set for manufacturing a molded article will be mainly described.

[First composition]
<Cellulosic material>
The first composition contains at least the cellulosic material of the present invention (containing a cellulose derivative having an amine structure in the molecule).

In the first composition, the cellulose derivative having an amine structure in the molecule is preferably a solid.

Thereby, the strength and dimensional accuracy of the finally obtained shaped article can be further improved. In addition, the productivity of the modeled product can be further improved.

In particular, the first composition preferably includes, as a cellulosic material, particles having at least a region including the surface composed of the cellulose derivative (cellulose derivative having an amine structure in the molecule).

Thereby, the mechanical strength etc. of the molded article manufactured can be made more excellent.
Moreover, when manufacturing a modeling thing using the method (three-dimensional modeling method) which is explained in full detail later, a 2nd composition can be suitably osmose | permeated in the clearance gap between particle | grains, and modeling with high dimensional accuracy. Things can be manufactured more efficiently.

In this case, the average particle diameter of the particles is not particularly limited, but is preferably 1 μm or more and 25 μm or less, and more preferably 1 μm or more and 15 μm or less.

Thereby, while being able to make the mechanical strength of a molded article more excellent, generation | occurrence | production of the unintentional unevenness in a manufactured molded article is prevented more effectively, and the dimensional accuracy of a molded article is more excellent. Can be. Moreover, moderate softness | flexibility can be provided to the molded article manufactured, for example, it can apply more suitably to medical devices, such as an artificial blood vessel and the member for dialysis which are mentioned later. Moreover, the fluidity | liquidity of the powder containing several said particle | grains and the fluidity | liquidity of the 1st composition containing the said powder can be made more excellent, and the productivity of a molded article can be made more excellent.

In the present specification, the average particle diameter means a volume-based average particle diameter. For example, a dispersion obtained by adding a sample to methanol and dispersing for 3 minutes with an ultrasonic disperser is a Coulter counter particle size distribution measuring instrument. (TA-II type manufactured by COULTER ELECTRONICS INS)
Thus, it can be obtained by measuring using a 50 μm aperture.

The Dmax of the particles is preferably 3 μm or more and 40 μm or less, and 5 μm or more and 30 μm or less.
More preferably, it is not more than μm. Thereby, while being able to make the mechanical strength of a molded article more excellent, generation | occurrence | production of the unintentional unevenness in a manufactured molded article is prevented more effectively, and the dimensional accuracy of a molded article is more excellent. Can be. Moreover, the fluidity | liquidity of the powder containing several said particle | grains and the fluidity | liquidity of the 1st composition containing the said powder can be made more excellent, and the productivity of a molded article can be made more excellent.

The particles may have any shape, but preferably have a spherical shape. As a result, the fluidity of the powder containing a plurality of the particles and the fluidity of the first composition containing the powder can be improved, and the productivity of the molded product can be improved. , More effectively prevent the occurrence of unintentional irregularities in the manufactured objects,
The dimensional accuracy of a model can be made more excellent.

The first composition may include a plurality of cellulose derivatives having an amine structure in the molecule.

When the first composition (particle-containing composition) contains a particulate cellulose material,
The content of the cellulosic material in the first composition (particle-containing composition) is preferably 8% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 75% by mass or less. Thereby, the mechanical strength of the finally obtained shaped article can be further improved while the fluidity of the first composition (particle-containing composition) is sufficiently excellent.

<Other ingredients>
In addition, the first composition may include components (other components) other than the cellulose-based material described above. Examples of such components include particles composed of materials other than cellulosic materials; liquid media that function as solvents or dispersion media; binders; polymerization initiators;
Polymerization accelerator; Cross-linking agent; Siloxane compound; Penetration accelerator; Wetting agent (moisturizing agent); Fixing agent; Antifungal agent; Preservative; Antioxidant; Various colorants; various fluorescent materials; various phosphorescent materials; various phosphorescent materials; infrared absorbing materials; dispersants; surfactants; thickeners; fillers;

Hereinafter, some of the other components constituting the first composition will be described more specifically.

(Particles made of materials other than cellulosic materials)
In the case of including particles composed of a material other than the cellulosic material, various inorganic materials, various organic materials, and composite materials thereof can be used as the particles.

As an inorganic material which comprises the said particle | grain (particle | grains comprised with materials other than a cellulosic material), various metals, a metal compound, etc. are mentioned, for example. Examples of the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide, and potassium titanate; various kinds such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide. Metal hydroxides; various metal nitrides such as silicon nitride, titanium nitride and aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; various metals such as calcium carbonate and magnesium carbonate Carbonates; sulfates of various metals such as calcium sulfate and magnesium sulfate; silicates of various metals such as calcium silicate and magnesium silicate; phosphates of various metals such as calcium phosphate; aluminum borate, magnesium borate, etc. And various metal borates and composites thereof.

Examples of the organic material constituting the particles (particles made of a material other than the cellulosic material) include synthetic resins and natural polymers, and more specifically, polyethylene resins;
Polypropylene; Polyethylene oxide; Polypropylene oxide, Polyethyleneimine; Polystyrene; Polyurethane; Polyurea; Polyester; Silicone resin; Acrylic silicone resin; Polymer containing (meth) acrylic acid ester such as polymethyl methacrylate; Methyl methacrylate cloth Cross polymer (ethylene acrylic acid copolymer resin, etc.) containing (meth) acrylic acid ester such as polymer as constituent monomer; Polyamide resin such as nylon 12, nylon 6, copolymer nylon, etc .; Polyimide; Gelatin; Starch; Chitin; Is mentioned.
The particles may be subjected to a surface treatment such as a hydrophobic treatment or a hydrophilic treatment.

(Liquid medium)
The liquid medium has a function of dissolving or dispersing the cellulosic material in the first composition.

By including such a liquid medium, for example, the fluidity of the first composition can be further improved. In addition, for example, when the first composition contains a cellulosic material as a particulate material, the first composition can be made into a paste-like material, and the productivity of the shaped article is more excellent It can be.

When the first composition contains a binder described later, the liquid medium preferably dissolves the binder. Thereby, the fluidity | liquidity of a 1st composition can be made more favorable, for example, when manufacturing a molded article using the method as mentioned above, it forms using a 1st composition. Unintentional variations in the thickness of the layer can be more effectively prevented. In addition, when a layer with the liquid medium removed is formed, the binder can be adhered to the particles with higher uniformity throughout the layer, and it is more effective that unintentional composition unevenness occurs. Can be prevented. For this reason, generation | occurrence | production of the unintentional dispersion | variation in mechanical strength in each site | part of the molded article finally obtained can be prevented more effectively, and the reliability of a molded article can be made higher. .

