WO2017130685A1

WO2017130685A1 - Method for producing three-dimensional model and modeling material

Info

Publication number: WO2017130685A1
Application number: PCT/JP2017/000519
Authority: WO
Inventors: 務塩山; 淳大西; 充山田
Original assignee: バンドー化学株式会社
Priority date: 2016-01-28
Filing date: 2017-01-10
Publication date: 2017-08-03
Also published as: JPWO2017130685A1; JP2018024249A; JP6220477B1; JP6220476B1

Abstract

The purpose of the present invention is to provide a method for easily and surely producing a three-dimensional model, said three-dimensional model comprising polyurethane, polyurethane urea or polyurea as a main component, using a 3D printer. The method according to the present invention for producing a three-dimensional model, whereby a three-dimensional model comprising polyurethane, polyurethane urea or polyurea as a main component is produced using an ink-jet type 3D printer, comprises a step for successively laminating on a substrate synthetic resin layers by jetting a first liquid composition and a second liquid composition which react with each other upon mixing, said method being characterized in that, in the successive lamination step, the first liquid composition and the second liquid composition are mixed together immediately before or immediately after jetting so that the first liquid composition reacts with the second liquid composition by a pseudo-prepolymer method. The ratio by mass of the jet amount of the first liquid composition to the jet amount of the second liquid composition preferably ranges from 100:250 to 100:40 inclusive.

Description

Manufacturing method and modeling material of three-dimensional structure

The present invention relates to a method for manufacturing a three-dimensional structure and a modeling material.

Polyurethane, polyurethaneurea and polyurea (hereinafter also referred to as “polyurethane”) are obtained by a curing reaction between an isocyanate component such as polyisocyanate and a polyol component such as a long-chain polyol and / or a polyamine component such as a long-chain polyamine. It is a synthetic resin, and it is easy to adjust physical properties such as elastic modulus and hardness, and is excellent in wear resistance and moldability. For this reason, molded articles made of polyurethane or the like are used in various products such as shoe soles, grips of motorcycles and motorcycles, personal use products such as glasses, masks, and ornaments, artificial limbs, and training equipment.

As a method for producing a three-dimensional molded body using polyurethane or the like, a reaction injection molding method using a mold or a casting molding method is generally used. On the other hand, in recent years, a method for producing a three-dimensional structure such as polyurethane using a 3D printer has also been proposed (see JP-A-2005-35299 and JP-T-2003-506228). In the production methods described in these documents, droplets of a first liquid composition containing polyisocyanate and liquid droplets of a second liquid composition containing a polyol are each ejected by an ink jet method, and two kinds of droplets are in the air. Are collided and landed on the support base, or two kinds of droplets landed on the support base are mixed. According to the above document, a polyurethane layer having a desired shape can be laminated on the support base by the above-described method. Therefore, it is said that a polyurethane three-dimensional structure can be manufactured by repeating the lamination of the polyurethane layer. The manufacturing method of three-dimensional shaped objects such as polyurethane using such a 3D printer is a single item such as manufacturing tailor-made products tailored to the demands of each customer, and manufacturing prototype parts required when designing assembly products. It is considered useful for the production of

In addition, the above-described conventional method changes the composition of the first liquid composition, the composition of the second liquid composition, the mixing ratio of the first liquid composition and the second liquid composition, etc. It is considered that the present invention can be applied to the production of three-dimensional shaped objects that differ from part to part, in particular, functionally graded material whose physical properties continuously change from part to part.

However, in the synthesis reaction of polyurethane, polyurethane urea and polyurea, it is usually necessary to use a polyol component and / or a polyamine component in a larger volume than an isocyanate component. Therefore, in the conventional manufacturing method, the discharge amount of the second liquid composition tends to be significantly larger than the discharge amount of the first liquid composition (for example, more than 2.5 times). In particular, in the above-described conventional method, when the mixing ratio or composition of the first liquid composition and the second liquid composition is changed during modeling in order to manufacture a three-dimensional model with different physical properties for each part, There is a possibility that the discharge amount of the two-component composition further increases. Here, in the above-described conventional method, when the discharge amounts of the first liquid composition and the second liquid composition are significantly different, they cannot be mixed uniformly, and as a result, there is a risk of causing poor curing. In addition, desired physical properties may not be obtained. For this reason, the three-dimensional structure obtained by the above-described conventional manufacturing method may cause a variation in physical properties for each part and a desired characteristic may not be obtained, or stress may be easily concentrated on a part where the physical property is changed. Therefore, there is a risk that the macro damage resistance is lowered.

JP 2005-35299 A Special table 2003-506228 gazette

The present invention has been made in view of these requirements, and a method for easily and reliably producing a three-dimensional structure mainly composed of polyurethane, polyurethane urea or polyurea using a 3D printer, and a modeling material used therefor It is an issue to provide.

The invention made in order to solve the above-mentioned problems is a method for producing a three-dimensional structure mainly comprising polyurethane, polyurethane urea or polyurea using an ink jet 3D printer, and reacts by mixing. A step of sequentially laminating a synthetic resin layer on a support by discharging a product and a second liquid composition, and immediately before or immediately after discharging the first liquid composition and the second liquid composition in the sequential layering step. And the first liquid composition and the second liquid composition react with each other by a pseudo prepolymer method.

The manufacturing method of the three-dimensional structure has a step of sequentially laminating a synthetic resin layer on a support by discharging a first liquid composition and a second liquid composition that react by mixing, The 1st liquid composition and the 2nd liquid composition are mixed immediately before or immediately after discharging, and the 1st liquid composition and the 2nd liquid composition react by the pseudo prepolymer method. Here, the pseudo prepolymer method means that in the synthesis of polyurethane or the like, a part of the long-chain polyol and / or long-chain polyamine to be used is pre-reacted with a polyisocyanate, and this prepolymer is combined with the polyisocyanate to form an isocyanate. It is a method used as a component. In this pseudo prepolymer method, since a part of the long-chain polyol and / or long-chain polyamine is used for the synthesis of the prepolymer and this prepolymer is used as the isocyanate component, the polyol component and / or the polyamine component in the modeling material to be used The volume ratio with the isocyanate component can be close to 1: 1. Thus, the manufacturing method of the said three-dimensional structure uses the 1st liquid composition and the 2nd liquid composition by using the 1st liquid composition and the 2nd liquid composition which react with a pseudo prepolymer method as a modeling material. Since the mixing volume ratio of the product can be in a range relatively close to 1: 1, the first liquid composition and the second liquid composition can be uniformly mixed and reliably cured. As a result, the method for manufacturing a three-dimensional structure can easily and reliably manufacture a three-dimensional structure having polyurethane or the like as a main component using a 3D printer.

The mass ratio of the discharge amounts of the first liquid composition and the second liquid composition (first liquid composition: second liquid composition) is preferably 100: 250 or more and 100: 40 or less. Since the specific gravity of the first liquid composition and the second liquid composition is generally substantially the same, by setting the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition in the above range, the volume ratio is Can be closer to 1: 1. Thereby, a 1st liquid composition and a 2nd liquid composition can be mixed more uniformly, As a result, the three-dimensional molded item which has a polyurethane etc. as a main component can be manufactured more easily and reliably.

In the manufacturing method of the three-dimensional structure, the density of the synthetic resin layer is changed for each part by changing the discharge amount of the first liquid composition and the second liquid composition in the sequential lamination step. Good. In this way, the manufacturing method of the three-dimensional structure is formed by sequentially changing the discharge amount of the first liquid composition and the second liquid composition in the laminating step and changing the density of the synthetic resin layer for each part. The physical properties such as tensile properties and wear resistance of the three-dimensional structure to be manufactured can be changed for each part. Therefore, according to the method for manufacturing a three-dimensional structure, a three-dimensional structure having polyurethane or the like as a main component and having different physical properties for each part can be easily and reliably manufactured.

In the manufacturing method of the three-dimensional structure, the porous region may be formed in at least a part of the synthetic resin layer in the sequential lamination step. In this way, the manufacturing method of the three-dimensional structure can sequentially change the density of the synthetic resin layer by forming the porous region in at least a part of the synthetic resin layer in the sequential lamination process, As a result, it is possible to more reliably manufacture a three-dimensional structure having different physical properties for each part.

In the manufacturing method of the three-dimensional structure, the porosity of the porous region may be changed in the range of more than 0% by volume and 45% by volume or less in the sequential lamination step. Thus, the manufacturing method of the said three-dimensional structure changes the porosity of a porous area | region in the said range by a lamination | stacking process one by one, and the physical property for every part is ensured, ensuring the intensity | strength of the three-dimensional structure formed. It can be easily changed.

The first liquid composition includes at least one prepolymer of a urethane prepolymer, a urethane urea prepolymer, and a urea prepolymer, and a polyisocyanate, and the second liquid composition includes a long chain polyol and a long chain. It is good to contain at least 1 sort (s) of soft segment components among polyamines and at least 1 sort (s) of hard segment components among a chain extender and a crosslinking agent. Thus, by using the first liquid composition containing the prepolymer and the polyisocyanate and the second liquid composition containing the soft segment component and the hard segment component, the reaction by the pseudo prepolymer method is more reliably performed. Can be made. Moreover, moderate elasticity modulus, hardness, etc. can be provided to the three-dimensional structure to be formed because the second liquid composition contains a hard segment component.

At least one of the first liquid composition and the second liquid composition may further contain a plasticizer. Thus, at least one of the first liquid composition and the second liquid composition further contains a plasticizer, thereby reducing the viscosity of the first liquid composition and / or the second liquid composition, Mixing can be promoted, and as a result, a three-dimensional structure mainly composed of polyurethane or the like can be produced more easily and reliably.

The manufacturing method of the said three-dimensional structure is the said sequential lamination process, The composition of the said 1st liquid composition, the composition of the said 2nd liquid composition, the said 1st liquid composition, and the said 2nd liquid composition It is preferable to change at least one of the mixing ratio. Thus, the manufacturing method of the said three-dimensional structure is a sequential lamination process, the composition of the first liquid composition, the composition of the second liquid composition, and the mixing of the first liquid composition and the second liquid composition. By changing at least one of the ratios, the constituent material of the three-dimensional structure to be formed can be changed for each part, and the physical properties can be changed for each part. In addition, since the first liquid composition and the second liquid composition are modeling materials whose mixing volume ratio that reacts by the pseudo prepolymer method is relatively close to 1: 1, the composition and the mixing ratio are changed during modeling. However, the mixing volume ratio is extremely difficult to deviate from 1: 1. Therefore, according to the method for manufacturing a three-dimensional structure, a three-dimensional structure having polyurethane or the like as a main component and having different physical properties for each part can be easily and reliably manufactured.

The second liquid composition further includes a plasticizer, and the plasticizer content in the second liquid composition may be changed in the sequential lamination step. As described above, the second liquid composition further includes a plasticizer that is a component having a relatively small influence on the curing reaction, and is cured by sequentially changing the content of the plasticizer in the second liquid composition in the laminating step. The physical properties of the formed three-dimensional modeling material can be changed for each part without significantly affecting the reaction. Thereby, it is possible to more easily and reliably manufacture a three-dimensional structure having polyurethane as a main component and different physical properties for each part.

In the manufacturing method of the three-dimensional structure, the first liquid composition and the second liquid composition further include a plasticizer, and in the sequential lamination step, the composition of the first liquid composition and the second liquid composition. It is preferable to change at least one of the composition of the product so that the mass ratio of the discharge amount of the first liquid composition and the second liquid composition is 100: 110 or more and 100: 90 or less. As described above, the manufacturing method of the three-dimensional structure is a three-dimensional structure formed by changing at least one of the composition of the first liquid composition and the composition of the second liquid composition in the sequential lamination step. The physical properties of the material can be changed for each part. In addition, since the plasticizer included in the first liquid composition and the second liquid composition is a component that has a relatively small influence on the curing reaction and can be blended in a relatively large amount, the first liquid composition and the second liquid composition It can be suitably used for adjusting the bulk of the two-component composition. Therefore, the first liquid composition and the second liquid composition contain a plasticizer, and by adjusting the content of this plasticizer, the discharge amount of the first liquid composition and the second liquid composition can be adjusted during modeling. It is possible to maintain the mass ratio in the above range, that is, to maintain the mixing volume ratio in a range closer to 1: 1. Thereby, it is possible to more easily and reliably manufacture a three-dimensional structure having polyurethane as a main component and different physical properties for each part.

In the method for producing the three-dimensional structure, at least one of the prepolymer composition of the first liquid composition and the hard segment component composition of the second liquid composition may be changed in the sequential lamination step. In this way, the manufacturing method of the three-dimensional structure changes at least one of the prepolymer composition of the first liquid composition and the hard segment component composition of the second liquid composition in the sequential lamination step. The variation of the physical property change for every part of the formed three-dimensional modeling material can be abundant.

Another invention made in order to solve the above-mentioned problems is a modeling material of a three-dimensional modeled object mainly composed of polyurethane, polyurethane urea or polyurea using an ink jet 3D printer, and reacts by mixing. A liquid composition and a second liquid composition are provided, and the first liquid composition and the second liquid composition are reacted by a pseudo prepolymer method.

Since the first liquid composition and the second liquid composition included in the modeling material react by the pseudo prepolymer method, the mixing volume ratio may be set to a range relatively close to 1: 1 so as to facilitate uniform mixing. it can. Therefore, the modeling material can easily and reliably manufacture a three-dimensional modeled product mainly composed of polyurethane, polyurethane urea, or polyurea using a 3D printer.

Here, the “main component” is a component having the largest content, for example, a component having a content of 50% by mass or more. “Discharge amount” means the discharge volume amount of the modeling material discharged during the formation of the synthetic resin layer having a predetermined area (area including pores when a porous region is formed). “Porosity” means that 100 mg samples are taken from any 10 locations of the three-dimensional structure, the apparent volume calculated from the dimensions of each sample is V _A [mm ³ ], and the mass of each sample is When the actual volume (volume excluding voids) calculated by dividing by the true density is V _B [mm ³ ], it means a value obtained by 100 × (V _A −V _B ) / _VA . In addition, when a sample of 100 mg cannot be collected from any 10 locations of the three-dimensional structure, the sample with the maximum mass that can be collected is used. “Composition” refers to the type of component to be contained and its content. “Viscosity” refers to a value measured using a B-type viscometer (for example, “BMII” manufactured by Toki Sangyo Co., Ltd.). The “gel time” refers to a value measured by the gel time A method in accordance with JIS-K6910: 2007 “Phenolic resin test method”. Further, the mixing mass ratio of the first liquid composition and the second liquid composition used as a sample in the above measurement is set to match the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition.

The manufacturing method and modeling material of the three-dimensional structure can easily and reliably manufacture a three-dimensional structure mainly composed of polyurethane, polyurethane urea, or polyurea using a 3D printer.

It is a typical front view showing one process of a manufacturing method of a three-dimensional structure of a 2nd embodiment of the present invention. It is a typical front view which shows 1 process of the manufacturing method of the three-dimensional structure according to the third embodiment of the present invention. It is a typical front view showing one process of a manufacturing method of a three-dimensional structure of a 4th embodiment of the present invention. It is typical sectional drawing which shows the three-dimensional structure manufactured with the manufacturing method of FIG. It is a conceptual diagram which shows one example of the modeling material supply system used for 6th Embodiment of this invention. It is a conceptual diagram which shows one example of the modeling material supply system used for 7th Embodiment of this invention. It is a conceptual diagram which shows one example of the modeling material supply system used for 8th Embodiment of this invention. It is a conceptual diagram which shows an example of the modeling material supply system used for 10th Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. In addition, the material illustrated below may be used independently or may use multiple, unless there is particular notice.

[First Embodiment]
<Modeling material>
The modeling material is a modeling material used in a method for manufacturing a three-dimensional structure mainly composed of polyurethane, polyurethane urea, or polyurea using an ink jet 3D printer, and the first liquid composition and the first liquid that react by mixing are used. A two-liquid composition is provided, and the first liquid composition and the second liquid composition react by a pseudo prepolymer method. In the modeling material, for example, the first liquid composition is an isocyanate component, and the second liquid composition is a polyol component and / or a polyamine component.

[First liquid composition]
It is preferable that a 1st liquid composition contains at least 1 sort (s) of prepolymer among a urethane prepolymer, a urethane urea prepolymer, and a urea prepolymer, and polyisocyanate. The modeling material contains a prepolymer such as a urethane prepolymer corresponding to a component in which the curing reaction between the isocyanate component and the polyol component and / or the polyamine component partially proceeds. The usage amount of the second liquid composition with respect to the usage amount of the composition can be reduced, whereby the mixing volume ratio of the first liquid composition and the second liquid composition can be made close to 1: 1. Moreover, the said modeling material is the 1st liquid composition because a 1st liquid composition contains the said prepolymer, ie, a part of hardening reaction with an isocyanate component, a polyol component, and / or a polyamine component is completed beforehand. Compared with the modeling material in which only polyisocyanate is contained in the product, the curing rate after mixing the first liquid composition and the second liquid composition is fast. Furthermore, when the first liquid composition contains a polyisocyanate having a molecular weight smaller than that of the prepolymer, the viscosity can be lowered as compared with a composition containing only the prepolymer.