Examples of the liquid medium constituting the first composition include water; alcohol solvents such as methanol, ethanol and isopropanol; ketone solvents such as methyl ethyl ketone and acetone; glycols such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether. Ether solvents; glycol ether acetate solvents such as propylene glycol 1-monomethyl ether 2-acetate, propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, polypropylene glycol and the like, and one or more selected from these Two or more kinds can be used in combination.

Among these, the first composition preferably contains an aqueous solvent as a liquid medium, and more preferably contains water.

Thereby, the fluidity | liquidity of a 1st composition and the uniformity of the composition of the layer formed using a 1st composition can be made more excellent. Moreover, water is easy to remove after the formation of the layer, and even when it remains in the modeled object, it is difficult to adversely affect the water. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems. In addition, when the first composition contains a water-soluble resin as a binder to be described in detail later, the water-soluble resin can be more suitably dissolved in the first composition, and will be described in detail later. The effect by including a suitable binder (water-soluble resin) is more effectively exhibited.

The aqueous solvent may be a solvent having high solubility in water, and specifically, for example, 25
Solubility in water at 30 ° C. (mass soluble in 100 g of water) is 30 [g / 100 g water]
It is preferable that it is the above, and it is more preferable that it is 50 [g / 100g water] or more.

When the first composition contains a liquid medium, the content of the liquid medium in the first composition is preferably 5% by mass or more and 92% by mass or less, and 25% by mass or more and 89% by mass or less. More preferably.

As a result, the effects of including the liquid medium as described above are more remarkably exhibited, and the liquid medium can be easily removed in a short time in the manufacturing process of the modeled object, so that the productivity of the modeled object is improved. From the viewpoint of

In particular, when the first composition contains water as a liquid medium, the content of water in the first composition is preferably 18% by mass or more and 92% by mass or less, and 47% by mass or more and 9% by mass.
It is more preferably 0% by mass or less.
Thereby, the effects as described above are more remarkably exhibited.

When the first composition contains a liquid medium, in the case of producing a shaped article using the method as described above, the liquid medium is removed from the layer before application of the second composition. It is preferable.

Thereby, the stability of the shape of the layer is improved, and even if the liquid medium has a low affinity with the constituent material of the second composition, the involuntary repelling of the second composition in the layer. Etc. can be more effectively prevented, and the second composition can be applied in a desired pattern more easily and reliably.

When the liquid medium constituting the first composition is removed from the layer before application of the second composition, the liquid medium may be completely removed from the layer, Only a part may be removed. Even in such a case, the effects described above are exhibited.

(binder)
The first composition may include a binder.

Thereby, in the case of manufacturing a shaped article using the method as described above, a plurality of particles are formed in the layer formed using the first composition (particularly, the layer from which the liquid medium has been removed). Can be suitably bonded (temporarily fixed), and unintentional scattering of particles can be effectively prevented. Thereby, the further improvement of a worker's safety and the dimensional accuracy of the molded article manufactured can be aimed at.

When the first composition contains a binder, the binder is preferably dissolved in the liquid medium in the first composition.

Thereby, the fluidity of the first composition can be made better, and the unintentional variation in the thickness of the layer formed using the first composition can be more effectively prevented. Can do.
In addition, when a layer with the liquid medium removed is formed, the binder can be adhered to the particles with higher uniformity throughout the layer, and it is more effective that unintentional composition unevenness occurs. Can be prevented. For this reason, generation | occurrence | production of the unintentional dispersion | variation in mechanical strength in each site | part of the molded article finally obtained can be prevented more effectively, and the reliability of a molded article can be made higher. .

As the binder, any binder may be used as long as it has a function of temporarily fixing a plurality of particles in a layer formed using the first composition (particularly, the layer P1 from which the liquid medium has been removed).
A water-soluble resin can be suitably used.

By including a water-soluble resin, when the first composition contains an aqueous solvent (particularly water) as a liquid medium, a binder (water-soluble resin) may be included in a dissolved state in the first composition. In addition, the fluidity and handleability (ease of handling) of the first composition can be further improved. As a result, the productivity of the shaped product can be made more excellent.

Moreover, when manufacturing a modeling thing using the method as mentioned above, the site | part which the 2nd composition of the layer was not provided is easily and efficiently provided with an aqueous solvent (especially water). Can be removed. As a result, the productivity of the shaped product can be made more excellent. In addition, it is possible to easily and reliably prevent the portion of the layer to be removed from adhering to and remaining on the finally obtained shaped object, and therefore, the dimensional accuracy of the shaped object should be improved. Can do.

Hereinafter, the water-soluble resin as the binder will be mainly described.
The water-soluble resin may be any resin that is at least partially soluble in an aqueous solvent.
The solubility in water (mass that can be dissolved in 100 g of water) at 25 ° C. is preferably 5 [g / 100 g water] or more, and more preferably 10 [g / 100 g water] or more.

Examples of water-soluble resins include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polycaprolactone diol, sodium polyacrylate, polyacrylamide, modified polyamide, polyethyleneimine, polyethylene oxide, and a random co-polymer of ethylene oxide and propylene oxide. Examples include synthetic polymers such as polymerized polymers, natural polymers such as corn starch, mannan, pectin, agar, alginic acid, dextran, glue, gelatin, semisynthetic polymers such as starch, oxidized starch, and modified starch, and the like. Species or a combination of two or more can be used.

Specific examples of water-soluble resin products include, for example, starch phosphate sodium sodium (I) (
Matsutani Chemical Co., Hoster 5100), Polyvinylpyrrolidone (Tokyo Chemical Co., PVP)
K-90), methyl vinyl ether / maleic anhydride copolymer (GAF Gauntlet, AN-139), polyacrylamide (Wako Pure Chemical Industries), modified polyamide (modified nylon) (Toray, AQ nylon), polyethylene Oxide (manufactured by Steel Manufacturing Chemical Co., PEO
-1, Meisei Chemical Industry Co., Ltd., Alcox), random copolymer of ethylene oxide and propylene oxide (Meisei Chemical Industry Co., Ltd., Alcox EP), sodium polyacrylate (Wako Pure Chemical Industries, Ltd.), carboxyvinyl Polymer / crosslinked acrylic water-soluble resin (manufactured by Sumitomo Seika Co., Ltd., Apekk) and the like.

Especially, when the water-soluble resin as a binder is polyvinyl alcohol, the mechanical strength of a molded article can be made more excellent. Also, by adjusting the degree of saponification and degree of polymerization, the characteristics of the binder (for example, water solubility, water resistance, etc.) and the characteristics of the first composition (for example, viscosity, particle fixing force, wettability, etc.) are more suitable. Can be controlled. For this reason, it can respond suitably by manufacture of various shaped objects. Polyvinyl alcohol is inexpensive and stable in supply among various water-soluble resins. For this reason, it is possible to manufacture a stable shaped article while suppressing the production cost.

When the water-soluble resin as the binder contains polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is preferably 85 or more and 90 or less. This
A decrease in the solubility of polyvinyl alcohol in an aqueous solvent (in particular, water) can be suppressed. Therefore, for example, in the case of manufacturing a shaped article using the method as described above,
When the first composition contains an aqueous solvent (particularly water), it is possible to more effectively suppress a decrease in adhesiveness between adjacent layers.

When the water-soluble resin as a binder contains polyvinyl alcohol, the polymerization degree of the polyvinyl alcohol is preferably 300 or more and 1000 or less. Thereby, when the 1st composition contains an aqueous solvent (especially water), the mechanical strength of each layer and the adhesiveness between adjacent layers can be made more excellent.

Moreover, when the water-soluble resin as a binder is polyvinylpyrrolidone (PVP),
The following effects are obtained. That is, in the case of manufacturing a modeled object using the method as described above, it is possible to improve the strength and shape stability of the portion of the layer to which the second composition is not applied, and finally obtain a modeled product. The dimensional accuracy of the object can be further improved. In addition, since polyvinylpyrrolidone exhibits high solubility in water, it is bound by the first composition (anionic compound or the like) among the particles constituting each layer in the unbound particle removal step (after the completion of modeling). What is not done can be removed easily and reliably. In addition, since polyvinylpyrrolidone has an appropriate affinity for the cellulose-based material as described above, the wettability with respect to the surface of the particles composed of the cellulose-based material is relatively high. For this reason, the temporary fixing function as described above can be more effectively exhibited. Moreover, since polyvinylpyrrolidone is excellent in affinity with various colorants, it is colored when the second composition containing the colorant is used in the liquid composition application step (second composition application step). It is possible to effectively prevent the agent from unintentionally diffusing. Further, when the paste-like first composition contains polyvinylpyrrolidone, it is possible to effectively prevent bubbles from being involved in the first composition, and in the layer forming step, the bubbles are involved. It is possible to effectively prevent the occurrence of defects due to.

When the water-soluble resin as the binder contains polyvinyl pyrrolidone, the polyvinyl pyrrolidone preferably has a weight average molecular weight of 10,000 to 170,000, and more preferably 30,000 to 1500,000.
Thereby, the function mentioned above can be exhibited more effectively.

In addition, when the water-soluble resin is polycaprolactone diol, the first composition can be suitably pelletized, and can more effectively prevent unintentional scattering of particles,
The handleability (ease of handling) of the first composition is improved, and it is possible to improve the safety of the worker and the dimensional accuracy of the molded article to be manufactured, and to melt at a relatively low temperature. Therefore, the energy and cost required for the production of the modeled object can be suppressed, and the productivity of the modeled object can be made sufficiently excellent.

When the water-soluble resin as a binder contains polycaprolactone diol,
The weight average molecular weight of the polycaprolactone diol is preferably 10,000 or more and 170,000 or less, and more preferably 30,000 or more and 1500,000 or less.
Thereby, the function mentioned above can be exhibited more effectively.

In the first composition, the binder is in a liquid state (for example, in the layer forming step).
It is preferable that it is in a dissolved state, a molten state, or the like.

Thereby, the uniformity of the thickness of the layer formed using the first composition can be easily and reliably obtained.
Can be higher.

When the first composition contains a binder, the binder content in the first composition is preferably 0.5% by mass or more and 25% by mass or less, and 1.0% by mass or more and 1% by mass.
It is more preferably 0% by mass or less.

Thereby, while the effect by including a binder as mentioned above is exhibited more notably, content rate of particles etc. in the 1st composition can be made sufficiently high,
The mechanical strength etc. of the manufactured molded article can be made more excellent. For example, you may use the multiple types of 1st composition from which the kind and content rate of a cellulose derivative differ.
For example, a plurality of types of first compositions may be used for manufacturing the modeled object.

[Second composition]
<Anionic compound>
The anionic compound has only to have a valence of 2 or more (the number of anionic atoms in the molecule is 2 or more), but preferably has a valence of 3 or more.

Thereby, in a molded article, an ionic bond between a cellulose derivative and an anionic compound can be formed more suitably, and the strength of the molded article can be improved, and a self-repair function Can be made more excellent, and the durability and reliability of the molded article can be made more excellent.

Examples of the anionic functional group that the anionic compound has include a carboxyl group, a phosphate group, a sulfo group (sulfonic acid group), and a phenolic hydroxyl group.
Among these, a carboxyl group and a phosphate group are preferable, and a phosphate group is more preferable.

Thereby, in a molded article, an ionic bond between a cellulose derivative and an anionic compound can be formed more suitably, and the strength of the molded article can be improved, and a self-repair function Can be made more excellent, and the durability and reliability of the molded article can be made more excellent. Moreover, many phosphate groups are contained in the living body and have high safety. Therefore, the safety of the modeled object, the biocompatibility, and the like can be further improved. For example, the modeled object can be suitably applied to a medical device or the like.

Further, the second composition may contain polyphosphoric acid as an anionic compound.

Thereby, in a molded article, an ionic bond between a cellulose derivative and an anionic compound can be more suitably formed, and the strength of the molded article can be further improved, and a self-repair function The durability and reliability of the molded article can be further improved. In addition, the polyphosphate structure is abundant in the living body and has high safety. Therefore, the safety of the modeled object, the biocompatibility, and the like can be further improved. For example, the modeled object can be more suitably applied to a medical device or the like.

Examples of the polyphosphoric acid structure include those represented by the following formula (8) and the following formula (9).

  The second composition may include a plurality of divalent or higher anionic compounds.

<Other ingredients>
In addition, the second composition may contain components (other components) other than the anionic compounds described above. Examples of such components include solvents, penetration enhancers, wetting agents (humectants), fixing agents, antifungal agents, antiseptics, antioxidants, various colorants such as pigments and dyes, various fluorescent materials, and various types. Phosphorescent materials; Various phosphorescent materials; Infrared absorbing materials; Dispersants; Curable resins (polymerizable compounds); Polymerization initiators; Polymerization accelerators; Crosslinking agents; Siloxane compounds;
A pH adjuster; a surfactant; a thickener; a filler; an aggregation inhibitor; an antifoaming agent, and the like.

Hereinafter, some of the other components constituting the second composition will be described more specifically.

The content of the divalent or higher anionic compound in the second composition is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more and 95% by mass or less, 30 More preferably, it is at least 90% by mass.