The upper limit of the viscosity of the first liquid composition at 80 ° C. is preferably 400 mPa · s, and more preferably 300 mPa · s. On the other hand, the lower limit of the viscosity of the first liquid composition at 80 ° C. is not particularly limited, but is, for example, 50 mPa · s. When the viscosity at 80 ° C. of the first liquid composition exceeds the above upper limit, it is difficult to mix with the second liquid composition, and as a result, the formed three-dimensional structure may be insufficiently cured or desired. The physical properties may not be obtained.

(Urethane prepolymer)
The urethane prepolymer used for the modeling material is an oligomer having a urethane bond (—NHCOO—) in the main chain, and can be obtained by reacting, for example, a polyisocyanate and a long chain polyol. The urethane prepolymer usually has isocyanate groups (—N═C═O) at both ends.

The lower limit of the number average molecular weight of the urethane prepolymer is preferably 800, more preferably 1,000. On the other hand, the upper limit of the number average molecular weight of the urethane prepolymer is preferably 5,000, more preferably 2,000. When the number average molecular weight of the urethane prepolymer is smaller than the lower limit, the curing rate after mixing the first liquid composition and the second liquid composition may be reduced, and the productivity in manufacturing the three-dimensional structure may be reduced. is there. On the other hand, when the number average molecular weight of the urethane prepolymer exceeds the upper limit, the viscosity of the first liquid composition increases and it may be difficult to mix with the second liquid composition. Here, the “number average molecular weight” is in accordance with JIS-K7252-1: 2008 “Plastics—Method for obtaining average molecular weight and molecular weight distribution of polymers by size exclusion chromatography—Part 1: General rules”, and polystyrene as a standard. The value measured using the gel permeation chromatography (GPC) made into a substance is pointed out.

(Polyisocyanate)
A polyisocyanate is a compound having two or more isocyanate groups in the molecule. Examples of the polyisocyanate used in the first liquid composition include aliphatic polyisocyanates (including alicyclic polyisocyanates), aromatic polyisocyanates, and the like. In addition, the said polyisocyanate does not have a urethane bond and a urea bond normally in a principal chain.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, isopropylidenebis (4-cyclohexylisocyanate), norbornane diisocyanate, modified products and multimers thereof. Examples of the aromatic isocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, modified products and multimers thereof, and the like. As said polyisocyanate, aromatic polyisocyanate is preferable and diphenylmethane diisocyanate is more preferable.

(Long chain polyol)
The long-chain polyol is a compound having a molecular weight of 300 or more having two or more hydroxyl groups (—OH) in the molecule. Examples of the long-chain polyol used in the first liquid composition include polyether polyol, polycarbonate polyol, and polyester polyol.

Examples of the polyether polyol include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, polytetramethylene ether glycol, polytetramethylene ether triol, co-condensates thereof, and side chains thereof. And derivatives having a branched structure and modified products.

Specific examples of the polycarbonate polyol and polyester polyol include compounds described in paragraphs [0017] to [0020] of JP-A-2015-209538, for example.

As the long-chain polyol, polyether polyol is preferable, and polytetramethylene ether glycol is more preferable.

The lower limit of the number average molecular weight of the long-chain polyol can be appropriately changed according to the use of the three-dimensional structure to be formed, but 500 is preferable, and 800 is more preferable. On the other hand, the upper limit of the number average molecular weight of the long-chain polyol is preferably 5,000, and more preferably 2,500. Thus, by setting the number average molecular weight of the long-chain polyol within the above range, the moldability and the physical properties such as the elastic modulus, hardness, wear resistance, and moldability of the formed three-dimensional structure are balanced. Can be improved.

(Urethane urea prepolymer)
The urethane urea prepolymer used for the modeling material is an oligomer having a urethane bond and a urea bond (-NHCONH-) in the main chain, and can be obtained by reacting, for example, a polyisocyanate, a long chain polyol, and a long chain polyamine. . The urethane urea prepolymer usually has isocyanate groups at both ends. Examples of the polyisocyanate and long-chain polyol used for the synthesis of the urethane urea prepolymer include the same polyisocyanates and long-chain polyols exemplified as the raw material of the urethane prepolymer.

The lower limit of the number average molecular weight of the urethane urea prepolymer is preferably 1,000, and more preferably 1,500. On the other hand, the upper limit of the number average molecular weight of the urethane urea prepolymer is preferably 15,000 and more preferably 10,000. When the number average molecular weight of the urethane urea prepolymer is smaller than the lower limit, the curing rate after mixing the first liquid composition and the second liquid composition may be reduced, and the productivity in manufacturing the three-dimensional structure may be reduced. There is. On the other hand, when the number average molecular weight of the urethane urea prepolymer exceeds the upper limit, the viscosity of the first liquid composition may increase and it may be difficult to mix with the second liquid composition.

(Long chain polyamine)
The long-chain polyamine is a compound having a molecular weight of 300 or more having two or more amino groups (including an alkylamino group, a dialkylamino group and an imino group) in the molecule.

Examples of the long-chain polyamine include poly (ethylene glycol) diamine, poly (propylene glycol) diamine, poly (tetramethylene ether glycol) diamine, and a long chain such as a diamine of a polycondensate of polytetramethylene ether glycol and polypropylene glycol. Examples include diamines, and long-chain triamines such as poly (ethylene glycol) triamine and poly (propylene glycol) triamine.

The long-chain polyamine is preferably a long-chain diamine, more preferably a diamine of a copolymer of polytetramethylene ether glycol and polypropylene glycol or polypropylene glycol diamine.

The lower limit of the number average molecular weight of the long-chain polyamine can be appropriately changed according to the use of the three-dimensional structure to be formed, but 500 is preferable, and 800 is more preferable. On the other hand, the upper limit of the number average molecular weight of the long-chain polyamine is preferably 5,000, and more preferably 2,500. Thus, by setting the number average molecular weight of the long-chain polyamine within the above range, the moldability and the physical properties such as the elastic modulus, hardness, and wear resistance of the formed three-dimensional structure can be improved in a balanced manner.

(Urea prepolymer)
The urea prepolymer used in the first liquid composition is an oligomer having a urea bond in the main chain, and is obtained, for example, by reacting a polyisocyanate and a long-chain polyamine. The urea prepolymer usually has isocyanate groups at both ends. Examples of the polyisocyanate and the long-chain polyamine used for the synthesis of the urea prepolymer include the same polyisocyanates and long-chain polyamines exemplified as the raw materials for the urethane prepolymer and the urethane urea prepolymer.

The lower limit of the number average molecular weight of the urea prepolymer is preferably 1,000, and more preferably 1,500. On the other hand, the upper limit of the number average molecular weight of the urea prepolymer is preferably 15,000, and more preferably 10,000. When the number average molecular weight of the urea prepolymer is smaller than the lower limit, the curing rate after mixing the first liquid composition and the second liquid composition may decrease, and the productivity in the production of the three-dimensional structure may decrease. is there. On the other hand, when the number average molecular weight of the urea prepolymer exceeds the upper limit, the viscosity of the first liquid composition increases and it may be difficult to mix with the second liquid composition.

When the first liquid composition contains the prepolymer, the lower limit of the content of the prepolymer in the first liquid composition is preferably 10% by mass, more preferably 20% by mass, further preferably 35% by mass, 40% by mass is particularly preferred. On the other hand, the upper limit of the content is preferably 80% by mass, more preferably 70% by mass, still more preferably 60% by mass, and particularly preferably 50% by mass. When the content is smaller than the lower limit, the polyol component and / or the polyamine component necessary for curing the first liquid composition is increased, so that the volume of the second liquid composition is increased and the first liquid composition is increased. May be difficult to mix with. On the other hand, when the content exceeds the upper limit, the content of the polyisocyanate in the first liquid composition is decreased, which may increase the viscosity and make it difficult to mix with the second liquid composition.

When the modeling material contains the prepolymer, the lower limit of the content of the prepolymer in the modeling material is preferably 10% by mass, more preferably 15% by mass, and even more preferably 20% by mass. On the other hand, the upper limit of the content is preferably 45% by mass, and more preferably 30% by mass. When the content is smaller than the lower limit, the content of the polyol component and / or the polyamine component increases, so that the curing speed after mixing the first liquid composition and the second liquid composition becomes too high, and the modeling material There is a risk that it may be difficult to manufacture a three-dimensional structure. On the contrary, when the content exceeds the upper limit, the content of the polyol component and / or the polyamine component is decreased, so that the curing rate after mixing the first liquid composition and the second liquid composition is decreased, and 3 There is a possibility that the productivity in the production of the three-dimensional structure decreases.

(Polyisocyanate)
As a polyisocyanate used for a 1st liquid composition, the thing similar to the polyisocyanate illustrated as a raw material of the said urethane prepolymer, etc. can be mentioned, for example. However, the polyisocyanate contained in the first liquid composition may be the same as or different from the polyisocyanate used in the synthesis of the prepolymer contained in the first liquid composition.

When the first liquid composition contains the polyisocyanate, the lower limit of the content of the polyisocyanate in the first liquid composition is preferably 20% by mass, more preferably 30% by mass, further preferably 35% by mass, 40% by mass is particularly preferred. On the other hand, as an upper limit of content of the said polyisocyanate, 90 mass% is preferable, 80 mass% is more preferable, and 60 mass% is further more preferable. When content of the said polyisocyanate is smaller than the said minimum, the viscosity of a 1st liquid composition increases and there exists a possibility that it may become difficult to mix a 1st liquid composition and a 2nd liquid composition. On the other hand, when the content of the polyisocyanate exceeds the upper limit, the polyol component and / or the polyamine component necessary for curing the first liquid composition increases, so that the volume of the second liquid composition increases. Therefore, it may be difficult to mix with the first liquid composition.

When the modeling material contains the polyisocyanate, the lower limit of the content of the polyisocyanate in the modeling material is preferably 10% by mass, more preferably 15% by mass, and even more preferably 20% by mass. On the other hand, as an upper limit of content of the said polyisocyanate, 50 mass% is preferable, 35 mass% is more preferable, and 30 mass% is further more preferable. When content of the said polyisocyanate is smaller than the said minimum, the hardening rate after mixing of a 1st liquid composition and a 2nd liquid composition may become too quick, and manufacture of the three-dimensional molded item by the said modeling material may become difficult. There is. On the other hand, when the content of the polyisocyanate exceeds the upper limit, the curing rate after mixing the first liquid composition and the second liquid composition is decreased, and the productivity in manufacturing the three-dimensional structure may be decreased. There is.

[Method for producing first liquid composition]
The first liquid composition can be obtained, for example, by a method in which the long-chain polyol and / or the long-chain polyamine is reacted with an excess amount of the polyisocyanate with respect to the long-chain polyol and / or the long-chain polyamine. it can. The first liquid composition can also be obtained by separately preparing the prepolymer and mixing the prepolymer and the polyisocyanate. In addition, what is necessary is just to add arbitrary components, such as a plasticizer mentioned later, at arbitrary timing as needed.

[Second liquid composition]
The second liquid composition preferably contains at least one soft segment component of a long-chain polyol and a long-chain polyamine and at least one hard segment component of a chain extender and a crosslinking agent.

The upper limit of the viscosity at 80 ° C. of the second liquid composition is preferably 400 mPa · s, more preferably 300 mPa · s. On the other hand, the lower limit of the viscosity of the second liquid composition at 80 ° C. is not particularly limited, but is, for example, 50 mPa · s. When the viscosity at 80 ° C. of the second liquid composition exceeds the above upper limit, it may be difficult to mix with the first liquid composition.

(Long chain polyol and long chain polyamine)
Examples of the long-chain polyol and the long-chain polyamine used in the second liquid composition include the same as the long-chain polyol and the long-chain polyamine exemplified as the raw material for the prepolymer. The long-chain polyol and the long-chain polyamine contained in the second liquid composition may be the same as or different from the long-chain polyol and the long-chain polyamine used for the synthesis of the prepolymer contained in the first liquid composition.

When the second liquid composition contains the soft segment component, the lower limit of the content of the soft segment component in the second liquid composition is preferably 30% by mass, more preferably 35% by mass, and further 45% by mass Preferably, 70% by mass is particularly preferable, and 80% by mass is even more particularly preferable. On the other hand, the upper limit of the content is preferably 97% by mass, more preferably 95% by mass, further preferably 93% by mass, particularly preferably 90% by mass, still more preferably 85% by mass, and most preferably 80% by mass. preferable. When the content is smaller than the lower limit, the volume of the second liquid composition necessary for curing the first liquid composition increases, and it is difficult to mix the first liquid composition and the second liquid composition. There is a risk of becoming. On the other hand, when the content exceeds the upper limit, the content of the chain extender, the crosslinking agent, etc. in the second liquid composition is lowered, and it is difficult to adjust the physical properties of the three-dimensional structure formed by the modeling material. There is a risk. In particular, when the second liquid composition contains the long-chain polyamine as the soft segment component and the content exceeds the upper limit, the curing rate after mixing the first liquid composition and the second liquid composition May become too fast, and it may be difficult to manufacture a three-dimensional structure using the modeling material.

When the modeling material includes the soft segment component, the lower limit of the content of the soft segment component in the modeling material is preferably 10% by mass, more preferably 15% by mass, further preferably 20% by mass, and 25% by mass. % Is particularly preferable, and 35% by mass is further particularly preferable. On the other hand, the upper limit of the content is preferably 65% by mass, more preferably 55% by mass, further preferably 50% by mass, and particularly preferably 45% by mass. When the said content is smaller than the said minimum, the hardening rate after mixing of a 1st liquid composition and a 2nd liquid composition falls, and there exists a possibility that the productivity in manufacture of a three-dimensional structure may fall. On the other hand, when the content exceeds the upper limit, the content of the prepolymer, chain extender, crosslinking agent, etc. may be reduced, making it difficult to adjust the physical properties of the three-dimensional structure formed by the modeling material. There is.

(Chain extender)
The chain extender used for the second liquid composition improves the toughness of a three-dimensional structure formed from the modeling material. As the chain extender, for example, a short chain diol, a short chain diamine or the like can be used.

A short chain diol used as a chain extender is a compound having a molecular weight of less than 300 and having two hydroxyl groups in the molecule. Examples of the short-chain diol include aliphatic diols such as 1,4-butanediol, and compounds described in paragraph [0018] of JP-A-2015-209538. As the short chain diol, an aliphatic diol is preferable, and 1,4-butanediol is more preferable.

The short chain diamine used as the chain extender is a compound having two amino groups in the molecule and having a molecular weight of less than 300. Examples of the short chain diamine include diethylmethylbenzenediamine (DETDA) and compounds described in paragraph [0040] of JP-T-2015-533383. As the short chain diamine, DETDA is preferable.

When the second liquid composition contains the chain extender, the lower limit of the content of the chain extender in the second liquid composition is preferably 1% by mass, more preferably 3% by mass, and further more preferably 5% by mass. 10% by mass is preferable. On the other hand, the upper limit of the content of the chain extender is preferably 50% by mass, more preferably 40% by mass, further preferably 35% by mass, particularly preferably 30% by mass, and particularly preferably 20% by mass. When content of the said chain extension agent is smaller than the said minimum, there exists a possibility that it may become difficult to adjust the physical property of the three-dimensional molded item formed with the said modeling material. Conversely, if the content of the chain extender exceeds the upper limit, the flexibility of the three-dimensional structure formed by the modeling material may be reduced.

When the modeling material contains the chain extender, the lower limit of the content of the chain extender in the modeling material is preferably 0.5% by mass, and more preferably 3% by mass. On the other hand, the upper limit of the content of the chain extender is preferably 30% by mass, more preferably 20% by mass, further preferably 15% by mass, and particularly preferably 8% by mass. When content of the said chain extension agent is smaller than the said minimum, there exists a possibility that it may become difficult to adjust the physical property of the three-dimensional molded item formed with the said modeling material. On the other hand, when the content of the chain extender exceeds the upper limit, the flexibility of the three-dimensional structure formed by the modeling material may be reduced or the chain extender may bleed out.

(Crosslinking agent)
The crosslinking agent used for the second liquid composition reduces the elastic modulus of the three-dimensional structure formed by the modeling material. As the crosslinking agent, for example, a short chain triol, a short chain tetraol, a short chain triamine, or the like can be used.

The short chain triol used as a crosslinking agent is a compound having a molecular weight of less than 300 and having three hydroxyl groups in the molecule. Examples of the short chain triol include trimethylolpropane, trimethylolethane, glycerin, hexanetriol and the like. Of these, trimethylolpropane is preferred as the short-chain triol.

The short-chain tetraol used as a crosslinking agent is a compound having a molecular weight of less than 300 and having four hydroxyl groups in the molecule. Examples of the short-chain tetraol include pentaerythritol.