(solvent)
When the second composition contains a solvent, the anionic compound can be ionized,
When it comes into contact with the cellulose derivative, it is possible to form an ionic bond with the cellulose derivative more rapidly, and to improve the productivity of the shaped article.

As the solvent, a polar solvent is preferably used. For example, dimethyl sulfoxide (DM
SO), acetonitrile, methylformamide, dimethylformamide, ethyl acetate, acetone, tetrahydrofuran and other aprotic solvents, distilled water, RO water, ion-exchanged water, pure water, tap water, etc., methanol, ethanol, propanol, butanol And protic solvents such as alcohols such as ethylene glycol, glycerin and alkoxyethanol, and carboxylic acids such as formic acid, acetic acid and propionic acid.
Of these, water is preferred.

(Coloring agent)
Moreover, when the 2nd composition contains a coloring agent, the molded article colored in the color corresponding to the color of a coloring agent can be obtained suitably.

In particular, by including a pigment as a colorant, the light resistance of the second composition and the shaped article can be improved. As the pigment, either an inorganic pigment or an organic pigment can be used.

Examples of the inorganic pigment include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, titanium oxide, and the like, and one kind selected from these. Alternatively, two or more kinds can be used in combination.
Among the inorganic pigments, titanium oxide is preferable in order to exhibit a preferable white color.

Examples of the organic pigment include insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, etc. 1 type or 2 types or more selected from these can be used in combination.

More specifically, as carbon black used as a black (black) pigment, for example, No. 2300, no. 900, MCF88, No. 33, no. 40, No
. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. (Mitsubishi Chemical Corporation), Ra
ven 5750, Raven 5250, Raven 5000, Raven 350
0, Raven 1255, Raven 700, etc. (above, Columbia Carbon (Car
Bon Columbia)), Rega1 400R, Rega1 330R, R
ega1 660R, Mogul L, Monarch 700, Monarch 80
0, Monarch 880, Monarch 900, Monarch 1000, M
onarch 1100, Monarch 1300, Monarch 1400, etc. (above, manufactured by CABOT JAPAN KK), Color Black
FW1, Color Black FW2, Color Black FW2V, Co
lor Black FW18, Color Black FW200, Color B
1ack S150, Color Black S160, Color Black S
170, Printex 35, Printex U, Printex V, Print
ex 140U, Special Black 6, Special Black 5,
Special Black 4A, Special Black 4 (manufactured by Degussa) and the like.

Examples of white pigments include C.I. I. Pigment White 6, 18,
21 etc. are mentioned.

Examples of yellow (yellow) pigments include C.I. I. Pigment Yellow 1, 2, 3
4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 3
7, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98
99, 108, 109, 110, 113, 114, 117, 120, 124, 128,
129, 133, 138, 139, 147, 151, 153, 154, 167, 172,
180 etc. are mentioned.

Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3
4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19,
21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca),
48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 14
4, 146, 149, 150, 166, 168, 170, 171, 175, 176, 17
7, 178, 179, 184, 185, 187, 202, 209, 219, 224, 24
5, or C.I. I. Pigment Violet 19, 23, 32, 33, 36, 38,
43, 50, etc.

Examples of the violet (cyan) pigment include C.I. I. Pigment Blue 1, 2, 3,
15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25
, 60, 65, 66, C.I. I. Bat Blue 4, 60 and the like.

Examples of other pigments include C.I. I. Pigment Green 7, 10, C
. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment Orange 1, 2
5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

When the second composition contains a pigment, the average particle size of the pigment is preferably 300 nm or less, and more preferably 50 nm or more and 250 nm or less. This
For example, the color developability of the pigment can be improved. In addition, the dispersion stability of the pigment in the second composition and the ejection stability of the second composition can be improved, and an image with better image quality can be formed.

Examples of the dye include acid dyes, direct dyes, reactive dyes, basic dyes, and the like, and one or more selected from these can be used in combination.

Specific examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44
79, 142, C.I. I. Acid Red 52,80,82,249,254,289
, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 2
4, 94, C.I. I. Food Black 1, 2, C.I. I. Direct yellow 1,12,
24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct blue
1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Direct Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3,
4, 35 etc. are mentioned.

(Fluorescent material)
Examples of the fluorescent material constituting the second composition include C.I. I. Direct yellow 8
7, C.I. I. Acid Red 52, C.I. I. Acid Red 92, Brilliant sulfoflavin, eosin, basic flavin, acridine orange, rhodamine 6G, rhodamine B and the like.

(Phosphorescent material)
Examples of phosphorescent materials constituting the second composition include various sulfides exemplified by alkaline earth sulfides such as zinc, calcium, strontium and barium, phosphorescent materials such as strontium aluminate, and zinc sulfide. Inorganic fluorescent materials such as materials and oxides.

(Phosphorescent material)
Examples of the phosphorescent material constituting the second composition include iridium complexes and cyclometalated complexes.

(Infrared absorbing material)
Examples of the infrared absorbing material constituting the second composition include ITO and ATO fine particles.

(Dispersant)
When the second composition contains a dispersoid such as a pigment, the dispersibility of the dispersoid (for example, a pigment or the like) can be further improved if it further contains a dispersant.

Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used in preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned.

Specific examples of the polymer dispersant include, for example, polyoxyalkylene polyalkylene polyamine, vinyl polymer and copolymer, acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer, silicon-containing polymer, and sulfur-containing polymer. , Fluorine-containing polymers, and epoxy resins having one or more types as main components.

Examples of commercially available polymer dispersants include, for example, Ajimoto series manufactured by Ajinomoto Fine-Techno Co., Ltd. and Solspers series (Solspe series available from Noveon).
rse 36000), BYK's Disperbic series, Enomoto Kasei's Disparon series, and the like.

(Curable resin)
When the second composition contains a curable resin, the mechanical strength, reliability, and the like of the shaped article can be further improved. Moreover, the stability of the shape at the time of modeling can be improved, and the dimensional accuracy of the manufactured model can be made more excellent.

Examples of the curable resin include a thermosetting resin; various photo-curing properties such as a visible light curable resin (a photocurable resin in a narrow sense) that is cured by light in the visible light region, an ultraviolet curable resin, and an infrared curable resin. Resin; X-ray curable resin etc. are mentioned, It can use combining 1 type (s) or 2 or more types selected from these.

As the ultraviolet curable resin (polymerizable compound), a resin in which addition polymerization or ring-opening polymerization is initiated by irradiation with ultraviolet rays by radical species or cationic species generated from a photopolymerization initiator, and a polymer is preferably used. . As the polymerization mode of addition polymerization, radical, cation,
Examples include anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.

Examples of the addition polymerizable compound include compounds having at least one ethylenically unsaturated double bond. As the addition polymerizable compound, a compound having at least one, preferably two or more terminal ethylenically unsaturated bonds can be preferably used.

The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a polyfunctional polymerizable compound, or a mixture thereof.

Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like.

As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic amine compound is used.

In addition, unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group and the like, addition products of isocyanates and epoxies, dehydration condensation products of carboxylic acids, etc. Can be used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with alcohols, amines and thiols, as well as removal of halogen groups, tosyloxy groups, etc. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasing substituent and an alcohol, amine or thiol can also be used.

Specific examples of the radical polymerizable compound that is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound include, for example, (meth) acrylic acid ester, which is either monofunctional or polyfunctional. Can also be used.

Specific examples of monofunctional (meth) acrylates include, for example, tolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, and cyclohexyl (meth).
Acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate, dipropylene glycol di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, (
Examples include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

Specific examples of the bifunctional (meth) acrylate include, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, penta Examples include erythritol di (meth) acrylate and dipentaerythritol di (meth) acrylate.

Specific examples of the trifunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri ( Data) acrylate, and the like.

Specific examples of the tetrafunctional (meth) acrylate include, for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate.

Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Specific examples of the hexafunctional (meth) acrylate include, for example, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, captolactone-modified dipentaerythritol hexa ( And (meth) acrylate.

Examples of the polymerizable compound other than (meth) acrylate include itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester and the like.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diesterate. Examples include itaconate and sorbitol tetritaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate,
Examples include pentaerythritol diisocrotonate and sorbitol tetraisocrotonate.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters, those having an aromatic skeleton, those containing an amino group, and the like.

Specific examples of the amide monomer of unsaturated carboxylic acid and aliphatic amine compound include, for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-
Examples include hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, (meth) acryloylmorpholine, and the like.

Examples of other preferred amide monomers include those having a cyclohexylene structure.

Also suitable are urethane-based addition-polymerizable compounds produced using an addition reaction between isocyanate and hydroxyl group. Specific examples of such compounds include polyisocyanate compounds having two or more isocyanate groups per molecule. Examples thereof include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by the following formula (1) is added.

_{CH 2 = C (R1) COOCH} 2 CH (R2) OH (1)
(Wherein (1), R1 and R2 each independently represent H or CH _3.)

In the present invention, a cationic ring-opening polymerizable compound having at least one cyclic ether group such as an epoxy group or an oxetane group in the molecule can be suitably used as the ultraviolet curable resin (polymerizable compound).

Examples of the cationic polymerizable compound include a curable compound containing a ring-opening polymerizable group, and among them, a heterocyclic group-containing curable compound is preferable. Examples of such a curable compound include cyclic imino ethers such as epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, oxazoline derivatives,
Examples include vinyl ethers, and among them, epoxy derivatives, oxetane derivatives, and vinyl ethers are preferable.

Examples of preferred epoxy derivatives include monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxies, polyfunctional alicyclic epoxies, and the like.

Specific examples of glycidyl ethers include, for example, diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc.), trifunctional or higher glycidyl ethers (for example, trimethylolethane triglycidyl). Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate),
Tetrafunctional or higher glycidyl ethers (for example, sorbitol tetraglycidyl ether,
Pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, Celoxide 2021P, Celoxide 2081, Epolide GT-30)
1, Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc.), oxetanes (for example, OX-SQ) , PNOX-1009 (above, manufactured by Toagosei Co., Ltd.) and the like.

As the polymerizable compound, an alicyclic epoxy derivative can be preferably used. The “alicyclic epoxy group” refers to a partial structure obtained by epoxidizing a double bond of a cycloalkene ring such as a cyclopentene group or a cyclohexene group with an appropriate oxidizing agent such as hydrogen peroxide or peracid.

The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy having two or more cyclohexene oxide groups or cyclopentene oxide groups in one molecule. Specific examples of the alicyclic epoxy compound include, for example, 4-vinylcyclohexene dioxide, (3,4-
Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate,
Di (3,4-epoxycyclohexyl) adipate, di (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, di (2,3
-Epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide and the like.

The glycidyl compound which has a normal epoxy group which does not have an alicyclic structure in a molecule | numerator can be used independently, or can also be used together with the said alicyclic epoxy compound.

Examples of such normal glycidyl compounds include glycidyl ether compounds and glycidyl ester compounds, but it is preferable to use glycidyl ether compounds in combination.

Specific examples of the glycidyl ether compound include 1,3-bis (2,3-epoxypropyloxy) benzene, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac. Type epoxy resin, aromatic glycidyl ether compound such as trisphenolmethane type epoxy resin,
Examples thereof include aliphatic glycidyl ether compounds such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, and trimethylolpropane tritriglycidyl ether. Examples of the glycidyl ester include a glycidyl ester of linolenic acid dimer.

As the polymerizable compound, a compound having an oxetanyl group which is a 4-membered cyclic ether (
Hereinafter, it is also simply referred to as “oxetane compound”. ) Can be used. An oxetanyl group-containing compound is a compound having one or more oxetanyl groups in one molecule.

(Polymerization initiator)
Examples of the polymerization initiator include azobisisobutyronitrile (AIBN), bis (2,
4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like can be used.

(Surfactant)
If the second composition contains a surfactant, the rub resistance of the shaped article can be made better.

The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used.

Specific examples of the surfactant include BYK-347, BYK-348, and BYK-U.
V3500, 3510, 3530, 3570 (the above-mentioned, the brand name by BYK company) etc. are mentioned.

The second composition is preferably a liquid.
Thereby, a modeling thing can be manufactured suitably using a method as mentioned above, and a modeling thing of higher dimensional accuracy can be manufactured with more excellent productivity.

Further, when the second composition is a liquid, the viscosity of the second composition is 2 mPa ·
It is preferably from s to 30 mPa · s, more preferably from 5 mPa · s to 20 mPa · s.

Thereby, for example, the ejection stability of the second composition by the ink jet method can be further improved.

For example, a plurality of types of second compositions may be used for manufacturing the shaped article.
For example, you may use the 2nd composition as an ink (color ink) containing a coloring agent, and the 2nd composition as an ink (clear ink) which does not contain a coloring agent. Accordingly, for example, the second composition containing the colorant is used as the second composition to be applied to the area that affects the color tone on the appearance of the modeled object, and the color tone is not affected on the appearance of the modeled object. The 2nd composition which does not contain a coloring agent as a 2nd composition provided to an area | region can be used.

For example, you may use the 2nd type of 2nd composition containing the coloring agent of a different composition. Thereby, the color reproduction area which can be expressed can be made wide by the combination of these 2nd compositions.