The short chain triamine used as a crosslinking agent is a compound having a molecular weight of less than 300 and having three amino groups in the molecule. Examples of the short chain triamine include diethylenetriamine, iminobispropylamine, and bishexamethylenetriamine.

When the second liquid composition contains the cross-linking agent, the lower limit of the content of the cross-linking agent in the second liquid composition is preferably 0.5% by mass, more preferably 1.5% by mass, and 3% by mass. Is more preferable. On the other hand, the upper limit of the content of the crosslinking agent is preferably 15% by mass, and more preferably 5% by mass. When content of the said crosslinking agent is smaller than the said minimum, there exists a possibility that it may become difficult to adjust the physical property of the three-dimensional molded item formed with the said modeling material. Conversely, when the content of the crosslinking agent exceeds the upper limit, the flexibility of the three-dimensional structure formed by the modeling material may be reduced.

When the modeling material contains the crosslinking agent, the lower limit of the content of the crosslinking agent in the modeling material is preferably 0.1% by mass, more preferably 0.3% by mass, and further 0.8% by mass. Preferably, 1.5 mass% is especially preferable. On the other hand, as an upper limit of content of the said crosslinking agent, 8 mass% is preferable, 5 mass% is more preferable, and 3 mass% is further more preferable. When content of the said crosslinking agent is smaller than the said minimum, there exists a possibility that it may become difficult to adjust the physical property of the three-dimensional molded item formed with the said modeling material. On the other hand, when the content of the crosslinking agent exceeds the upper limit, the flexibility of the three-dimensional structure formed by the modeling material may be reduced, or the crosslinking agent may bleed out.

(Plasticizer)
The first liquid composition and / or the second liquid composition may further include a plasticizer as a suitable optional component. The plasticizer used for the modeling material decreases the viscosity of the first liquid composition and / or the second liquid composition, and facilitates mixing of the first liquid composition and the second liquid composition. Moreover, the said plasticizer adjusts the elasticity modulus etc. of the three-dimensional structure formed with the said modeling material. Furthermore, since the plasticizer is a component that has a relatively small influence on the curing reaction and can be blended in a relatively large amount, by adjusting the content thereof, the physical properties of the formed three-dimensional structure can be improved. Can adjust the volume of the first liquid composition and / or the second liquid composition without much influence. Thereby, the mixing volume ratio of the first liquid composition and the second liquid composition can be made closer to 1: 1.

Examples of the plasticizer include diethyl hexyl phthalate, diisononyl phthalate (DINP), dibutyl phthalate, trischloroethyl phosphate, trischloropropyl phosphate (TCPP), 1,2-cyclohexanedicarboxylic acid diisononyl ester, and the like. As the plasticizer, 1,2-cyclohexanedicarboxylic acid diisononyl ester is preferable.

When both the 1st liquid composition and the 2nd liquid composition contain a plasticizer, it is preferred that the 1st liquid composition and the 2nd liquid composition contain the same kind of plasticizer.

When the modeling material contains the plasticizer, the lower limit of the plasticizer content in the modeling material is preferably 3% by mass, more preferably 5% by mass, and even more preferably 10% by mass. On the other hand, as an upper limit of content of the said plasticizer, 40 mass% is preferable, 30 mass% is more preferable, 20 mass% is further more preferable, 15 mass% is especially preferable. When content of the said plasticizer is smaller than the said minimum, there exists a possibility that it may become difficult to adjust the elasticity modulus etc. of the three-dimensional structure formed with the said modeling material. In addition, when adjusting the volume of the first liquid composition and / or the second liquid composition by adjusting the content of the plasticizer, the mixing volume ratio of the first liquid composition and the second liquid composition is sufficient. There is also a possibility that it may not be close to 1: 1. Conversely, when the content of the plasticizer exceeds the upper limit, bleeding out may occur in the three-dimensional structure formed by the method for manufacturing the three-dimensional structure.

When the first liquid composition contains the plasticizer, the lower limit of the plasticizer content in the first liquid composition is preferably 0.5% by mass, and more preferably 2% by mass. On the other hand, as an upper limit of content of the said plasticizer, 50 mass% is preferable and 30 mass% is more preferable. When the volume of the first liquid composition is adjusted by adjusting the content of the plasticizer by adjusting the content of the plasticizer within the above range, the mixed volume of the first liquid composition and the second liquid composition The ratio can be closer to 1: 1.

When the second liquid composition contains the plasticizer, the lower limit of the content of the plasticizer in the second liquid composition is preferably 0.1% by mass, more preferably 0.5% by mass, and 5% by mass. Is more preferable, and 10% by mass is particularly preferable. On the other hand, the upper limit of the content of the plasticizer is preferably 50% by mass, more preferably 40% by mass, further preferably 35% by mass, particularly preferably 30% by mass, further particularly preferably 25% by mass, and 20% by mass. % Is most preferred. When adjusting the liquid amount of the first liquid composition and / or the second liquid composition by adjusting the content of the plasticizer, the content of the plasticizer is within the above range so that the first liquid composition is within the above range. And the mixing volume ratio of the second liquid composition can be made closer to 1: 1. When content of the said plasticizer is smaller than the said minimum, there exists a possibility that it may become difficult to adjust the elasticity modulus etc. of the three-dimensional structure formed with the said modeling material. Conversely, when the content of the plasticizer exceeds the upper limit, the second liquid necessary for curing the first liquid composition by reducing the content of the long-chain polyol and / or the long-chain polyamine. The volume of the composition increases, and it may be difficult to uniformly mix the first liquid composition and the second liquid composition.

(Optional component)
The second liquid composition preferably further contains a catalyst. The second liquid composition may further contain optional components such as a colorant, a light stabilizer, a heat stabilizer, an antioxidant, an antifungal agent, and a flame retardant. In addition, although the said arbitrary component is normally contained in a 2nd liquid composition from a viewpoint of the storage stability of an isocyanate component, it may be contained in the 1st liquid composition.

(catalyst)
The catalyst used for the second liquid composition accelerates the curing reaction between the polyisocyanate component of the first liquid composition and the polyol component of the second liquid composition. Examples of the catalyst include organic tin compounds such as di-n-butyltin dilaurate, dimethyltin dilaurate, dibutyltin oxide, and stannous octylate, organic titanium compounds, organic zirconium compounds, and carboxylate tin salts. And amine-based catalysts such as bismuth carboxylate and triethylenediamine. As said catalyst, from a viewpoint of suppressing discoloration of the three-dimensional structure formed with the said modeling material, catalysts other than an amine catalyst are preferable, an organic tin compound is more preferable, and dimethyl tin dilaurate is further more preferable.

When the second liquid composition contains the catalyst, the lower limit of the content of the catalyst in the second liquid composition is preferably 0.005% by mass, and more preferably 0.02% by mass. On the other hand, the upper limit of the content of the catalyst in the second liquid composition is preferably 0.2% by mass, more preferably 0.1% by mass, further preferably 0.05% by mass, and particularly preferably 0.1% by mass. preferable. When the modeling material includes the catalyst, the lower limit of the content of the catalyst in the modeling material is preferably 0.003 mass%, more preferably 0.006 mass%, and further 0.01 mass%. preferable. On the other hand, the upper limit of the content of the catalyst in the modeling material is preferably 0.15% by mass, more preferably 0.07% by mass, further preferably 0.05% by mass, and particularly preferably 0.025% by mass. . When content of the said catalyst is smaller than the said minimum, the cure rate after mixing of a 1st liquid composition and a 2nd liquid composition falls, and there exists a possibility that the productivity in manufacture of a three-dimensional molded item may fall. On the contrary, when the content of the catalyst exceeds the upper limit, the curing rate after mixing the first liquid composition and the second liquid composition becomes too fast, and it is difficult to produce a three-dimensional structure using the modeling material. There is a risk.

The lower limit of the mass ratio of the first liquid composition and the second liquid composition (first liquid composition: second liquid composition) in the modeling material is preferably 100: 250, more preferably 100: 180, and 100. : 120 is more preferable, 100: 110 is particularly preferable, and 100: 105 is further particularly preferable. On the other hand, the upper limit of the mass ratio is preferably 100: 40, more preferably 100: 70, still more preferably 100: 90, and particularly preferably 100: 95. Thus, a 1st liquid composition and a 2nd liquid composition can be mixed more uniformly by making the said mass ratio into the said range.

[Method for producing second liquid composition]
The second liquid composition can be obtained by, for example, a method of stirring and mixing a long-chain polyol, a long-chain polyamine, or a combination thereof, a chain extender, a crosslinking agent, or a combination thereof, and an optional component. In this case, the stirring time can be, for example, 30 seconds or more and 3 minutes or less.

The prepolymer of the first liquid composition is a urethane prepolymer, the soft segment component of the second liquid composition is a long chain polyol, the hard segment component of the second liquid composition is a short chain diol as a chain extender and a crosslinker It is good that it is a short chain triol. Thus, the prepolymer of the first liquid composition is a urethane prepolymer, the soft segment component of the second liquid composition is a long chain polyol, the hard segment component of the second liquid composition is a short chain diol as a chain extender, and By being a short-chain triol as a cross-linking agent, a three-dimensional structure having polyurethane as a main component can be easily and reliably manufactured using the modeling material.

The prepolymer of the first liquid composition is a urethane prepolymer, the soft segment component of the second liquid composition is a long chain polyol and a long chain polyamine, and the hard segment component of the second liquid composition is a short chain diamine as a chain extender. There should be. Thus, the prepolymer of the first liquid composition is a urethane prepolymer, the soft segment component of the second liquid composition is a long chain polyol and a long chain polyamine, and the hard segment component of the second liquid composition is a chain extender. By being a short-chain diamine, a three-dimensional structure having polyurethane urea as a main component can be easily and reliably manufactured with the modeling material.

<Advantages>
Since the modeling material is easy to mix the first liquid composition and the second liquid composition, the modeling material can be suitably used in a method for manufacturing the three-dimensional structure to be described later.

[Second Embodiment]
<Method for manufacturing a three-dimensional structure>
The method for producing a three-dimensional structure is a method for producing a three-dimensional structure mainly composed of polyurethane or the like using an inkjet 3D printer, and is a first liquid composition that reacts by a pseudo prepolymer method by mixing. And a step of sequentially laminating a synthetic resin layer on the support (sequential laminating step) by discharging the second liquid composition. In the sequential laminating step, the first liquid composition and the second liquid composition are discharged by a 3D printer. Mix immediately before starting.

(3D printer)
As shown in FIG. 1, in the manufacturing method of the three-dimensional structure, the support base A <b> 1 that is a support having a flat upper surface is disposed downward in the vertical direction so as to face the upper surface of the support base A <b> 1. An ink jet 3D printer mainly including the mixed liquid discharge nozzle A2 is used.

[Sequential lamination process]
The method of mixing immediately before discharging the first liquid composition and the second liquid composition in this step is not particularly limited. For example, the first liquid composition and the second liquid composition are mixed from their dedicated tanks or the like. Examples include a method of joining pipes supplied to the discharge portion of the liquid discharge nozzle A2 inside the mixed liquid discharge nozzle A2. Accordingly, the first liquid composition and the second liquid composition are mixed immediately before being discharged from the mixed liquid discharge nozzle A2 of the 3D printer.

Mixing mass ratio of the first liquid composition and the second liquid composition in this step (first liquid composition: second liquid composition), that is, a mass ratio of the discharge amounts of the first liquid composition and the second liquid composition Is preferably 100: 250, more preferably 100: 180, still more preferably 100: 120, particularly preferably 100: 110, and still more preferably 100: 105. On the other hand, the upper limit of the mass ratio is preferably 100: 40, more preferably 100: 70, still more preferably 100: 90, and particularly preferably 100: 95. Thus, the mixing volume ratio can be made closer to 1: 1 by setting the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition in the above range. Thereby, a 1st liquid composition and a 2nd liquid composition can be mixed more uniformly.

The mass ratio of the discharge amounts of the first liquid composition and the second liquid composition in this step is preferably kept substantially constant during modeling. Here, the mass ratio of the discharge amount is “substantially constant” when R _A / R _B is 0 when the maximum value of the mass ratio of the discharge amount is 100: R _A and the minimum value is 100: R _B. .95 or more.

The lower limit of the gelation time at 80 ° C. after mixing the first liquid composition and the second liquid composition is preferably 3 seconds and more preferably 5 seconds. On the other hand, the upper limit of the gelation time is preferably 10 seconds and more preferably 8 seconds. When the gelation time is smaller than the lower limit, curing starts before the first liquid composition and the second liquid composition are sufficiently mixed, and as a result, the uniformity of mixing may be reduced. In addition, when the first liquid composition and the second liquid composition are mixed and then discharged by the mixed liquid discharge nozzle A2, the mixed liquid discharge nozzle A2 may be easily clogged. On the contrary, when the gelation time exceeds the upper limit, the productivity in the production of the three-dimensional structure may be reduced.

In this step, the mixed liquid of the first liquid composition and the second liquid composition mixed is discharged from the mixed liquid discharge nozzle A2 immediately after mixing. Specifically, the support base A1 is moved while discharging the mixed liquid droplet X1 of the first liquid composition and the second liquid composition from the mixed liquid discharge nozzle A2 to the upper surface of the support base A1. As a result, the mixed droplet X1 is landed on the upper surface of the support base A1, and the synthetic resin layer Y1 is formed by curing the landed mixed droplet X1.

In this step, the three-dimensional structure can be formed by sequentially laminating the synthetic resin layer Y1 having a planar shape that matches the cross-sectional shape of the three-dimensional structure to be formed. The shape of the synthetic resin layer Y1 to be formed is based on the cross-sectional shape data of the three-dimensional structure created based on, for example, CAD (Computer Aided Design) data, and the movement of the support base A1 and the mixed liquid discharge nozzle A2 It is adjusted by controlling the discharge timing of the mixed droplet X1.

The lower limit of the average volume of the mixed droplet X1 discharged from the mixed liquid discharge nozzle A2 in this step is preferably 1 nL, and more preferably 5 nL. On the other hand, the upper limit of the average volume is preferably 20 μL, and more preferably 1 μL. When the average volume is smaller than the lower limit, it is difficult to control the landing position of the mixed droplet X1 due to the influence of static electricity or the like, and as a result, the modeling accuracy of the formed three-dimensional model may be lowered. On the other hand, when the average volume exceeds the upper limit, the shape of the synthetic resin layer Y1 becomes rough, and as a result, the modeling accuracy of the formed three-dimensional structure may be lowered.

The lower limit of the discharge interval of the mixed droplet X1 in this step is preferably 2 msec, and more preferably 5 msec. On the other hand, the upper limit of the discharge interval is preferably 50 msec, and more preferably 20 msec. When the discharge interval is smaller than the lower limit, it is difficult to control the landing position by combining the plurality of mixed droplets X1 after discharge, and as a result, the modeling accuracy of the formed three-dimensional structure may be lowered. . On the other hand, when the discharge interval exceeds the upper limit, productivity in manufacturing a three-dimensional structure may be reduced.

The lower limit of the nozzle diameter of the mixed liquid discharge nozzle A2 is preferably 0.01 mm, and more preferably 0.05 mm. On the other hand, the upper limit of the nozzle diameter of the mixed liquid discharge nozzle A2 is preferably 0.5 mm, and more preferably 0.3 mm. When the nozzle diameter is smaller than the above lower limit, the average volume of the mixed droplet X1 to be discharged becomes too small, which may reduce the productivity in manufacturing the three-dimensional structure, and the discharge pressure of the mixed droplet X1 increases. If it passes, it will scatter to the circumference after landing, and there is a possibility that the modeling accuracy of the formed three-dimensional model may fall. On the contrary, when the nozzle diameter exceeds the upper limit, the average volume of the mixed droplet X1 to be discharged becomes too large, so that the shape of the synthetic resin layer Y1 becomes rough. As a result, the three-dimensional structure to be formed is formed. There is a possibility that the modeling accuracy is lowered.

The lower limit of the discharge pressure of the mixed droplet X1 is preferably 0.02 MPa, more preferably 0.05 MPa. On the other hand, the upper limit of the discharge pressure of the mixed droplet X1 is preferably 0.5 MPa, and more preferably 0.2 MPa. When the discharge pressure of the mixed droplet X1 is smaller than the lower limit, an error is likely to occur in the landing position of the mixed droplet X1 due to static electricity or the like, and as a result, the modeling accuracy of the formed three-dimensional structure may be lowered. . On the contrary, when the discharge pressure of the mixed droplet X1 exceeds the upper limit, the mixed droplet X1 may scatter around after landing and the modeling accuracy of the formed three-dimensional structure may be lowered.

The liquid temperature of the first liquid composition and the second liquid composition discharged in this step can be set to 20 ° C. or more and 60 ° C. or less, for example. Moreover, as temperature of support stand A1, it can be set as 15 to 150 degreeC, for example.

The average thickness of one layer of the synthetic resin layer Y1 formed in this step can be, for example, 0.05 mm or more and 2 mm or less.