When a plurality of types of second compositions (inks) are used, it is preferable to use at least a cyan-purple (cyan) ink, a red-violet (magenta) ink, and a yellow (yellow) ink. Thereby, the color reproduction area which can be expressed can be made wider by the combination of these 2nd compositions (ink).

<Modeling>
Next, the modeled object (three-dimensional modeled object) of the present invention will be described.

The shaped article of the present invention includes a cellulose derivative having an amine structure in the molecule and an anionic compound having a valence of 2 or more, and an ion is formed between the amine structure and the anionic functional group of the anionic compound. A bond is formed.
Thereby, a highly reliable shaped article having a self-repair function can be provided.

Such a shaped article can be suitably produced using the cellulose-based material of the present invention and the composition set for producing a shaped article as described above.

The shaped article of the present invention preferably contains polyphosphoric acid as an anionic compound.

Thereby, since the ionic bond between a cellulose derivative and an anionic compound can be formed more suitably, the mechanical strength etc. of a molded article can be made more excellent. In addition, the self-repair function can be exhibited more effectively. From such a thing, durability and reliability of a molded article can be made more excellent.

The shaped article of the present invention may be applied to any of prototypes, mass-produced products, and custom-made products.

Since the shaped article of the present invention has the excellent characteristics as described above, it can be applied to various uses.

Although the use of the shaped article of the present invention is not particularly limited, for example, a mobile phone, a smartphone,
Protective film that protects display parts of electronic devices with display parts such as digital cameras, digital video cameras, car navigation devices, etc .; Appreciation and display items such as dolls and figures; Medical treatments such as artificial blood vessels, artificial dialysis devices, and implants Equipment; Printing paper; Optical members such as lenses (including variable focus lenses), retardation films and deflecting plates; Gel materials such as culture scaffolds used for culturing various cells and various bacteria; Vehicles such as bicycles; Wheelchairs, etc. Nursing care / nursing supplies, and their components.

In particular, the present invention is preferably applied to a medical device that requires higher reliability and safety.

Thereby, the effect of the present invention that has a self-repair function and high reliability is more remarkably exhibited.

In particular, an artificial blood vessel is difficult to replace once applied to a human body and the like, and higher safety and reliability are required. However, since the present invention can meet such requirements, It can be suitably applied to blood vessels.

Moreover, it is known that the dialysis member generally has a large surface area, and even if a part of them has a defect, its function is significantly reduced. In particular, if a dialysis member used for artificial dialysis is defective, it is more serious because it causes a life-threatening problem. On the other hand, in the present invention, as described above, it has high safety and reliability, and in particular, even if a scratch or the like occurs, it can be repaired at an early stage by a self-repair function, These functions can be suitably retained. Therefore, the present invention can be suitably applied to a dialysis member.

[Dialysis members]
Hereinafter, the member for dialysis as an example of the shaped article of the present invention will be described in detail.

FIG. 4 is a side view schematically showing a preferred embodiment of a member for dialysis as a modeled article of the present invention.

As shown in FIG. 4, the dialysis member (molded article) P100 includes a first flow path P21 and a second flow path P22 through which different fluids flow as a plurality of tubular flow paths.

These channels are made of a material containing a cellulose derivative having an amine structure in the molecule and an anionic compound having a valence of 2 or more, and are separated by a wall portion P23 formed integrally. And in the wall part P23, the ionic bond is formed between the said amine structure and the anionic functional group which the said anionic compound has.

Thus, it is composed of a material containing the cellulose derivative and the anionic compound,
An ionic bond is formed between the amine structure and the anionic functional group, and a plurality of channels (first channel P21, second channel P22) are separated by the integrally formed wall portion P23. Therefore, the strength, safety and reliability of the dialysis member P100 can be improved.

In addition, in the conventional structure in which a plurality of hollow fibers are bundled and incorporated in a housing, there is a problem that not only there is a risk of the hollow fibers being damaged during manufacturing or dialysis, but productivity is low. Such a problem can be solved by the dialysis member P100. Further, even when a minute scratch or the like occurs, the self-repair function allows the self-repair at an early stage, so that the function as a dialysis member can be suitably maintained.

The first fluid flowing in the first flow path P21 is different from the second fluid flowing in the second flow path P22.
The wall P23 functions as a semipermeable membrane.

Therefore, for example, when the dialysis member P100 is used for artificial dialysis (hemodialysis therapy), waste in the blood can be suitably removed while maintaining the electrolyte and water content in the blood.

When the dialysis member P100 is used for artificial dialysis (hemodialysis therapy), for example, the first flow path P
The blood as the first fluid can be circulated through 21, and the dialysate as the second fluid can be circulated through the second flow path P22.

In the following description, the dialysis member P100 causes blood as the first fluid to flow through the first flow path P21 and allows dialysate as the second fluid to flow through the second flow path P22. Thus, the case of using for artificial dialysis (hemodialysis therapy) will be described representatively.

In the dialysis member P100, the first flow path P21 and the second flow path P22 are configured such that fluid flows in the opposite direction.

Thereby, the efficiency of dialysis can be made more excellent, and waste products can be more efficiently removed while suitably maintaining the electrolyte in blood (first fluid).

The dialysis member P100 includes a plurality of first flow paths P21 and second flow paths P22.

Thereby, the area of the wall part P23 per unit volume of the dialysis member P100 (the area of the part functioning as a semipermeable membrane) can be increased, and the dialysis efficiency can be further improved. .

A plurality of second flow paths P22 are arranged along the longitudinal direction of the flow path so as to surround the first flow path P21.

Thereby, the removal efficiency of the waste material as a solute contained in blood (1st fluid) can be made more excellent.

Although the cross-sectional shape of the flow path (the first flow path P21 and the second flow path P22) is not particularly limited,
In this embodiment, the cross-sectional shape in the direction perpendicular to the longitudinal direction of the flow paths (the first flow path P21 and the second flow path P22) has a honeycomb shape, that is, each flow path has a hexagonal shape. Is.

Thereby, while making the mechanical strength and shape stability of the dialysis member P100 more excellent, the area of the wall portion per unit volume of the dialysis member P100 (area of the part functioning as a semipermeable membrane) is increased. The dialysis efficiency can be further improved.
In particular, even when the flow paths (the first flow path P21 and the second flow path P22) are relatively large (larger than the hollow portion of the conventional hollow fiber), the dialysis member P100. The mechanical strength, shape stability, and dialysis efficiency can be made excellent. Therefore, the characteristics of the manufactured dialysis member P100 can be improved while the dialysis member P100 is more easily manufactured.

The width of the flow path (the first flow path P21 and the second flow path P22) is 300 μm or more and 500 μm.
Or less, more preferably 350 μm or more and 450 μm or less.

Thereby, the flow rate of the fluid can be easily increased, and the dialysis efficiency can be further improved. In addition, the time required for dialysis (treatment time) can be shortened, and the burden on the patient can be reduced. In addition, even when the pressure applied when the fluid is circulated is relatively small, a sufficient flow rate can be secured, so that the fluid is damaged by the pressure while improving the efficiency of dialysis. This can be effectively prevented. More specifically, it is possible to effectively prevent damage to components (for example, blood cells and the like) constituting blood that is the first fluid. In addition, dialysis member P10
0 can be manufactured more easily.

In addition, as the width of the flow path, for example, when the cross-sectional shape in a cross section perpendicular to the longitudinal direction of the flow path is circular, the value of the diameter can be adopted, and when it is non-circular The value of the diameter of a circle having the same area as the cross-sectional area can be adopted for.

It should be noted that the plurality of flow paths constituting the dialysis member (for example, the first flow path P21 and the second flow path P
22), the cross-sectional shape and the cross-sectional area may be different from each other, but are preferably the same. Thereby, these flow paths can be arranged with high density, and the dialysis member P10.
The mechanical strength of 0 can be more reliably improved. In addition, dialysis member P10
The manufacture of 0 is also easy.

The thickness of the wall portion P23 is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 80 μm or less.

As a result, the dialysis efficiency can be further improved while the mechanical strength and shape stability of the dialysis member P100 are further improved. In addition, the dialysis member P100 can be easily manufactured.

The number of flow paths (first flow path P21 and second flow path P22) fractionated by the wall portion P23 is preferably 5000 or more and 50000 or less, and more preferably 8000 or more and 30000 or less.

Thereby, the dialysis efficiency can be further improved while preventing the dialysis member P100 from being enlarged. In addition, the mechanical strength and shape stability of the dialysis member P100 are further improved.

Also, each flow path (the first flow path P21 and the second flow path P2) constituting the dialysis member P100.
2) is a spiral.

Thereby, the area of the wall portion P23 per unit volume of the dialysis member P100 (the area of the part functioning as a semipermeable membrane) can be increased while preventing the dialysis member P100 from becoming large. Since the fluid can be circulated more reliably and smoothly, the dialysis efficiency can be further improved.

《Dializer》
Next, the dialyzer of the present invention will be described.

The dialyzer of the present invention is provided with the shaped article (dialysis member) of the present invention as described above.
Thereby, a safe and highly reliable dialyzer can be provided.

The dialyzer of the present invention is at least a molded article (dialysis member) of the present invention as described above.
However, it is usually provided with a housing for housing the dialysis member of the present invention,
The housing is connected to the first flow path P21, connected to the first flow path P21, and a first fluid inlet that selectively supplies the first fluid to the first flow path P21. The first fluid outlet through which the first fluid flowing through the first channel P21 selectively flows out to the outside and the second channel P22 are selectively connected to the second channel P22. A second fluid inlet for supplying the second fluid and a second fluid connected to the second flow path P22 and selectively allowing the second fluid flowing through the second flow path P22 to flow out to the outside. And an outlet.

Examples of the constituent material of the housing include various plastic materials and various metal materials.

As a plastic material constituting the housing, for example, polyethylene, polypropylene,
Polybutadiene, polyolefin such as ethylene-vinyl acetate copolymer, polyvinyl chloride,
Polyester such as polyurethane, polystyrene, polymethyl methacrylate, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, acrylic resin such as polymethyl methacrylate, ABS resin, AS resin, ionomer, polyacetal, polyphenylene sulfide, polyether ether ketone, etc. Can be mentioned.

Examples of the metal material constituting the housing include Al, Ti, alloys containing these, and stainless steel.

《Dialysis device》
Next, the dialysis apparatus of the present invention will be described.

Hereinafter, as a specific example of the dialysis apparatus, what is used for hemodialysis therapy will be described representatively.

FIG. 5 is a schematic view showing a preferred embodiment of the dialysis apparatus of the present invention.
The dialysis apparatus D100 of the present embodiment includes a dialyzer D1 including the dialysis member (modeled object) P100 of the present invention described above, a fresh dialysate circuit D2 for supplying a dialysate (second fluid) to the dialyzer D1, and a dialyzer D1. A dialysate circuit D4 comprising a used dialysate circuit D3 through which the returning dialysate (second fluid) flows, an arterial extracorporeal circulation blood circuit D5 and a dialyzer D1 for guiding blood (first fluid) from the dialyzed patient D10 to the dialyzer D1. This includes an extracorporeal circulation circuit D7 including a venous extracorporeal circulation blood circuit D6 for returning blood after dialysis (first fluid) to a dialysis patient D10, and a dialysis device D8.

The dialysis machine D8 optionally includes a blood water content measuring means, a temperature setting mechanism including a temperature sensor for monitoring and adjusting the temperature of the dialysate, a control means for the flow rate of the dialysate flowing into the dialyzer D1, and the dialyzer D1. A water removal mechanism (viscous chamber method, using a water removal pump, etc.) that creates a pressure difference between the blood and the dialysate to transfer the water in the blood to the dialysate side, in the extracorporeal circulation blood circuit A control unit D9 for controlling a blood pump for flowing blood, a water removal mechanism, a blood pump, and the like is provided.
Thereby, a highly safe and reliable dialysis apparatus can be provided.

《Dialysis method》
Next, the dialysis method of the present invention will be described.

The dialysis method of the present invention is characterized in that dialysis is performed using the above-described shaped article (dialysis member) of the present invention.

More specifically, in the dialysis member of the present invention described above, dialysis is performed by circulating the first fluid through the first flow path and the second fluid through the second flow path. .
Thereby, a safe and highly reliable dialysis method can be provided.

Such a dialysis method can be more suitably performed by using the dialyzer of the present invention provided with the shaped article (dialysis member) of the present invention and the dialysis apparatus of the present invention.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

For example, in the above-described embodiment, the case where the squeegee is used as the flattening unit has been mainly described, but a roller or the like may be used instead.

Moreover, the manufacturing apparatus used for manufacture of the shaped article of the present invention includes a recovery mechanism (not shown) for recovering a composition supplied from the composition supply unit that has not been used for forming a layer. There may be. Thereby, it is possible to supply a sufficient amount of the composition while preventing the surplus composition from accumulating in the layer forming portion, and thus more effectively preventing the occurrence of defects in the layer. A molded article can be manufactured stably. In addition, the recovered composition
Since it can be used again for manufacturing a modeled object, it can contribute to the reduction of the manufacturing cost of the modeled object, and is also preferable from the viewpoint of resource saving.