<Advantages>
The manufacturing method of the three-dimensional structure uses a first liquid composition and a second liquid composition that react with each other by a pseudo prepolymer method, so that the mixing volume ratio of the first liquid composition and the second liquid composition is 1. Since it can be in a range relatively close to 1, the first liquid composition and the second liquid composition can be uniformly mixed and reliably cured. As a result, the manufacturing method of the three-dimensional structure can easily and reliably manufacture the three-dimensional structure. Therefore, the manufacturing method of the three-dimensional structure is to manufacture a three-dimensional structure used for personal use products such as shoe soles, grips of motorcycles and bicycles, glasses, masks, ornaments, artificial limbs, training equipment, and the like. It can be used suitably.

In addition, the manufacturing method of the three-dimensional structure is compared with the manufacturing method of the third embodiment to be described later, and after the first liquid composition and the second liquid composition are sufficiently mixed by a line mixer or the like, the mixed liquid is discharged. Since it can discharge with nozzle A2, a three-dimensional structure can be manufactured more reliably. Furthermore, since the manufacturing method of the three-dimensional structure is easier to reduce the average volume of the mixed droplet X1 than the manufacturing method of the third embodiment described later, the modeling accuracy of the formed three-dimensional structure is more improved. Can be improved.

[Third Embodiment]
The method for producing a three-dimensional structure is a method for producing a three-dimensional structure mainly composed of polyurethane or the like using an inkjet 3D printer, and is a first liquid composition that reacts by a pseudo prepolymer method by mixing. And a step of sequentially laminating a synthetic resin layer on the support (sequential laminating step) by discharging the second liquid composition, and the first liquid composition and the second liquid composition are mixed immediately after discharging in the sequential laminating step. To do.

That is, the manufacturing method of the three-dimensional structure is characterized in that in the manufacturing method of the second embodiment, instead of mixing immediately before discharging the first liquid composition and the second liquid composition, mixing is performed immediately after discharging. And

(3D printer)
As shown in FIG. 2, in the manufacturing method of the three-dimensional structure, the support base A11 having a flat upper surface, and the first liquid discharge nozzle A12a and the second liquid discharge nozzle A12b disposed above the support base A11. Inkjet 3D printers are mainly used. The first liquid discharge nozzle A12a and the second liquid discharge nozzle A12b are arranged obliquely downward in the vertical direction so that virtual straight lines passing through the respective central axes merge immediately above the support base A11.

[Sequential lamination process]
In this step, the first liquid composition is discharged by the first liquid discharge nozzle A12a, and the second liquid composition is discharged by the second liquid discharge nozzle A12b. Specifically, the first liquid discharge nozzle A12a and the second liquid discharge nozzle A12b are supported while discharging the first liquid composition droplet X11a and the second liquid composition droplet X11b onto the upper surface of the support base A11. The table A11 is moved. The discharged liquid droplet X11a of the first liquid composition and the liquid droplet X11b of the second liquid composition are combined at the same spot on the upper surface of the support base A11 to form a mixed liquid droplet X11c. The synthetic resin layer Y11 is formed by curing the droplet X11c.

In this step, as in the manufacturing method of the second embodiment, the three-dimensional structure can be formed by sequentially laminating the synthetic resin layer Y11 having a planar shape that matches the cross-sectional shape of the three-dimensional structure to be formed. .

The average volume of the mixed droplet X11c formed in this step can be the same as the average volume of the mixed droplet X1 discharged from the mixed liquid discharge nozzle A2 in the manufacturing method of the second embodiment, for example.

Other conditions and applications in the manufacturing method of the three-dimensional structure can be the same as the conditions in the manufacturing method of the second embodiment.

<Advantages>
Compared with the manufacturing method of the second embodiment, the method for manufacturing the three-dimensional structure can suppress clogging of the nozzle even when the first liquid composition and the second liquid composition that are excellent in reactivity are used.

Moreover, the manufacturing method of the said three-dimensional molded item suppresses a droplet compared with the manufacturing method which collides the droplet of a 1st liquid composition and the 2nd liquid composition in the air in other embodiment mentioned later in the air. it can.

[Fourth Embodiment]
<Method for manufacturing a three-dimensional structure>
The manufacturing method of the three-dimensional structure is a method of manufacturing a three-dimensional structure mainly composed of polyurethane, polyurethane urea or polyurea using an ink jet 3D printer, and reacts by a pseudo prepolymer method by mixing. A step (sequential lamination step) of sequentially laminating a synthetic resin layer on the support by discharging the one-liquid composition and the second liquid composition, and in the sequential lamination step, the first liquid composition and the second liquid composition Mix immediately before dispensing. Also, in the sequential laminating process, the density of the synthetic resin layer is changed for each part by changing the discharge amount of the first liquid composition and the second liquid composition, and thereby the three-dimensional structure having different physical properties for each part. Manufacturing.

(3D printer)
As shown in FIG. 3, in the manufacturing method of the three-dimensional structure, the support base A21 that is a support having a flat upper surface and a mixture that is disposed downward in the vertical direction so as to face the upper surface of the support base A21. An ink jet 3D printer mainly including the liquid discharge nozzle A22 is used.

[Sequential lamination process]
In this step, the mixed liquid of the first liquid composition and the second liquid composition is discharged immediately after mixing by the mixed liquid discharge nozzle A22 of the 3D printer, and the synthetic resin layer Y21 is sequentially stacked on the support base A21. Specifically, the support base A21 is moved while discharging the mixed droplet X21 of the first liquid composition and the second liquid composition from the mixed liquid discharge nozzle A22 onto the upper surface of the support base A21. As a result, the mixed liquid droplet X21 is landed on the upper surface of the support base A21, and the synthetic liquid layer Y21 is formed by curing the landed mixed liquid droplet X21. Next, a mixed droplet X21 is discharged on the formed synthetic resin layer Y21 by the same operation, and a plurality of synthetic resin layers are sequentially stacked.

In this step, the density of the synthetic resin layer Y21 to be formed is changed for each part by changing the discharge pitch in three stages of low pitch, medium pitch or high pitch in the middle. Specifically, at a certain stage during the formation of the synthetic resin layer Y21, the first liquid composition and the second liquid composition are sufficiently discharged by lowering the discharge pitch, and a high density in which no void is formed. The low pitch area Y21a is formed. In another stage, the discharge pitch of the first liquid composition and the second liquid composition is decreased by increasing the discharge pitch as compared with the formation of the low pitch region Y21a, and the medium density with some voids formed. The middle pitch region Y21b is formed. In yet another stage, the discharge amount of the first liquid composition and the second liquid composition is further reduced by increasing the discharge pitch as compared with the formation of the middle pitch region Y21b, and a low density in which a large number of voids are formed. High pitch region Y21c is formed. Thus, the medium pitch region Y21b and the high pitch region Y21c, which are porous regions, are formed in a part of the synthetic resin layer Y21. Thereby, the synthetic resin layer Y21 having three types of regions having different densities and void ratios, that is, the low pitch region Y21a, the middle pitch region Y21b, and the high pitch region Y21c can be formed. Here, the “ejection pitch” means an average interval between the centers of the plurality of mixed droplets X21 landed on the support base A21 in a plan view.

An example of the three-dimensional structure formed in this way is shown in FIG. The three-dimensional structure includes a synthetic resin portion Z and pores H dispersed in the synthetic resin portion Z, and is derived from a nonporous region Za derived from the low pitch region Y21a and a medium pitch region Y21b. It is comprised by three types of area | regions from which the porosity differs from the low porosity area | region Zb and the high porosity area | region Zc originating in the high pitch area | region Y21c. Each region of the three-dimensional structure has different physical properties such as tensile properties and wear resistance due to differences in density and porosity. Specifically, the tensile properties and the wear resistance decrease in a region having a lower density, that is, a region having a higher porosity. Therefore, the three-dimensional structure has the same constituent material but different physical properties for each part. Specifically, the tensile properties and wear resistance of the three-dimensional structure are maximized in the nonporous region Za, minimized in the high porosity region Zc, and non-porous region Za and high in the low porosity region Zb. It is in the middle of the porosity region Zc.

However, the one step shown in FIG. 3 is merely an example of a method of changing the discharge amount of the first liquid composition and the second liquid composition in the manufacturing method of the three-dimensional structure. Specifically, in one step shown in FIG. 3, the discharge amount of the first liquid composition and the second liquid composition was changed by changing the discharge pitch, but the size of the liquid droplets to be discharged was changed. The discharge amount of the first liquid composition and the second liquid composition may be changed. Further, in one step shown in FIG. 3, three types of regions having different densities and porosity are formed by changing the discharge amounts of the first liquid composition and the second liquid composition in three stages. May be changed in two steps, or may be changed in four or more steps. Moreover, the functionally gradient material whose physical properties continuously change can be formed by continuously changing the discharge amount.

Further, in one step shown in FIG. 3, the density and the porosity are changed in the planar direction of the synthetic resin layer Y21 (left and right direction in FIG. 3), but the thickness direction of the synthetic resin layer Y21 (up and down in FIG. 3). Direction) and the density and porosity may be varied. Further, in one step shown in FIG. 3, the porous region is formed only on a part of the synthetic resin layer Y21. However, the porous region may be formed on the entire synthetic resin layer Y21. Furthermore, in FIG. 4, the shape of the hole H of the three-dimensional structure is substantially circular in cross section, but the shape of the hole is not particularly limited. For example, a spherical shape, an elliptical shape, a rectangular parallelepiped shape, a cylindrical shape, a polygonal column, and the like can do. Moreover, in the manufacturing method of the said three-dimensional structure, for example, you may form a honeycomb structure by introduce | transducing a regular hexagonal column-shaped hole at equal intervals. Furthermore, in the manufacturing method of the three-dimensional structure, the porosity may be changed by changing the diameter of the holes H to be introduced, and the number of holes H per volume of the three-dimensional structure is changed. The porosity may be changed.

The lower limit of the discharge pitch in this step is preferably 0.1 mm, and more preferably 0.2 mm. On the other hand, the upper limit of the discharge pitch is preferably 1.2 mm, more preferably 0.9 mm. By making the said discharge pitch into the said range, a physical property can be changed reliably, ensuring the intensity | strength of a three-dimensional molded item. When the said discharge pitch exceeds the said upper limit, there exists a possibility that the intensity | strength of the three-dimensional structure formed may become inadequate.

The lower limit of the discharge pitch change magnification in this step is preferably 2 times, more preferably 2.5 times. On the other hand, the upper limit of the discharge pitch change magnification is preferably 5 times, and more preferably 4 times. When the change rate of the said discharge pitch is smaller than the said minimum, there exists a possibility that the physical property of the three-dimensional structure to be formed cannot fully be changed for every site | part. Conversely, when the change rate of the discharge pitch exceeds the upper limit, the density of a part of the formed three-dimensional structure becomes extremely low, and there is a possibility that breakage starting from that part is likely to occur. Here, “change rate of discharge pitch” means a value obtained by dividing the maximum discharge pitch [mm] during modeling by the minimum discharge pitch [mm].

In this step, the porosity of the porous region may be changed in the range of more than 0 volume% and 45 volume% or less. When the porosity exceeds the upper limit, the strength of the three-dimensional structure may be partially insufficient.

In this step, the apparent density of the three-dimensional structure to be formed may be changed in the range of 0.5 g / cm ^{3 to} 1.2 g / cm ³ . When the porosity is smaller than the lower limit, the strength of the three-dimensional structure may be partially insufficient. Here, “apparent density” means that a sample of 100 mg is taken from any 10 locations of a three-dimensional structure, and the mass (100 mg) is divided by the apparent volume [mm ³ ] calculated from the dimensions of this sample. Means a value calculated by In addition, when a sample of 100 mg cannot be collected from any 10 locations of the three-dimensional structure, the sample with the maximum mass that can be collected is used.

Further, the lower limit of the average porosity of the three-dimensional structure to be formed is preferably 1% by volume, and more preferably 5% by volume. On the other hand, the upper limit of the average porosity is preferably 30% by volume, more preferably 20% by volume. When the said average porosity is smaller than the said minimum, there exists a possibility that the change width for every site | part of the physical property of the said three-dimensional structure may become small. On the contrary, when the average porosity exceeds the upper limit, the strength of the three-dimensional structure may be insufficient. Here, the “average porosity” means an arithmetic average value of the porosity measured at 10 locations.

The average diameter of the holes H of the three-dimensional structure formed in this step is not particularly limited, but the lower limit is preferably 10 μm and more preferably 50 μm. On the other hand, the upper limit of the average diameter of the holes H is preferably 1 mm, and more preferably 200 μm. When the lower limit of the average diameter of the holes H is smaller than the lower limit, the change width of each part of the physical properties of the three-dimensional structure may be small. On the contrary, when the lower limit of the average diameter of the holes H exceeds the upper limit, the strength of the three-dimensional structure may be insufficient. Here, the “average diameter of the holes” means that the cross-section of the three-dimensional structure is observed with a microscope or the like, and the arithmetic average value of the diameters in a perfect circle having the same area as that of any 10 holes. Say.

Other conditions in the manufacturing method of the three-dimensional structure can be the same as those in the second embodiment and the third embodiment.

[Usage]
The manufacturing method of the said three-dimensional structure can be used suitably for manufacture of the molded object from which a physical property differs for every site | part. The physical properties to be changed are not particularly limited, and examples thereof include elastic modulus, hardness, abrasion resistance, and color. Specifically, for example, when producing a sheet-like shaped article, the elongation modulus (M50) when stretched 50% is 3 MPa or more and 40 MPa or less, the tensile strength (TB) is 5 MPa or more and 60 MPa or less, and the elongation at break (EB). May be changed within a range of 100% to 400%, a JIS-A hardness of 60 ° to 100 °, and a DIN wear amount of 200 mm ³ or less.

Here, the elongation modulus, tensile strength, and elongation at break when 50% are stretched are values measured in accordance with JIS-K7312: 1996 “Physical Test Method for Thermosetting Polyurethane Elastomer Moldings”, respectively. Say. The JIS-A hardness is a value measured in accordance with the former JIS-K6301: 1995 “Vulcanized Rubber Physical Test Method”. Further, the DIN wear amount is a value measured in accordance with JIS-K6264-2: 2005 “vulcanized rubber and thermoplastic rubber—determination of wear resistance—part 2: test method”.

The manufacturing method of the three-dimensional structure can be suitably used for manufacturing personal use products such as shoe soles, grips of motorcycles and motorcycles, glasses, masks, ornaments, artificial limbs, training equipment, and the like. Among these, it is necessary to change the physical properties of each shoe sole for each part, and there is a demand for tailor-made to change the shape, physical properties, etc. according to the user. Therefore, the manufacturing method of the said three-dimensional structure can be used especially suitably for manufacture of a shoe sole.

<Advantages>
The manufacturing method of the said three-dimensional structure can manufacture easily and reliably the three-dimensional structure which has a polyurethane, a polyurethane urea, or a polyurea as a main component, and a physical property differs for every site | part.

In addition, the manufacturing method of the three-dimensional structure is compared with the manufacturing method of the fifth embodiment to be described later, and after the first liquid composition and the second liquid composition are sufficiently mixed by a line mixer or the like, the mixed liquid is discharged. Since it can discharge with nozzle A22, a three-dimensional structure can be manufactured more reliably. Furthermore, since the method for manufacturing the three-dimensional structure easily reduces the average volume of the mixed droplet X21, it is possible to further improve the modeling accuracy of the formed three-dimensional structure.

Furthermore, the manufacturing method of the said three-dimensional structure is compared with the manufacturing method from 6th Embodiment to 9th Embodiment mentioned later, and mix volume ratio of a 1st liquid composition and a 2nd liquid composition during modeling. Even if it is not changed, the physical properties of the three-dimensional structure to be formed can be changed for each part, so that it is possible to suppress poor curing due to a change in the mixing volume ratio.

[Fifth Embodiment]
<Method for manufacturing a three-dimensional structure>
The manufacturing method of the three-dimensional structure is a method of manufacturing a three-dimensional structure mainly composed of polyurethane, polyurethane urea or polyurea using an ink jet 3D printer, and reacts by a pseudo prepolymer method by mixing. A step (sequential lamination step) of sequentially laminating a synthetic resin layer on the support by discharging the one-liquid composition and the second liquid composition, and in the sequential lamination step, the first liquid composition and the second liquid composition Mix immediately after discharge. Further, in the sequential lamination process, the density of the synthetic resin layer is changed for each part by changing the discharge amount of the first liquid composition and the second liquid composition, and thereby the three-dimensional modeling having different physical properties for each part. Manufacturing things.

That is, the manufacturing method of the three-dimensional structure is characterized in that in the manufacturing method of the fourth embodiment, instead of mixing the first liquid composition and the second liquid composition immediately before discharge, they are mixed immediately after discharge. To do.

Other conditions and applications in the manufacturing method of the three-dimensional structure can be the same as those in the manufacturing method of the second to fourth embodiments.

<Advantages>
Compared with the manufacturing method of the fourth embodiment, the method for manufacturing the three-dimensional structure can suppress clogging of the nozzle even when the first liquid composition and the second liquid composition having excellent reactivity are used.

[Sixth Embodiment]
<Method for manufacturing a three-dimensional structure>
The manufacturing method of the three-dimensional structure is a manufacturing method of a three-dimensional structure mainly composed of polyurethane or the like using an ink jet 3D printer, and reacts by mixing with a pseudo prepolymer method, which will be described later. A step of sequentially laminating a synthetic resin layer on the support by discharging the composition and the second liquid composition (sequential laminating step), and immediately before discharging the first liquid composition and the second liquid composition in the sequential laminating step To mix. Moreover, in the manufacturing method of the said three-dimensional structure, the three-dimensional structure from which a physical property differs for every site | part is manufactured by changing the mixing ratio of a 1st liquid composition and a 2nd liquid composition in a lamination | stacking process one by one.

That is, the manufacturing method of the three-dimensional structure is compared with the manufacturing method of the fourth embodiment, instead of sequentially changing the discharge amounts of the first liquid composition and the second liquid composition in the stacking step. The difference is that the mixing ratio of the composition and the second liquid composition is changed.

The first liquid composition used in the manufacturing method of the three-dimensional structure includes at least one prepolymer of urethane prepolymer, urethane urea prepolymer, and urea prepolymer, and polyisocyanate. The second liquid composition contains at least one soft segment component of a long-chain polyol and a long-chain polyamine, and at least one hard segment component of a chain extender and a crosslinking agent.

(3D printer)
In the manufacturing method of the three-dimensional structure, a 3D printer in which the modeling material supply system Z1 shown in FIG. 5 is applied to the 3D printer used in one step of FIG. 1 described in the manufacturing method of the second embodiment is used. Can do.

The modeling material supply system Z1 in FIG. 5 supplies the mixed liquid of the first liquid composition and the second liquid composition to the mixed liquid discharge nozzle A2 of the 3D printer. This modeling material supply system Z1 mainly includes a second liquid tank B and a first liquid tank C. A second liquid supply line b is connected to the second liquid tank B. A first liquid supply line c is connected to the first liquid tank C. The end of the second liquid supply line b opposite to the second liquid tank B and the end of the first liquid line c opposite to the first liquid tank C are one end of the mixed liquid supply line d. It is connected to the. The other end of the mixed liquid supply line d is connected to the mixed liquid discharge nozzle A2 in FIG. The second liquid composition stored in the second liquid tank B and the first liquid composition stored in the first liquid tank C are respectively connected via the second liquid supply line b or the first liquid supply line c. It is supplied to the mixed solution supply line d. The first liquid composition and the second liquid composition supplied to the mixed liquid supply line d are mixed in the mixed liquid supply line d, and then supplied to the mixed liquid discharge nozzle A2 in FIG. The mixed solution supply line d may be provided with a line mixer such as a microstatic mixer in the middle as necessary.

The modeling material supply system Z1 is configured to increase or decrease the supply amounts of the first liquid composition supplied from the first liquid tank C and the second liquid composition supplied from the second liquid tank B, respectively. The mixing ratio of the first liquid composition and the second liquid composition in the mixed liquid supplied to A2 can be changed.

[Sequential lamination process]
In this step, the first liquid composition and the second liquid composition are mixed by the above-described modeling material supply system Z1 and discharged immediately thereafter to form a synthetic resin layer on the support. In this step, the mixing ratio of the first liquid composition and the second liquid composition is changed by increasing or decreasing the supply amount of the first liquid composition and the second liquid composition. Thereby, the physical property of the three-dimensional structure to be formed can be changed for each part.

The number of times of changing the mixing ratio of the first liquid composition and the second liquid composition in this step may be only once or may be multiple times. In this step, the mixing ratio of the first liquid composition and the second liquid composition may be changed stepwise, or may be gradually changed, but is preferably changed gradually. As described above, the gradient functional material can be formed by gradually changing the mixing ratio of the first liquid composition and the second liquid composition in this step.

As a method of changing the mixing ratio of the first liquid composition and the second liquid composition in this step, a method of increasing or decreasing the other while keeping one supply amount constant among the first liquid composition and the second liquid composition And a method of increasing or decreasing both supply amounts.

The lower limit of the mixing ratio change rate of the first liquid composition and the second liquid composition during modeling is preferably 3%, and more preferably 7%. On the other hand, the upper limit of the change ratio of the mixing ratio is preferably 20%, and more preferably 12%. When the mixing ratio change rate is smaller than the lower limit, the width of change for each part of the physical properties of the formed three-dimensional structure may be reduced. On the contrary, when the mixing ratio change rate exceeds the upper limit, one of the isocyanate component and the polyol component and / or the polyamine component is excessive in the mixed liquid of the first liquid composition and the second liquid composition, and the curing reaction May become insufficient. Here, the “mixing ratio change rate” refers to the minimum value of the mixing mass ratio (first liquid composition / second liquid composition) of the first liquid composition and the second liquid composition during modeling “R _min ”. , A value represented by the following formula when the maximum value is “R _max ”.
Rate of change in mixing ratio (%) = 100 × (R _max −R _min ) / R _min

[Usage]
The manufacturing method of the said three-dimensional structure can be used suitably for manufacture of the molded object from which a physical property differs for every site | part. The physical properties to be changed are not particularly limited, and examples thereof include elastic modulus, hardness, abrasion resistance, and color. Specifically, for example, when producing a sheet-like shaped article, the elongation modulus (M50) at 50% elongation is 1.5 MPa to 12 MPa, the tensile strength (TB) is 5 MPa to 60 MPa, and elongation at break ( EB) may be changed within a range of 200% to 400%, a JIS-A hardness of 50 ° to 100 °, and a DIN wear amount of 120 mm ³ or less.

The composition of the first liquid composition and the second liquid composition, other conditions, applications, and the like in the method for manufacturing the three-dimensional structure can be the same as those in the manufacturing method of the second embodiment.

<Advantages>
The manufacturing method of the said three-dimensional structure can change the physical property of the formed three-dimensional structure for every site | part by changing the mixing ratio of a 1st liquid composition and a 2nd liquid composition during modeling. it can. Moreover, since the manufacturing method of the said three-dimensional structure uses the 1st liquid composition and 2nd liquid composition which react with a pseudo prepolymer method as a modeling material, even if it changes a mixing ratio during modeling, its mixing volume It is easy to maintain the ratio in a range relatively close to 1: 1. Therefore, the manufacturing method of the three-dimensional structure can easily and reliably manufacture a three-dimensional structure having polyurethane or the like as a main component and having different physical properties for each part.

Further, the manufacturing method of the three-dimensional structure is simpler than the structure of the modeling material supply system of the 3D printer to be used, as compared with the seventh embodiment, the eighth embodiment, the tenth embodiment, and the eleventh embodiment described later. Therefore, it is easy to reduce the equipment cost. Furthermore, the manufacturing method of the three-dimensional structure is compared with the manufacturing method of the ninth embodiment to be described later, and the first liquid composition and the second liquid composition are reliably mixed and then discharged by the mixed liquid discharge nozzle A2. Therefore, a three-dimensional structure can be manufactured more reliably. Furthermore, since the method for manufacturing the three-dimensional structure easily reduces the average volume of the mixed droplet X1, the modeling accuracy of the formed three-dimensional structure can be further improved.

[Seventh Embodiment]
<Method for manufacturing a three-dimensional structure>
The method for producing a three-dimensional structure is a method for producing a three-dimensional structure mainly composed of polyurethane or the like using an inkjet 3D printer, and is a first liquid composition that reacts by a pseudo prepolymer method by mixing. And a step of sequentially laminating a synthetic resin layer on the support by discharging the second liquid composition (sequential lamination step), and mixing immediately before discharging the first liquid composition and the second liquid composition in the sequential lamination step To do. In the manufacturing method of the three-dimensional structure, at least one of the composition of the first liquid composition and the composition of the second liquid composition is changed in a sequential lamination step.

The manufacturing method of the three-dimensional structure is compared with the manufacturing method of the sixth embodiment, instead of sequentially changing the mixing ratio of the first liquid composition and the second liquid composition in the stacking step, the first liquid composition. The point which changes the physical property of the three-dimensional structure formed by changing the composition of this and / or the composition of a 2nd liquid composition for every site | part differs. However, in the present embodiment, the composition may be changed and the mixing ratio of the first liquid composition and the second liquid composition may be changed.

(3D printer)
In the manufacturing method of the three-dimensional structure, the first liquid composition and / or the first liquid composition is preliminarily mixed with a 3D printer used in one step of FIG. 1 described in the manufacturing method of the second embodiment by premixing plural kinds of raw materials. A 3D printer to which a modeling material supply system for preparing a two-component composition is applied can be used. An example of such a modeling material supply system is shown in FIG.

The modeling material supply system Z2 in FIG. 6 supplies the mixed liquid of the first liquid composition and the second liquid composition to the mixed liquid discharge nozzle A2 of the 3D printer. This modeling material supply system Z2 mainly includes two second liquid material tanks E and a first liquid tank C. A second liquid material supply line e1 is connected to each of the two second liquid material tanks E. The ends of the two second liquid material supply lines e1 opposite to the second liquid material tank E are connected to the line mixer F, respectively. A second liquid supply line e2 is connected to the line mixer F. A first liquid supply line c is connected to the first liquid tank C. An end of the second liquid supply line e2 opposite to the line mixer F and an end of the first liquid line c opposite to the first liquid tank C are connected to one end of the mixed liquid supply line d. Has been. The other end of the mixed liquid supply line d is connected to the mixed liquid discharge nozzle A2 in FIG.

In the two second liquid raw material tanks E, two kinds of raw materials constituting the second liquid composition are respectively stored. The two kinds of raw materials are respectively supplied to the line mixer F via the second liquid raw material supply line e1. The two types of raw materials supplied to the line mixer F are mixed to prepare a second liquid composition, and then supplied to the mixed liquid supply line d via the second liquid supply line e2. The first liquid composition stored in the first liquid tank C is supplied to the mixed liquid supply line d via the first liquid supply line c. The first liquid composition and the second liquid composition supplied to the mixed liquid supply line d are mixed in the mixed liquid supply line d, and then supplied to the mixed liquid discharge nozzle A2 in FIG. The mixed solution supply line d may be provided with a line mixer such as a microstatic mixer in the middle as necessary.

The modeling material supply system Z2 changes the composition of the second liquid composition supplied to the mixed liquid supply line d by changing the supply amounts of the two kinds of raw materials supplied from the two second liquid raw material tanks E. Can be made.

The raw material constituting the second liquid composition is not particularly limited as long as it can be prepared into the second liquid composition by mixing, and may include only one component among the components included in the second liquid composition. In addition, it may contain two or more components. The raw material may include a soft segment component and a hard segment component, and may be a composition that can be used alone or as the second liquid composition.

The line mixer F is preferably a microstatic mixer which is a kind of static mixer without a drive unit from the viewpoint of efficiently mixing the raw materials constituting the second liquid composition.

In FIG. 6, the modeling material supply system Z <b> 2 that stores the two kinds of raw materials constituting the second liquid composition in separate tanks and prepares the second liquid composition by mixing the two kinds of raw materials has been described. However, other modeling material supply systems can be applied to the 3D printer. Specifically, three or more kinds of raw materials constituting the second liquid composition may be stored in separate tanks, and the second liquid composition may be prepared by mixing these three or more kinds of raw materials. In order to change the composition of the first liquid composition, two or more kinds of raw materials constituting the first liquid composition are stored in separate tanks, and the first liquid composition is mixed by mixing the two or more kinds of raw materials. May be adjusted. In this case, in order to change the composition of the second liquid composition, one prepared by mixing two or more kinds of raw materials stored in separate tanks may be supplied. And may be supplied in a constant composition. Further, the line mixer F may be omitted.

[Sequential lamination process]
In this step, the first liquid composition and / or the second liquid composition prepared by premixing two or more kinds of raw materials, and the first liquid composition or the second liquid composition separately prepared as necessary. A synthetic resin layer is formed on the support by further mixing the product and discharging immediately after that. In this step, the composition of the first liquid composition and / or the second liquid composition is changed by changing the blending amount of the two or more kinds of raw materials to be premixed. Thereby, the physical property of the three-dimensional structure to be formed can be changed for each part. The number of times of changing the composition of the first liquid composition and / or the second liquid composition in this step may be only once or may be multiple. Further, in this step, the composition of the first liquid composition and / or the second liquid composition may be changed stepwise or may be gradually changed. From the above, it is preferable to change gradually. In this step, the composition of the first liquid composition and / or the second liquid composition may be changed, and the mixing ratio of the first liquid composition and the second liquid composition may be changed.

Examples of the method of changing the composition of the first liquid composition and / or the second liquid composition in this step include (A) a method of changing the composition of the prepolymer of the first liquid composition, and (B) the second liquid. A method of changing the composition of the soft segment component of the composition, (C) a method of changing the composition of the hard segment component of the second liquid composition, (D) any of the first liquid composition and / or the second liquid composition Examples thereof include a method for changing the composition of the components. In this step, the methods (A) to (D) can be performed alone or in combination.

((A) Method of changing composition of prepolymer of first liquid composition)
Examples of the method for changing the composition of the prepolymer of the first liquid composition include a method of preparing two or more kinds of prepolymers having different number average molecular weights and changing the blending ratio of the two or more kinds of prepolymers. It is done.

((B) Pattern for changing the composition of the soft segment component of the second liquid composition)
As a method for changing the composition of the soft segment component of the second liquid composition, for example, two or more types of soft segment components having different number average molecular weights are prepared, and the mixing ratio of the two or more types of soft segment components is changed. Or a method of increasing or decreasing the content of one kind of soft segment component.

When changing the blending ratio of two or more kinds of soft segment components of the second liquid composition, the lower limit of the change width of the content of the specific one kind of soft segment component in the second liquid composition is 5% by mass. Preferably, 15 mass% is more preferable. On the other hand, the upper limit of the change width is preferably 50% by mass, and more preferably 35% by mass. By making the said change width into the said range, the physical property of the three-dimensional structure to be formed can be changed moderately. Here, the “change width of the content” means that the content [mass%] when the content of the specific component in the first liquid composition or the second liquid composition is maximized in the sequential lamination step, from the above A value obtained by subtracting the content [% by mass] when the content of a specific component is minimized.

((C) Method of changing the composition of the hard segment component of the second liquid composition)
As a method for changing the composition of the hard segment component of the second liquid composition, for example, a chain extender and a crosslinking agent are prepared as the hard segment component, and the blending ratio of the chain extender and the crosslinking agent is changed. The method of increasing / decreasing content of a hard segment component of a seed | species etc. is mentioned.

When changing the composition of the hard segment component of the second liquid composition, the lower limit of the change width of the chain extender content in the second liquid composition is preferably 2% by mass, and more preferably 8% by mass. On the other hand, the upper limit of the change width of the chain extender content is preferably 25% by mass, and more preferably 15% by mass. Moreover, as a minimum of the change width of content of the crosslinking agent in a 2nd liquid composition, 0.5 mass% is preferable and 2 mass% is more preferable. On the other hand, the upper limit of the change width of the content of the crosslinking agent is preferably 15% by mass and more preferably 7% by mass. By setting the change width of the chain extender and the crosslinking agent in the above range, the physical properties of the formed three-dimensional structure can be appropriately changed.

((D) Method of changing the composition of optional components of the first liquid composition and / or the second liquid composition)
As a method of changing the composition of the optional components of the first liquid composition and / or the second liquid composition, for example, a method of including a plasticizer in the second liquid composition and changing the content of the plasticizer, Examples thereof include a method of adding a pigment to the second liquid composition and changing the content of the pigment.

When the plasticizer is included in the second liquid composition and the content of the plasticizer is changed, the lower limit of the change width of the plasticizer content in the second liquid composition is preferably 3% by mass, and 10% by mass. % Is more preferable. On the other hand, the upper limit of the change width of the plasticizer content is preferably 35% by mass, and more preferably 20% by mass. By setting the change width of the plasticizer within the above range, the physical properties of the formed three-dimensional structure can be appropriately changed.

As a method of changing the composition of the first liquid composition and / or the second liquid composition, from the viewpoint of increasing the change width of the physical property for each part of the formed three-dimensional modeling material, the pre-treatment of the first liquid composition is performed. A method of changing at least one of the composition of the polymer and the composition of the soft segment component of the first liquid composition is preferable. Further, from the viewpoint of suppressing the influence on the curing reaction, a method in which a plasticizer is included in the second liquid composition and the content of the plasticizer is changed is also preferable.

In this step, the mixing ratio of the first liquid composition and the second liquid composition usually changes by changing the composition of the first liquid composition and the second liquid composition. However, in this step, from the viewpoint of more reliably mixing the first liquid composition and the second liquid composition, the mixing ratio change rate of the first liquid composition and the second liquid composition during modeling may be reduced. Preferably, the mixing ratio change rate is most preferably 0%. On the other hand, the upper limit of the mixing ratio change rate of the first liquid composition and the second liquid composition during modeling is preferably 100%, and more preferably 30%. When the change ratio of the mixing ratio exceeds the upper limit, the difference in discharge amount between the first liquid composition and the second liquid composition increases, and it may be difficult to mix the first liquid composition and the second liquid composition. There is.