Moreover, the manufacturing apparatus used for manufacture of the molded article of this invention may be equipped with the collection | recovery mechanism for collect | recovering the compositions removed by the unbound particle removal process.

Further, in the above-described embodiment, it has been described that the coupling portion (substance portion) is formed with respect to all layers. However, a layer in which the coupling portion (substance portion) is not formed may be included. For example, a coupling portion (substance portion) may not be formed with respect to a layer formed immediately above the stage, and may function as a sacrificial layer.

In the above-described embodiment, the case where the liquid composition applying step is performed by an ink jet method has been mainly described. However, the liquid composition applying step is performed by another method (for example, another printing method).
It may be performed using

Further, in the present invention, a cellulose-based material containing a cellulose derivative as described above may be used for forming at least a part of the substantial part of the molded article, and the cellulose-based material containing a cellulose derivative is not used. It may have a part.

In the production of the shaped article of the present invention, if necessary, a pretreatment step, an intermediate treatment step,
You may perform a post-processing process.
Examples of the pretreatment process include a stage cleaning process.

As the intermediate treatment step, for example, when the particle-containing composition is in the form of pellets,
You may have the process (binder solidification process) of stopping heating etc. between a layer formation process and a liquid composition provision process. Thereby, the binder which comprises a pellet will be in a solid state,
The layer can be obtained with a stronger bonding force between the particles.

As a post-processing process, for example, a cleaning process, a shape adjustment process for performing deburring, a coloring process,
Examples include a coating layer forming step.

In the above-described embodiment, the flattening means is described as moving on the stage. However, the movement of the stage changes the positional relationship between the stage and the squeegee, and flattening is performed. Also good.

Moreover, you may perform chemical reactions other than what was mentioned above at the time of manufacture of the molded article of this invention. For example, when the cellulose derivative contained in the cellulosic material has an acetylated hydroxyl group, a reaction (deacetylation) for eliminating the acetyl group may be performed at the time of manufacturing the shaped article.

In the production of the shaped article of the present invention, the liquid composition is a method other than the inkjet method (
For example, it may be given by another printing method.

Moreover, the shaped article of the present invention may not be manufactured using the method and apparatus as described above.

For example, in the above-described embodiment, a molded article using a particle-containing composition (first composition) containing a particulate cellulose material and a liquid composition (second composition) containing an anionic compound. However, in the present invention, a shaped article may be produced using a composition containing a liquid cellulosic material. More specifically, for example, an ink for forming a solid part as a liquid composition containing a cellulose derivative having an amine structure and used for forming the solid part, and an ink for forming a support part used for forming a support part that supports the solid part. (Liquid composition) is ejected in a predetermined pattern by an ink jet method to sequentially repeat the process of forming the substantial part and the support part to obtain a temporary molded body, and then the process of removing the support part (support part removal) You may manufacture using the method which has a process.

In the above-described embodiment, the case where the dialysis member is used for artificial dialysis (hemodialysis therapy) has been representatively described. However, in the present invention, the dialysis member (molded article) and a dialyzer including the dialysis member The dialysis apparatus may be used other than artificial dialysis (hemodialysis therapy).

P10 ... Modeled object (three-dimensional modeled object)
P1 '... Particle-containing composition (first composition)
P1 ... layer P12 ... liquid composition (second composition, ink)
P13 ... coupling part (substance part)
P100: Dialysis member (molded article)
P21 ... 1st flow path P22 ... 2nd flow path P23 ... Wall part 100 ... Modeling object manufacturing apparatus 2 ... Control part 21 ... Computer 22 ... Drive control part 3 ... Composition supply part (particle-containing composition supply part)
4 ... Layer forming part 41 ... Stage 42 ... Squeegee (flattening means)
43 ... guide rail 44 ... composition temporary placement part (particle-containing composition temporary placement part)
45 ... Side support (frame)
5 ... Liquid composition discharge part (liquid composition application means)
6 ... Energy beam irradiation means D100 ... Dialyzer D1 ... Dialyzer D2 ... Fresh dialysate circuit D3 ... Used dialysate circuit D4 ... Dialysate circuit D5 ... Arterial extracorporeal circulation blood circuit D6 ... Vein side extracorporeal circulation blood circuit D7 ... Extracorporeal Circulation circuit D8 ... Dialysis machine D9 ... Control unit D10 ... Dialysis patient

Claims (19)

A cellulosic material comprising a cellulose derivative,
The cellulose derivative is characterized in that it has an amine structure in the molecule. The cellulosic material according to claim 1, wherein the amine structure is introduced into a repeating unit of a polymer chain having a repeating structure introduced into a cellulose skeleton structure of the cellulose derivative. The cellulose material according to claim 1, wherein the cellulose derivative has a primary amine or a salt thereof as the amine structure. The cellulose material according to claim 3, wherein the cellulose derivative has a polyallylamine structure. The cellulose system according to any one of claims 1 to 4, wherein the amine structure is provided in a substituent introduced into a hydroxyl group bonded to the 6-position carbon of β-glucose constituting cellulose. material. A first composition comprising the cellulosic material according to any one of claims 1 to 5;
A composition set for manufacturing a molded article, comprising: a second composition containing a divalent or higher anionic compound. The composition set for manufacturing a molded article according to claim 6, wherein the first composition includes, as the cellulosic material, particles in which at least a region including the surface is composed of the cellulose derivative. The composition set for manufacturing a molded article according to claim 6 or 7, wherein the second composition is in a liquid state. A shaped article produced using the cellulosic material according to any one of claims 1 to 5. A shaped article produced using the composition set for producing a shaped article according to any one of claims 6 to 8. Including a cellulose derivative having an amine structure in the molecule and a divalent or higher anionic compound,
A shaped article, wherein an ionic bond is formed between the amine structure and the anionic functional group of the anionic compound. The shaped article according to any one of claims 9 to 11, which contains polyphosphoric acid as the anionic compound.   The modeled object according to any one of claims 9 to 12, wherein the modeled object is a medical device.   The shaped article according to claim 13, wherein the shaped article is an artificial blood vessel.   The shaped article according to claim 13, wherein the shaped article is a member for dialysis.   A dialyzer comprising the shaped article according to claim 15.   A dialysis machine comprising the shaped article according to claim 15.   Dialysis is performed using the shaped article according to claim 15. A layer forming step of forming a layer having a predetermined thickness using a particle-containing composition containing particles;
A binding liquid applying step of applying a binding liquid to a predetermined region of the layer;
It is a method for producing a shaped article by sequentially repeating these steps,
The particle-containing composition contains a cellulose derivative having an amine structure in the molecule,
The method for producing a shaped article, wherein the binding liquid contains a divalent or higher anionic compound.

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