The composition of the first liquid composition and the second liquid composition, other conditions, usage, and the like in the method for manufacturing a three-dimensional structure can be the same as those in the manufacturing method of the sixth embodiment.

<Advantages>
Compared with the manufacturing method of the sixth embodiment and the eighth embodiment, the manufacturing method of the three-dimensional structure has abundant variations of physical property changes for each part of the formed three-dimensional structure. Moreover, since the manufacturing method of the said three-dimensional molded item is easy to maintain the molar ratio of an isocyanate component, a polyol component, and / or a polyamine component in modeling within modeling compared with the manufacturing method of 6th Embodiment. It is easy to suppress local curing failure of the formed three-dimensional structure.

[Eighth Embodiment]
<Method for manufacturing a three-dimensional structure>
The method for producing a three-dimensional structure is a method for producing a three-dimensional structure mainly composed of polyurethane or the like using an inkjet 3D printer, and is a first liquid composition that reacts by a pseudo prepolymer method by mixing. And a step of sequentially laminating a synthetic resin layer on the support by discharging the second liquid composition (sequential lamination step), and mixing immediately before discharging the first liquid composition and the second liquid composition in the sequential lamination step To do. Moreover, in the manufacturing method of the said three-dimensional structure, the three-dimensional structure from which a physical property differs for every site | part is manufactured by changing the mixing ratio of a 1st liquid composition and a 2nd liquid composition in a lamination | stacking process one by one.

The manufacturing method of the three-dimensional structure is a manufacturing method in which the modeling material supply system used for the 3D printer is different in the manufacturing method of the seventh embodiment.

(3D printer)
In the manufacturing method of the three-dimensional structure, a 3D printer in which the modeling material supply system Z3 shown in FIG. 7 is applied to the 3D printer used in one step of FIG. 1 described in the manufacturing method of the second embodiment is used. Can do.

The modeling material supply system Z3 shown in FIG. 7 supplies the mixed liquid of the first liquid composition and the second liquid composition to the mixed liquid discharge nozzle A2 of the 3D printer. This modeling material supply system Z3 mainly includes three second liquid tanks G and a first liquid tank C. A second liquid supply subline g1 is connected to each of the three second liquid tanks G. The three second liquid supply sublines g1 are joined together to form one second liquid supply line g2. A first liquid supply line c is connected to the first liquid tank C. The end of the second liquid supply line g2 opposite to the second liquid supply subline g1 and the end of the first liquid line c opposite to the first liquid tank C are one end of the mixed liquid supply line d. Connected to the department. The other end of the mixed liquid supply line d is connected to the mixed liquid discharge nozzle A2 in FIG.

In the three second liquid tanks G, three kinds of second liquid compositions having different compositions are respectively stored and supplied to the mixed liquid supply line d via the second liquid supply subline g1 and the second liquid supply line g2. The The first liquid composition stored in the first liquid tank C is supplied to the mixed liquid supply line d via the first liquid supply line c. The first liquid composition and the second liquid composition supplied to the mixed liquid supply line d are mixed in the mixed liquid supply line d, and then supplied to the mixed liquid discharge nozzle A2 in FIG. The mixed solution supply line d may be provided with a line mixer such as a microstatic mixer in the middle as necessary.

The modeling material supply system Z3 supplies the second liquid composition from one specific second liquid tank G among the three second liquid tanks G to the mixed liquid supply line d. Further, the modeling material supply system Z3 arbitrarily switches the second liquid tank G supplying the second liquid composition during modeling, and thereby the composition of the second liquid composition supplied to the mixed liquid supply line d. Can be changed in three ways.

In addition, although FIG. 7 demonstrated the modeling material supply system Z3 which stores three types of 2nd liquid compositions in a separate tank, and changes the composition of the 2nd liquid composition to supply in three ways, the said three-dimensional It is also possible to employ other configurations in the manufacturing method of the shaped article. Specifically, two or four or more second liquid compositions may be stored in separate tanks, and the composition of the supplied second liquid composition may be changed to two or four or more. Further, two or more kinds of first liquid compositions may be stored in separate tanks, and the composition of the first liquid composition may be changed in two or more by switching the tank that supplies the first liquid composition. In this case, with respect to the second liquid composition, two or more kinds of second liquid compositions are stored in separate tanks, and the composition is changed in two or more by switching the tank that supplies the second liquid composition. Alternatively, the composition may be constant by storing in one tank.

[Sequential lamination process]
In this step, the first liquid composition and the second liquid composition are mixed and discharged immediately thereafter to form a synthetic resin layer on the support. Moreover, in this process, the composition of the 1st liquid composition and / or 2nd liquid composition which are provided for mixing is changed by switching the tank which supplies a 1st liquid composition and a 2nd liquid composition. Thereby, the physical property of the three-dimensional structure to be formed can be changed for each part. The number of times of changing the composition of the first liquid composition and / or the two-liquid composition in this step may be only once or may be multiple times. In this step, the composition of the first liquid composition and / or the second liquid composition may be changed, and the mixing ratio of the first liquid composition and the second liquid composition may be changed.

In this step, examples of the method for changing the composition of the first liquid composition and the second liquid composition include the same methods as those described in the seventh embodiment.

The composition of the first liquid composition and the second liquid composition, the other conditions, the use, and the like in the manufacturing method of the three-dimensional structure can be the same as those of the manufacturing method of the seventh embodiment.

[advantage]
Since the manufacturing method of the said three-dimensional structure does not need to prepare the 1st liquid composition and / or the 2nd liquid composition by mixing 2 or more types of raw materials compared with the manufacturing method of 7th Embodiment, There is no risk of component fluctuations in the first liquid composition and / or the second liquid composition due to poor mixing of the raw materials.

[Ninth Embodiment]
<Method for manufacturing a three-dimensional structure>
The method for producing a three-dimensional structure is a method for producing a three-dimensional structure mainly composed of polyurethane or the like using an inkjet 3D printer, and is a first liquid composition that reacts by a pseudo prepolymer method by mixing. And a step of sequentially laminating a synthetic resin layer on the support (sequential laminating step) by discharging the second liquid composition, and the first liquid composition and the second liquid composition are mixed immediately after discharging in the sequential laminating step. . The manufacturing method of the said three-dimensional structure is a sequential lamination process, among the composition of a 1st liquid composition, the composition of a 2nd liquid composition, and the mixing ratio of a 1st liquid composition and a 2nd liquid composition. Change at least one.

That is, the manufacturing method of the three-dimensional structure is compared with the manufacturing method of the sixth to eighth embodiments, instead of mixing the first liquid composition and the second liquid composition immediately before discharging, immediately after discharging. It differs in that it is mixed.

(3D printer)
For the manufacturing method of the three-dimensional structure, for example, a modeling material used in the manufacturing method of the sixth to eighth embodiments for the 3D printer used in one step of FIG. 2 described in the manufacturing method of the third embodiment. A 3D printer to which a modeling material supply system in which the mixed liquid supply line is omitted from the supply system can be used. That is, for example, end portions of the first liquid supply line and the second liquid supply line of the modeling material supply system used in the manufacturing method of the sixth embodiment to the eighth embodiment are the first liquid discharge nozzle A12a and the second liquid in FIG. A 3D printer connected to each of the discharge nozzles A12b can be used.

The composition of the first liquid composition and the second liquid composition, other conditions, applications, etc. in this step can be the same as in the manufacturing method of the sixth embodiment to the eighth embodiment.

<Advantages>
Even if the manufacturing method of the said three-dimensional structure uses the 1st liquid composition and 2nd liquid composition which are excellent in the reactivity compared with the manufacturing method of 6th Embodiment-8th Embodiment, it is clogged with a nozzle. Can be suppressed.

[Tenth embodiment]
<Method for manufacturing a three-dimensional structure>
The manufacturing method of the three-dimensional structure is a manufacturing method of a three-dimensional structure mainly composed of polyurethane or the like using an ink jet 3D printer, and reacts by mixing with a pseudo prepolymer method, which will be described later. A step of sequentially laminating a synthetic resin layer on the support by discharging the composition and the second liquid composition (sequential laminating step), and immediately before discharging the first liquid composition and the second liquid composition in the sequential laminating step To mix. Moreover, in the manufacturing method of the said three-dimensional structure, three-dimensional modeling from which a physical property differs for every site | part by changing at least one among the composition of a 1st liquid composition and a composition of a 2nd liquid composition in a lamination | stacking process one by one. Manufacturing things. Furthermore, in the manufacturing method of the said three-dimensional structure, let mass ratio of the discharge amount of a 1st liquid composition and a 2nd liquid composition be 100: 110 or more and 100: 90 or less in a lamination | stacking process one by one.

The first liquid composition used in the method for producing a three-dimensional structure includes at least one prepolymer among a urethane prepolymer, a urethane urea prepolymer, and a urea prepolymer, a polyisocyanate, and a plasticizer. The second liquid composition contains at least one soft segment component of a long-chain polyol and a long-chain polyamine, at least one hard segment component of a chain extender and a crosslinking agent, and a plasticizer.

That is, the manufacturing method of the three-dimensional structure requires a plasticizer in the first liquid composition and the second liquid composition as compared with the manufacturing methods of the seventh embodiment and the eighth embodiment, and sequentially stacks the steps. However, the difference is that the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition is 100: 110 or more and 100: 90 or less.

(3D printer)
The 3D model manufacturing method uses a 3D printer in which the modeling material supply system Z4 shown in FIG. 8 is applied to the 3D printer used in one step of FIG. 1 described in the manufacturing method of the second embodiment. Can do.

The modeling material supply system Z4 shown in FIG. 8 supplies the mixed liquid of the first liquid composition and the second liquid composition to the mixed liquid discharge nozzle A2 of the 3D printer. This modeling material supply system Z4 mainly includes a soft segment component tank I, a hard segment component tank J, a plasticizer tank K, and a first liquid raw material tank L. A soft segment component supply line i is connected to the soft segment component tank I. A hard segment component supply line j is connected to the hard segment component tank J. Two plasticizer supply lines k are connected to the plasticizer tank K. A first liquid material supply line 1 is connected to the first liquid material tank L.

The end of the soft segment component supply line i opposite to the soft segment component tank I, the end of the hard segment component supply line j opposite to the hard segment component tank J, and the one plasticizer supply line k The end opposite to the plasticizer tank K is connected to the second liquid mixing line mixer M. A second liquid supply line m is connected to the second liquid mixing line mixer M. The end of the other plasticizer supply line k opposite to the plasticizer tank K and the end of the first liquid raw material supply line l opposite to the first liquid raw material tank L are the first liquid mixing line. It is connected to the mixer N. A first liquid supply line n is connected to the first liquid mixing line mixer N. An end of the second liquid supply line m opposite to the second liquid mixing line mixer M and an end of the first liquid supply line n opposite to the first liquid mixing line mixer N are mixed liquid supply. It is connected to one end of the line d. The other end of the mixed liquid supply line d is connected to the mixed liquid discharge nozzle A2 in FIG. The mixed solution supply line d may be provided with a line mixer such as a microstatic mixer in the middle as necessary.

In the soft segment component tank I and the hard segment component tank J, a soft segment component or a hard segment component constituting a part of the second liquid composition is stored. The plasticizer tank K stores a plasticizer constituting a part of the first liquid composition and the second liquid composition. The first liquid raw material tank L stores a mixed liquid of a prepolymer and a polyisocyanate constituting a part of the first liquid composition. The soft segment component, the hard segment component and the plasticizer constituting the second liquid composition are the soft segment component supply line i and the hard segment component supply line from the soft segment component tank I, the hard segment component tank J or the plasticizer tank K, respectively. j or a plasticizer supply line k to be supplied to the second liquid mixing line mixer M. Each component supplied to the second liquid mixing line mixer M is prepared by mixing into a second liquid composition, and then supplied to the mixed liquid supply line d via the second liquid supply line m. The plasticizer constituting the first liquid composition and the mixed liquid are supplied from the plasticizer tank K or the first liquid raw material tank L through the plasticizer supply line k or the first liquid raw material supply line l, respectively. Supplied to the mixer N. Each component supplied to the first liquid mixing line mixer N is prepared into a first liquid composition by mixing, and then supplied to the mixed liquid supply line d via the first liquid supply line n. The first liquid composition and the second liquid composition supplied to the mixed liquid supply line d are mixed in the mixed liquid supply line d, and then supplied to the mixed liquid discharge nozzle A2 in FIG.

The modeling material supply system Z4 increases or decreases the supply amount of each component supplied from the soft segment component tank I, the hard segment component tank J, the plasticizer tank K, and the first liquid raw material tank L, thereby allowing the mixed liquid discharge nozzle A2 to The composition of the first liquid composition and / or the second liquid composition in the supplied mixed liquid can be changed.

It should be noted that the modeling material supply system used in the method for manufacturing the three-dimensional structure can adopt other configurations besides the one described in FIG. Specifically, the raw materials constituting the second liquid composition may be stored in two or four or more tanks, respectively. Moreover, you may store the raw material which comprises a 1st liquid composition in three or more tanks, respectively. Further, the second liquid mixing line mixer M and the first liquid mixing line mixer N may be omitted. Further, the plasticizer used for the preparation of the first liquid composition and the plasticizer used for the preparation of the second liquid composition may be stored in separate tanks.

The raw material constituting the first liquid composition and the raw material constituting the second liquid composition are not particularly limited as long as they can be prepared into the first liquid composition and the second liquid composition by mixing. Only the seed component may be included, or two or more components may be included. In addition, the raw material may be a composition that can be used alone as the first liquid composition or the second liquid composition.

As the line mixer, from the viewpoint of efficient mixing, a micro static mixer which is a kind of static mixer without a drive unit is preferable.

[Sequential lamination process]
In this step, the first liquid composition and / or the second liquid composition prepared by premixing two or more kinds of raw materials, and the first liquid composition or the second liquid composition separately prepared as necessary. A synthetic resin layer is formed on the support by further mixing the product and discharging immediately after that. In this step, the composition of the first liquid composition and / or the second liquid composition is changed by changing the blending amount of the two or more kinds of raw materials. Thereby, the physical property of the three-dimensional structure to be formed can be changed for each part. The number of times of changing the composition of the first liquid composition and / or the second liquid composition in this step may be only once or may be multiple. Further, in this step, the composition of the first liquid composition and / or the second liquid composition may be changed stepwise or may be gradually changed. From the above, it is preferable to change gradually.

Examples of the method for changing the composition of the first liquid composition and / or the second liquid composition in this step include (a) a method of changing the type and / or content of the prepolymer of the first liquid composition, ( b) a method of changing the type and / or content of the plasticizer of the first liquid composition, (c) a method of changing the type and / or content of the soft segment component of the second liquid composition, (d) the first. Examples thereof include a method of changing the type and / or content of the hard segment component of the two-component composition, and (e) a method of changing the type and / or content of the plasticizer of the second solution composition. In this step, the methods (a) to (e) can be performed alone or in combination.

In the case where the composition of the first liquid composition and the second liquid composition is changed by a method such as (a), (c), (d) in this step, the first liquid composition and / or the second liquid composition It is preferable to suppress the change in the mixing volume ratio of the first liquid composition and the second liquid composition by increasing or decreasing the content of the plasticizer. That is, in this step, the first liquid composition and the second liquid composition are obtained by combining the methods (a), (c), (d) and the like and the methods (b) and / or (e). It is preferable to change the composition of the product. Specifically, for example, when the total content of the hard segment component and the soft segment component of the second liquid composition is reduced in this step, the plasticizer content of the first liquid composition is reduced, and / or Or it is good to suppress the change of the mixing volume ratio of a 1st liquid composition and a 2nd liquid composition by the increase in content of the plasticizer of a 2nd liquid composition. Conversely, when the total content of the hard segment component and the soft segment component of the second liquid composition is increased, the plasticizer content of the first liquid composition is increased and / or the second liquid composition The change in the mixing volume ratio of the first liquid composition and the second liquid composition may be suppressed by reducing the plasticizer content of the product.

((A) Method of changing the type and / or content of the prepolymer of the first liquid composition)
As a method of changing the kind and / or content of the prepolymer of the first liquid composition, for example, two or more kinds of prepolymers having different number average molecular weights are prepared, and the blending ratio of the two or more kinds of prepolymers is changed. And a method of replacing a specific prepolymer contained in the first liquid composition with another type of prepolymer.

((B) Method of changing the type and / or content of the plasticizer of the first liquid composition)
As a method of changing the kind and / or content of the plasticizer of the first liquid composition, for example, a method of increasing or decreasing the content of one kind of plasticizer, or a specific plasticizer contained in the first liquid composition A method of replacing with another type of plasticizer is included. When increasing / decreasing content of the specific 1 type of plasticizer contained in a 1st liquid composition, 5 mass% is preferable as a minimum of the change width of the content, and 10 mass% is more preferable. On the other hand, the upper limit of the change width is preferably 35% by mass, and more preferably 25% by mass. By making the fluctuation range within the above range, the mixing volume ratio of the first liquid composition and the second liquid composition is close to 1: 1 when combined with the methods (a), (c), (d), etc. Easy to maintain in range. In addition, in this process, content of the plasticizer in a 1st liquid composition may be temporarily 0 mass% by reducing the content of the plasticizer of a 1st liquid composition.

((C) Method of changing the type and / or content of the soft segment component of the second liquid composition)
As a method for changing the type and / or content of the soft segment component of the second liquid composition, for example, two or more types of soft segment components having different number average molecular weights are prepared, and the combination of the two or more types of soft segment components is prepared. Examples include a method of changing the ratio, a method of increasing or decreasing the content of one kind of soft segment component, a method of replacing a specific soft segment component contained in the second liquid composition with another type of soft segment component, and the like. .

In the case where the content of the specific one kind of soft segment component contained in the second liquid composition is increased or decreased in this step, the lower limit of the change width of the content is preferably 5% by mass, more preferably 20% by mass. . On the other hand, the upper limit of the change width is preferably 50% by mass, and more preferably 40% by mass. By making the said change width into the said range, the physical property of the three-dimensional structure to be formed can be changed moderately.

((D) Method of changing the type and / or content of the hard segment component of the second liquid composition)
As a method of changing the type and / or content of the hard segment component of the second liquid composition, for example, a method of increasing or decreasing the content of one chain extender or the content of one type of crosslinking agent is increased or decreased. Examples thereof include a method and a method of replacing a specific hard segment component contained in the second liquid composition with another type of hard segment component.

When increasing or decreasing the content of the specific one kind of chain extender contained in the second liquid composition in this step, the lower limit of the change width of the content is preferably 1% by mass, more preferably 7% by mass. . On the other hand, the upper limit of the change width of the content of the chain extender is preferably 25% by mass, and more preferably 18% by mass. Further, when the content of the specific one kind of crosslinking agent contained in the second liquid composition is increased or decreased, the lower limit of the change width of the content is preferably 0.5% by mass, and more preferably 2% by mass. . On the other hand, the upper limit of the change width of the content of the crosslinking agent is preferably 15% by mass and more preferably 7% by mass. By setting the change width of the chain extender and the crosslinking agent in the above range, the physical properties of the formed three-dimensional structure can be appropriately changed.

((E) Method of changing the type and / or content of the plasticizer of the second liquid composition)
Examples of the method for changing the type and / or content of the plasticizer in the second liquid composition include, for example, a method for increasing or decreasing the content of one type of plasticizer, and a specific plasticizer contained in the second liquid composition. And a method of replacing with a plasticizer of the above type. In the case where the content of the specific one type of plasticizer contained in the second liquid composition is increased or decreased in this step, the lower limit of the change width of the content is preferably 5% by mass, and more preferably 10% by mass. On the other hand, the upper limit of the change width is preferably 35% by mass, and more preferably 25% by mass. By making the fluctuation range within the above range, the mixing volume ratio of the first liquid composition and the second liquid composition is close to 1: 1 when combined with the methods (a), (c), (d), etc. Easy to maintain in range. In addition, in this process, content of the plasticizer in a 2nd liquid composition may be temporarily 0 mass% by reducing the content of the plasticizer contained in a 2nd liquid composition.

In this step, it is preferable that the total content of plasticizers contained in the first liquid composition and the second liquid composition is constant. That is, when the content of the plasticizer contained in one of the first liquid composition and the second liquid composition is increased by a specific amount, the content of the plasticizer contained in the other composition is It is good to reduce a specific amount. Thus, by making the total content of the plasticizers contained in the first liquid composition and the second liquid composition constant, it is possible to suppress the occurrence of local bleed out in the formed three-dimensional structure. it can.

In this step, the content of one of the hard segment component and the soft segment component contained in the second liquid composition may be increased and the content of the other component may be decreased. In addition, when increasing or decreasing the content of the hard segment component and / or the soft segment component, the content of the plasticizer contained in one of the first liquid composition and the second liquid composition is increased by a specific amount. Moreover, it is good to suppress the fluctuation | variation of the mixing volume ratio of a 1st liquid composition and a 2nd liquid composition by reducing specific content of the plasticizer contained in the other composition. That is, the composition of the first liquid composition and the second liquid composition may be changed by combining the methods (b) and (e) described above and the methods (c) and / or (d). In this way, by changing the composition of the first liquid composition and the second liquid composition, both the good molding state of the formed three-dimensional structure and the magnitude of physical property change for each part are balanced. Can do.

The lower limit of the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition to be mixed in this step (first liquid composition: second liquid composition) is 100: 110, and 100: 105 is preferable. On the other hand, the upper limit of the mass ratio is 100: 90, preferably 100: 95. Thus, by setting the mass ratio within the above range, the volume ratio of the discharge amounts of the first liquid composition and the second liquid composition can be adjusted to a range relatively close to 1: 1. The first liquid composition and the second liquid composition can be mixed more uniformly.

Further, in this step, it is preferable to keep the mass ratio of the discharge amount substantially constant. Specifically, in this step, the variation rate of the mass ratio of the discharge amount is preferably within 5%, and more preferably within 1%. Thus, the quality of the modeling thing obtained can be stabilized by making the fluctuation rate of the mass ratio of the said discharge amount into the said range. Here, the “rate of change in the mass ratio of the discharge amount” is the maximum of the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition (first liquid composition / second liquid composition) in this step. The value is represented by the following formula when the value is R _max and the minimum value is R _min .
Variation rate of mass ratio of discharge amount = 100 × (R _max −R _min ) / R _min

[Usage]
The manufacturing method of the said three-dimensional structure can be used suitably for manufacture of the molded object from which a physical property differs for every site | part. The physical properties to be changed are not particularly limited, and examples thereof include elastic modulus, hardness, abrasion resistance, and color. Specifically, for example, when producing a sheet-like shaped article, the elongation modulus (M50) when stretched 50% is 3 MPa or more and 25 MPa or less, the tensile strength (TB) is 10 MPa or more and 60 MPa or less, and the elongation at break (EB). May be changed within a range of 200% to 400%, a JIS-A hardness of 60 ° to 100 °, and a DIN wear amount of 100 mm ³ or less.

Other conditions, uses, etc. in the method for manufacturing the three-dimensional structure can be the same as those in the manufacturing method of the seventh embodiment and the eighth embodiment.

<Advantages>
Even if the manufacturing method of the said three-dimensional structure compared with the manufacturing method of 7th Embodiment and 8th Embodiment, and changed the composition of a 1st liquid composition and / or a 2nd liquid composition during modeling. The mixing volume ratio can be maintained in a range closer to 1: 1 by adjusting the plasticizer content. Therefore, the manufacturing method of the three-dimensional structure can more easily and reliably manufacture a three-dimensional structure having polyurethane or the like as a main component and having different physical properties for each part.

Furthermore, the manufacturing method of the said three-dimensional structure is compared with the manufacturing method of 11th Embodiment mentioned later, and after mixing a 1st liquid composition and a 2nd liquid composition fully with a line mixer etc., liquid mixture discharge Since it can discharge with nozzle A2, a three-dimensional structure can be manufactured more reliably. Furthermore, since the method for manufacturing the three-dimensional structure easily reduces the average volume of the mixed droplet X1, the modeling accuracy of the formed three-dimensional structure can be further improved.

[Eleventh embodiment]
<Method for manufacturing a three-dimensional structure>
The method for producing a three-dimensional structure is a method for producing a three-dimensional structure mainly composed of polyurethane or the like using an inkjet 3D printer, and is a first liquid composition that reacts by a pseudo prepolymer method by mixing. And a step of sequentially laminating a synthetic resin layer on the support by discharging the second liquid composition (sequential lamination step), and mixing immediately after discharging the first liquid composition and the second liquid composition in the sequential lamination step To do. Moreover, in the manufacturing method of the said three-dimensional structure, three-dimensional modeling from which a physical property differs for every site | part by changing at least one among the composition of a 1st liquid composition and a composition of a 2nd liquid composition in a lamination process sequentially. Manufacturing things. Furthermore, in the manufacturing method of the said three-dimensional structure, let mass ratio of the discharge amount of a 1st liquid composition and a 2nd liquid composition be 100: 110 or more and 100: 90 or less in a lamination process sequentially.

That is, this embodiment is different from the manufacturing method of the tenth embodiment in that the first liquid composition and the second liquid composition are mixed immediately after discharge instead of being mixed immediately before discharge.

(3D printer)
In the manufacturing method of the three-dimensional structure, a mixed liquid is supplied from the modeling material supply system used in the manufacturing method of the tenth embodiment to the 3D printer used in one step of FIG. 2 described in the manufacturing method of the third embodiment. A 3D printer to which a modeling material supply system in which the line is omitted can be used. That is, for example, end portions of the first liquid supply line and the second liquid supply line of the modeling material supply system used in the manufacturing method of the sixth embodiment to the eighth embodiment are the first liquid discharge nozzle A12a and the second liquid in FIG. A 3D printer connected to each of the discharge nozzles A12b can be used.

The composition of the first liquid composition and the second liquid composition, other conditions, applications, etc. in this step can be the same as in the manufacturing method of the tenth embodiment.

<Advantages>
Compared with the manufacturing method of the tenth embodiment, the manufacturing method of the three-dimensional structure can suppress clogging of the nozzle even when the first liquid composition and the second liquid composition that are excellent in reactivity are used.

<Other embodiments>
The present invention is not limited to the above-described embodiment, and can be implemented in a mode in which various changes and improvements are made in addition to the above-described mode.

For example, the first liquid discharge nozzle and the second liquid discharge nozzle included in the 3D printer used in one step of FIG. 2 are arranged obliquely downward in the vertical direction so that a virtual straight line passing through the central axis merges immediately above the support base. However, the virtual straight line may be arranged obliquely downward in the vertical direction so as to join in the air above the support base. That is, after the discharged droplets of the first liquid composition and the liquid droplets of the second liquid composition collide with each other in the air, the formed mixed liquid droplets may land on the upper surface of the support base. . However, from the viewpoint of suppressing the generation of splashes due to the collision of the first liquid composition and the second liquid composition, the 3D printer used in one step of FIG. It is preferable to form mixed droplets by simultaneously landing droplets of the two-component composition on the same location on the upper surface of the support base.

Further, in the manufacturing methods of the sixth embodiment to the eleventh embodiment, the density of the synthetic resin layer is changed for each part by changing the discharge amount of the first liquid composition and the second liquid composition in the sequential lamination process. You may let them.

Furthermore, in the manufacturing method of the second embodiment to the eleventh embodiment, the support base is moved in a state in which the mixed liquid discharge nozzles or the first liquid discharge nozzle and the second liquid discharge nozzle are fixed in sequential lamination. Instead, each nozzle may be moved in a state where the support base is fixed. However, from the viewpoint of ejection accuracy, it is preferable to move the support base with each nozzle fixed.

Furthermore, in the manufacturing methods of the third embodiment, the fifth embodiment, the ninth embodiment, and the eleventh embodiment, the liquid of the first liquid composition discharged from the first liquid discharge nozzle and the second liquid discharge nozzle in sequential lamination. The first liquid composition and the second liquid composition are mixed by simultaneously landing the droplet and the second liquid composition on the same location, but the droplets are landed on the same location with a time difference. The first liquid composition and the second liquid composition may be mixed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[material]
First, the compounds used as raw materials for polyurethane and polyurethane urea in this test example are shown below.

(Polyisocyanate and urethane prepolymer)
Urethane prepolymer: Urethane prepolymer included in Mitsui Chemicals' “L5299” (reaction product of polytetramethylene ether glycol (PTMG) and 4,4′-diphenylmethane diisocyanate (4,4′-MDI))
Polyisocyanate 1: 4,4'-MDI contained in "L5299" of Mitsui Chemicals
Polyisocyanate 2: Pure MDI from Mitsui Chemicals

(Long chain polyol and long chain polyamine)
Long chain polyol: “TERATHANE® 1000” from INVISTA, polytetramethylene ether glycol (PTMG) polyol, number average molecular weight 1,000
Long-chain polyamine 1: “ELASTAMINE (registered trademark) RT1000” manufactured by HANTSMAN, diamine of a copolymer of PTMG and polypropylene glycol, number average molecular weight 1,000
Long-chain polyamine 2: “JEFFAMINE (registered trademark) D2000” from HANTSMAN, polypropylene glycol diamine, number average molecular weight 2,000

(Chain extender and crosslinker)
Chain extender 1 (short chain diol): Mitsubishi Chemical's “1,4 butanediol”, 1,4 butanediol Chain extender 2 (short chain diamine): Ihara Chemical Industry's “Heart Cure 10”, diethylmethyl Benzenediamine (DETDA)
Cross-linking agent (short-chain triol): "Trimethylolpropane" from Mitsubishi Gas Chemical Company, Trimethylolpropane (TMP)

(Plasticizer and catalyst)
Plasticizer: “DINCH®” from BASF, 1,2-cyclohexanedicarboxylic acid diisononyl ester Catalyst: “Fomrez catalyst UL-28” from Momentive, dimethyltin dilaurate

<Manufacture of shaped objects (1)>
In Test Examples 1 to 8 below, a sheet-like molded article mainly composed of polyurethane or the like was manufactured using a desktop coating robot. From these test examples, it was confirmed that by using a modeling material that reacts by the pseudo prepolymer method, it is possible to easily and reliably manufacture a three-dimensional structure using an inkjet 3D printer.

[Test Example 1]
“L5299” of Mitsui Chemicals, which contains a urethane prepolymer and polyisocyanate 1, was used as the first liquid composition. Further, 73.97 parts by mass of the long-chain polyol, 8.93 parts by mass of the chain extender 1, 3.8 parts by mass of the crosslinking agent, and 0.037 parts by mass of the catalyst are reciprocated by Shimazaki Engineering Co., Ltd. The mixture was stirred and mixed for 1 minute and 30 seconds with an agitator “Agitator (registered trademark)”, and the resulting mixture was used as the second liquid composition.

“L5299” is prepared by reacting PTMG having a number average molecular weight of 1,000 with 4,4′-MDI having a molecular weight of 250 and adjusting the isocyanate group content (NCO content) to 20% by mass. is there. Most of the urethane prepolymers contained in this “L5299” are considered to have 4,4′-MDI bonded to both ends of PTMG, so the number average molecular weight is estimated to be about 1,500. The Here, the isocyanate group content of “L5299” can be represented by the following formula (1). According to the following formula (1), when the molecular weight of the isocyanate group is 42 and the number average molecular weight of the urethane prepolymer is 1,500, “L5299” has a urethane prepolymer content of about 49% by mass, 4 , 4′-MDI content is estimated to be about 51 mass%.

(Content of urethane prepolymer [% by mass] × molecular weight of two isocyanate groups / number average molecular weight of urethane prepolymer) + (content of MDI [mass%] × molecular weight of two isocyanate groups / molecular weight of MDI) ) = Isocyanate group content [% by mass] (1)

The first liquid composition and the second liquid composition described above were put into dedicated tanks of a desktop coating robot “SHOTMASTER (registered trademark) 300DS-S” of Musashi Engineering. Thereafter, the first liquid composition and the second liquid composition are discharged from the two nozzles of the desktop type application robot under the following discharge conditions, and each droplet is landed on the same position on the table as a support base. The mixture was reacted to form a cured product. This was repeated to form a 150 mm × 150 mm × 2 mm sheet-like shaped article. The mass ratio of the discharge amounts of the first liquid composition and the second liquid composition (first liquid composition: second liquid composition) was 100 parts by mass: 86.73 parts by mass.

(Discharge condition)
Nozzle diameter: 0.2mm
Discharge pressure: 0.1 MPa
Liquid temperature: 30 ° C
Table temperature: 20 ° C
Discharge interval: 10msec
Average volume of mixed droplets: ~ 10 ⁴ pL

[Test Examples 2 to 8]
A sheet-like shaped article was formed in the same manner as in Test Example 1 except that the components having the types and contents shown in Table 1 were used. In the table, “-” indicates that the component was not used.

Here, since the first liquid composition and the second liquid composition of Test Examples 1 to 8 both have a specific gravity of about 1.1, the mass ratio of the discharge amount substantially matches the volume ratio of the discharge amount. .

Here, the first liquid composition and the second liquid composition used in Test Examples 1 to 4 react by a pseudo prepolymer method. On the other hand, the first liquid composition and the second liquid composition used in Test Examples 5 to 8 react by a so-called one-shot method in which a polyisocyanate and a long-chain polyol and / or a long-chain polyamine are directly reacted.

<Evaluation (Part 1)>
The tensile properties (elongation modulus, tensile strength and elongation at break), hardness, abrasion resistance, and molding state of the sheet-like shaped articles formed in Test Examples 1 to 4 were evaluated by the following methods. Since the surface of the sheet-like shaped articles formed in Test Examples 5 to 8 was not completely cured, only the molded state was evaluated. The evaluation results are shown in Table 2.

[Tensile properties]
In accordance with JIS-K7312: 1996 “Physical Test Method for Thermosetting Polyurethane Elastomer Moldings”, the elongation modulus (M50), tensile strength (TB) and elongation at break (50%) of the sheet-shaped molded article ( EB) was measured. The elongation modulus [MPa] when stretched by 50% can be evaluated as “pass” when 1.5 MPa or more and “fail” when less than 1.5 MPa. The tensile strength [MPa] can be evaluated as “pass” when 5 MPa or more and “fail” when less than 5 MPa. The elongation at break [%] can be evaluated as “pass” when 105% or more and “fail” when less than 105%. These tensile characteristics can be evaluated to be a shaped product obtained by curing the uniformly mixed first liquid composition and second liquid composition when it is acceptable, and uniform when it is unacceptable. It can be evaluated that the molded product is obtained by curing the first liquid composition and the second liquid composition which are not mixed in the first liquid composition.

[hardness]
Using a JIS-A hardness meter, the hardness of the sheet-like shaped article was measured in accordance with the former JIS-K6301: 1995 “Vulcanized Rubber Physical Test Method”. Hardness [°] indicates that the larger the value, the harder it is. When it is 60 ° or more and 95 ° or less, it is moderately hard and can be evaluated as “pass”, and when it is less than 60 °, it is too soft and evaluated as “fail”. If it exceeds 95 °, it is too hard and can be evaluated as “failed”.

[Abrasion resistance]
A DIN abrasion test was performed on a sheet-like shaped article in accordance with JIS-K6264-2: 2005 “Vulcanized rubber and thermoplastic rubber – Determination of wear resistance – Part 2: Test method”, and the amount of wear was measured. . Wear amount in DIN abrasion test [mm ^3] indicates that excellent wear resistance higher the number is less, "pass" in the case of 160 mm ³ or less, the case of 160 mm ³ than can be evaluated as "fail".

[Molded state]
The appearance of the sheet-like shaped product was visually observed and evaluated. The molding state was evaluated as “pass (A)” when the surface was completely cured, and “failed (B)” when at least a part of the surface was in a gel form.

As shown in Table 2, the sheet-like shaped articles formed in Test Examples 1 to 4 passed all of the elongation modulus, tensile strength, elongation at break, hardness, wear resistance, and molding state. From this, in the manufacturing method of a three-dimensional structure mainly composed of polyurethane or the like using an ink jet 3D printer, the first liquid composition and the second liquid composition that react by the pseudo prepolymer method are used. The volume ratio of the discharge amount can be made close to 1: 1, and as a result, it is determined that a three-dimensional structure can be manufactured easily and reliably.

On the other hand, the sheet-like shaped articles formed in Test Examples 5 to 8 failed in the molding state. This is because the first liquid composition and the second liquid composition that react by the one-shot method are used, so the difference in the discharge amount becomes large, and a part of the discharged first liquid composition and the second liquid composition It is determined that this is because of a mixing failure.

<Manufacture of shaped objects (2)>
In the following Test Examples 9 to 11, it was confirmed that a three-dimensional structure with different physical properties can be manufactured for each part by changing the discharge amounts of the first liquid composition and the second liquid composition during modeling. In Test Examples 9 to 11, instead of changing the discharge amounts of the first liquid composition and the second liquid composition during modeling, the discharge amounts of the first liquid composition and the second liquid composition are changed for each test example. As a result, three types of sheet-shaped objects having different densities and void ratios were produced.

[Test Example 9]
The sheet-like shaped article of Test Example 9 was manufactured in the same manner as in Test Example 1 except that the composition and discharge amount of each component were as shown in Table 3 and the discharge pitch of the mixed droplets was 0.25 mm. . In addition, the 1st liquid composition and 2nd liquid composition which are shown in Table 3 are modeling materials which react with a pseudo prepolymer method. Moreover, since the specific gravity of the first liquid composition and the second liquid composition is about 1.1, the mass ratio and the volume ratio of the discharge amount are substantially the same.

[Test Examples 10 to 11]
Except that the discharge pitch was changed as shown in Table 4, the same operation as in Test Example 9 was performed, and the sheet-like shaped articles of Test Examples 10 to 11 were formed.

<Measurement (2)>
The apparent density, porosity, tensile properties (elongation modulus, tensile strength and elongation at break), abrasion resistance, and molding state of the sheet-like shaped articles formed in Test Examples 9 to 11 were measured. Apparent density and porosity were measured by the following methods. Tensile properties, abrasion resistance and molding conditions were measured by the same methods as in Test Examples 1-8. The evaluation results are shown in Table 4.

[Apparent density]
The apparent density [g / cm ³ ] of the sheet-shaped molded article was obtained by dividing the mass by the apparent volume calculated from the overall dimensions.

[Porosity]
The porosity of the above-mentioned sheet-like shaped product is [volume%] obtained by dividing the apparent volume calculated from the overall dimensions by V _a [mm ³ ] and the mass by the true density (1.1 g / cm ³ ). Was calculated by substituting each numerical value for 100 × (V _a −V _b ) / V _a, where V _b [mm ³ ] is the actual volume calculated in (1).

As shown in Table 4, in Test Examples 9 to 11, by changing the discharge pitch for each test example, three types of sheets having good formability and different density, porosity, and various physical properties are shown. A shaped object could be manufactured. From these test examples, in the manufacturing method of the three-dimensional structure, the discharge amount of the first liquid composition and the second liquid composition is changed during modeling, and the density of the formed three-dimensional structure is changed for each part. By doing so, it is determined that the physical properties can be changed for each part while maintaining a good molding state.

<Manufacture of shaped objects (3)>
In Test Examples 12 to 19 below, in the method for producing a three-dimensional structure using the first liquid composition and the second liquid composition that react by the pseudo prepolymer method, the first liquid composition and the second liquid composition are formed during modeling. It was confirmed that by changing the composition and mixing ratio of the liquid composition, it is possible to produce a three-dimensional structure having different physical properties for each part. In Test Examples 12 to 19, instead of changing the composition or mixing ratio of the first liquid composition and the second liquid composition during modeling, the composition of the first liquid composition, the composition of the second liquid composition, Using a plurality of types of modeling materials in which at least one of the mixing ratios of the first liquid composition and the second liquid composition is different, a plurality of types of sheet-shaped modeling objects having different constituent materials were manufactured.

[Test Examples 12 to 19]
Except that the composition of each component was as shown in Table 5 and Table 6, the same operation as in Test Example 1 was carried out to produce sheet-like shaped articles of Test Examples 12 to 19. In Test Examples 12 to 15, a plurality of modeling materials having different compositions or mixing ratios of the first liquid composition and the second liquid composition are used.

Here, since the first liquid composition and the second liquid composition of Test Examples 12 to 19 both have a specific gravity of about 1.1, the mass of the discharge amounts of the first liquid composition and the second liquid composition The ratio substantially coincides with the volume ratio of the discharge amount.

The first liquid composition and the second liquid composition used in Test Examples 12 to 15 are modeling materials that react by a pseudo prepolymer method. On the other hand, the first liquid composition and the second liquid composition used in Test Examples 16 to 19 are modeling materials that react by a so-called one-shot method in which a polyisocyanate and a long-chain polyol and / or a long-chain polyamine are directly reacted. is there.

<Evaluation (Part 3)>
Evaluation of tensile properties (elongation modulus, tensile strength and elongation at break), hardness, abrasion resistance, and molding state of the sheet-like shaped articles formed in Test Examples 12 to 19 by the same methods as in Test Examples 1 to 8 did. Since the surface of the sheet-like shaped articles formed in Test Examples 16 to 19 was not completely cured, only the molded state was evaluated. Table 7 shows the evaluation results.

As shown in Test Examples 12 to 15 in Table 7, using the first liquid composition and the second liquid composition that react by the pseudo prepolymer method as the modeling material, the composition of the first liquid composition and the second liquid composition By changing at least one of the composition of the product and the mixing ratio of the first liquid composition and the second liquid composition, it is possible to produce sheet-like shaped articles having different physical properties while maintaining a good molding state. It was. Hereinafter, Test Examples 12 to 15 will be described in detail.

As can be seen from the blends 12a to 12c of Test Example 12, the blends 13a and 13b of Test Example 13, the blends 14a, 14c and 14d of Test Example 14, and the blends 15a and 15b of Test Example 15, the first liquid composition By changing the composition of the second liquid composition and the mixing ratio of the first liquid composition and the second liquid composition while keeping the composition constant, the physical properties such as tensile properties can be maintained while maintaining a good molding state. I was able to change it. Further, as can be seen from the blends 14a and 14b of Test Example 14, the tensile strength is maintained while maintaining a good molding state by changing the mixing ratio while keeping the compositions of the first liquid composition and the second liquid composition constant. The physical properties such as characteristics could be changed. Further, as can be seen from the blends 14b and 14c of Test Example 14, the composition of the second liquid composition while keeping the composition of the first liquid composition and the mixing ratio of the first liquid composition and the second liquid composition constant. It was possible to change physical properties such as tensile properties while maintaining a good molding state.

From the above, according to the method for manufacturing a three-dimensional structure, it is determined that a three-dimensional structure having polyurethane as a main component and having different physical properties for each part can be easily and reliably manufactured.

On the other hand, the sheet-like shaped articles formed in Test Examples 16 to 19 using the first liquid composition and the second liquid composition that react by the one-shot method as the modeling material failed in the molding state. This is because the first liquid composition and the second liquid composition that react by the one-shot method are used, and thus the difference in the discharge amount between the first liquid composition and the second liquid composition becomes large, and the discharged first liquid composition It is determined that a part of the product and the second liquid composition caused poor mixing. Therefore, when the 1st liquid composition and the 2nd liquid composition which react by a one shot method are used, it is judged that it is naturally difficult to manufacture the three-dimensional molded item from which a physical property differs for every site | part.

<Manufacture of shaped objects (4)>
In Test Examples 20 to 22 below, in the method for producing a three-dimensional structure using the first liquid composition and the second liquid composition that react by the pseudo prepolymer method, the first liquid composition and the second liquid composition are formed during modeling. When changing the composition of the liquid composition, a plasticizer is blended with the first liquid composition and the second liquid composition, and the physical properties are different for each part by adjusting the mass ratio of the discharge amount to a specific range. It was confirmed that a three-dimensional structure can be manufactured more easily and reliably. In Test Examples 20 to 22, instead of changing the composition of the first liquid composition and the second liquid composition during modeling, a plurality of types of modeling with different compositions of the first liquid composition and / or the second liquid composition By using the material, a plurality of types of sheet-shaped objects having different constituent materials were manufactured.

[Test Examples 20 to 22]
Except that the composition of each component was as shown in Tables 8 and 9, operation was performed in the same manner as in Test Example 1 to form sheet-like shaped articles of Test Examples 20 to 22. When the first liquid composition was prepared by blending a plurality of raw materials, the stirring and mixing conditions were the same as the stirring and mixing conditions of the second liquid composition.

These test examples confirmed the relationship between the mixing ratio of the first liquid composition and the second liquid composition and the molding state of the formed object.

Here, since the first liquid composition and the second liquid composition of Test Examples 20 to 22 each have a specific gravity of about 1.1, the mass of the discharge amounts of the first liquid composition and the second liquid composition The ratio substantially coincides with the volume ratio of the discharge amount.

The first liquid composition and the second liquid composition used in Test Examples 20 and 21 are modeling materials that react by the pseudo prepolymer method. The first liquid composition and the second liquid composition used in Test Example 22 are modeling materials that react by the one-shot method.

<Evaluation>
The tensile properties (elongation modulus, tensile strength and elongation at break), hardness, abrasion resistance, and molding state of the sheet-like shaped articles formed in Test Examples 20 to 22 were evaluated by the same methods as in Test Examples 1 to 8. Since the surface of the sheet-shaped article formed in Test Example 22 was not completely cured, only the molded state was evaluated. Table 10 shows the evaluation results.

As shown in Test Example 20 of Table 10, the composition of the first liquid composition / and the second liquid composition is changed, and the discharge amounts of the first liquid composition and the second liquid composition are made substantially equal. Thus, it was confirmed that sheet-like shaped articles having different physical properties such as tensile properties can be produced while maintaining a good molded state. Moreover, as shown in Test Example 21, if the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition is in the range of 100: 110 or more and 100: 90 or less, a good molding state is maintained. I was able to.

On the other hand, as shown in Test Example 22, when the first liquid composition and the second liquid composition that react by the one-shot method are used, the difference in the discharge amounts of the first liquid composition and the second liquid composition is large. Therefore, the first liquid composition and the second liquid composition could not be sufficiently mixed, and as a result, the molding state was rejected.

From these test examples, a plasticizer is contained in the first liquid composition and the second liquid composition that react by the pseudo prepolymer method, and the mass ratio of the discharge amounts of the first liquid composition and the second liquid composition is 100. : It is determined that the physical properties can be changed for each part while maintaining a good molding state by adjusting to 110 or more and 100: 90 or less.

A1, A11, A21 Supports A2, A12, A22 Mixed liquid discharge nozzle A12a First liquid discharge nozzle A12b Second liquid discharge nozzle B Second liquid tank C First liquid tank b Second liquid supply line c First liquid supply line d Mixed liquid supply line E Second liquid raw material tank F Line mixer e1 Second liquid raw material supply line e2 Second liquid supply line G Second liquid tank g1 Second liquid supply subline g2 Second liquid supply lines X1, X11c, X21 Droplet X11a Droplet X11b of the first liquid composition Droplets Y1, Y11, Y21 of the second liquid composition Synthetic resin layer Y21a Low pitch area Y21b Medium pitch area Y21c High pitch area Z Synthetic resin part Za Nonporous area Zb Low porosity region Zc High porosity region H Holes Z1, Z2, Z3, Z4 Modeling material supply system

Claims

A method for producing a three-dimensional structure mainly composed of polyurethane, polyurethane urea or polyurea using an inkjet 3D printer,
A step of sequentially laminating a synthetic resin layer on a support by discharging a first liquid composition and a second liquid composition that react by mixing;
In the sequential lamination step, mixing immediately before or after discharging the first liquid composition and the second liquid composition,
The method for producing a three-dimensional structure, wherein the first liquid composition and the second liquid composition are reacted by a pseudo prepolymer method.
The method for producing a three-dimensional structure according to claim 1, wherein a mass ratio of discharge amounts of the first liquid composition and the second liquid composition is 100: 250 or more and 100: 40 or less.
The density | concentration of the said synthetic resin layer is changed for every site | part by changing the discharge amount of the said 1st liquid composition and the said 2nd liquid composition at the said sequential lamination process. A manufacturing method of a three-dimensional structure.
The method for producing a three-dimensional structure according to claim 3, wherein a porous region is formed in at least a part of the synthetic resin layer in the sequential lamination step.
The method for producing a three-dimensional structure according to claim 4, wherein the porosity of the porous region is changed in the range of more than 0% by volume and 45% by volume or less in the sequential lamination step.
The first liquid composition includes at least one prepolymer of urethane prepolymer, urethane urea prepolymer and urea prepolymer, and polyisocyanate,
The said 2nd liquid composition contains at least 1 sort (s) of soft segment components among a long chain polyol and a long chain polyamine, and at least 1 sort (s) hard segment component among a chain extender and a crosslinking agent. 5. The method for producing a three-dimensional structure according to claim 5.
The method for producing a three-dimensional structure according to claim 6, wherein at least one of the first liquid composition and the second liquid composition further contains a plasticizer.
In the sequential lamination step, at least one of the composition of the first liquid composition, the composition of the second liquid composition, and the mixing ratio of the first liquid composition and the second liquid composition is changed. The manufacturing method of the three-dimensional structure according to claim 6.
The second liquid composition further comprises a plasticizer,
The method for producing a three-dimensional structure according to claim 8, wherein the content of the plasticizer in the second liquid composition is changed in the sequential lamination step.
The first liquid composition and the second liquid composition further include a plasticizer,
In the sequential lamination step, at least one of the composition of the first liquid composition and the composition of the second liquid composition is changed,
The method for producing a three-dimensional structure according to claim 8, wherein a mass ratio of discharge amounts of the first liquid composition and the second liquid composition is 100: 110 or more and 100: 90 or less.
The three-dimensional according to claim 8 or 10, wherein in the sequential lamination step, at least one of a prepolymer composition of the first liquid composition and a hard segment component composition of the second liquid composition is changed. Manufacturing method of a model.
A modeling material for a three-dimensional structure mainly composed of polyurethane, polyurethane urea or polyurea using an inkjet 3D printer,
Comprising a first liquid composition and a second liquid composition that react by mixing;
A modeling material for a three-dimensional structure, wherein the first liquid composition and the second liquid composition are reacted by a pseudo prepolymer method.