JP2023147991A - Hydraulic composition for additive manufacturing device - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 239000000654 additive Substances 0.000 title claims abstract description 75
- 230000000996 additive effect Effects 0.000 title claims abstract description 75
- 239000004568 cement Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000011398 Portland cement Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- -1 expanded shale Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- Producing Shaped Articles From Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、付加製造装置用水硬性組成物に関する。 The present invention relates to a hydraulic composition for additive manufacturing equipment.
近年、付加製造装置（３Ｄプリンタ）の積層用の台の上面に、ノズルから光硬化性樹脂を押し出して、二次元形状として予め設計された未硬化の層状体を形成させ、次いで、この未硬化の層状体に対して光照射を行って硬化させて、硬化した層状体を得て、その後、この硬化した層状体の上に、以上の操作と同様の操作を繰り返して、一層ずつ造形及び硬化を行い、最終的に、三次元形状として予め設計された所望の立体形状を有する積層体である造形物（例えば、精巧な三次元形状を有するもの）を得る技術が、普及している。この技術は、付加製造技術と称されている。
光硬化性樹脂以外の種々の材料（例えば、セメント）を用いた付加製造技術も、開発されている。
自立性及び強度発現性に優れた建設向け立体造形用セメント質材料として、特許文献１には、セメント、（Ａ）骨材、（Ｂ）リグニンスルホン酸系分散剤（Ｒ）とメラミンスルホン酸系分散剤（Ｍ）との質量割合が、Ｒ：Ｍ＝１００：８０～４００である分散剤、（Ｃ）増粘剤、（Ｄ）凝結遅延剤、（Ｅ）酸化物換算でＳｉＯ２を１０～２５質量％含有する非晶質カルシウムアルミノシリケート、（Ｆ）セッコウ、及び（Ｇ）短繊維、を含有する建設向け立体造形用セメント質材料が記載されている。
In recent years, a photocurable resin is extruded from a nozzle onto the top surface of a lamination stand of an additive manufacturing device (3D printer) to form an uncured layered body designed in advance as a two-dimensional shape. The layered body is irradiated with light and cured to obtain a hardened layered body, and then the above-mentioned operations and similar operations are repeated on this hardened layered body to form and harden it layer by layer. BACKGROUND OF THE INVENTION A technique for finally obtaining a shaped object (for example, one having an elaborate three-dimensional shape) that is a laminate having a desired three-dimensional shape designed in advance as a three-dimensional shape has become widespread. This technology is called additive manufacturing technology.
Additive manufacturing techniques using various materials other than photocurable resins (eg, cement) have also been developed.
As a cementitious material for three-dimensional modeling for construction with excellent self-reliance and strength development, Patent Document 1 describes cement, (A) aggregate, (B) ligninsulfonic acid-based dispersant (R), and melaminesulfonic acid-based dispersant (R). A dispersant whose mass ratio with the dispersant (M) is R:M=100:80 to 400, (C) a thickener, (D) a setting retarder, and (E) 10% of SiO 2 in terms of oxide. A cementitious material for three-dimensional modeling for construction is described, which contains ~25% by mass of amorphous calcium aluminosilicate, (F) gypsum, and (G) short fibers.
押出し方式の付加製造装置を用いて水硬性組成物からなる造形物を製造する場合、通常、型枠等が設置されないため、水硬性組成物には、付加製造装置のノズルから押し出された後、硬化するまでの自立性（押し出された水硬性組成物の上部に、新たに水硬性組成物が積層された場合でも、形状を維持する性能）が求められる。
本発明の目的は、付加製造装置用水硬性組成物が硬化するまでの自立性を確保することができ、かつ、収縮の小さい造形物を製造することができる付加製造装置用水硬性組成物を提供することである。
When manufacturing a shaped object made of a hydraulic composition using an extrusion-type additive manufacturing device, a mold or the like is usually not installed. Self-supporting properties until hardening (ability to maintain the shape even when a new hydraulic composition is layered on top of the extruded hydraulic composition) are required.
An object of the present invention is to provide a hydraulic composition for additive manufacturing equipment that can ensure self-reliance until it hardens, and that can produce shaped objects with small shrinkage. That's true.
本発明者は、上記課題を解決するために鋭意検討した結果、セメント及び軽量骨材を含み、セメント１００質量部に対する軽量骨材の量が、８０～１，１００質量部である付加製造装置用水硬性組成物によれば、上記目的を達成できること見出し、本発明を完成した。
すなわち、本発明は、以下の［１］～［７］を提供するものである。
［１］ セメント及び軽量骨材を含む付加製造装置用水硬性組成物であって、上記セメント１００質量部に対する上記軽量骨材の量が、８０～１，１００質量部であることを特徴とする付加製造装置用水硬性組成物。
［２］ 上記軽量骨材は、絶乾密度が２．０ｇ／ｃｍ３以下でかつ吸水率が１０～２０％の人工軽量細骨材である前記［１］に記載の付加製造装置用水硬性組成物。
［３］ 上記付加製造装置用水硬性組成物は、上記軽量骨材以外の骨材を含まない、または、上記軽量骨材１００質量部に対して５０質量部以下の量で、上記軽量骨材以外の骨材を含む前記［１］又は［２］に記載の付加製造装置用水硬性組成物。
As a result of intensive studies to solve the above problems, the present inventor has found that water for additive manufacturing equipment contains cement and lightweight aggregate, and the amount of lightweight aggregate is 80 to 1,100 parts by mass relative to 100 parts by mass of cement. The inventors have discovered that the above object can be achieved by using a hard composition, and have completed the present invention.
That is, the present invention provides the following [1] to [7].
[1] A hydraulic composition for additive manufacturing equipment containing cement and lightweight aggregate, characterized in that the amount of the lightweight aggregate is 80 to 1,100 parts by mass relative to 100 parts by mass of the cement. Hydraulic composition for manufacturing equipment.
[2] The hydraulic composition for additive manufacturing equipment according to [1] above, wherein the lightweight aggregate is an artificial lightweight fine aggregate with an absolute dry density of 2.0 g/cm 3 or less and a water absorption rate of 10 to 20%. thing.
[3] The hydraulic composition for additive manufacturing equipment does not contain aggregates other than the lightweight aggregates, or does not contain aggregates other than the lightweight aggregates in an amount of 50 parts by mass or less based on 100 parts by mass of the lightweight aggregates. The hydraulic composition for an additive manufacturing device according to [1] or [2] above, comprising an aggregate of:
［４］ 上記付加製造装置用水硬性組成物は、「ＪＩＳ Ａ １１２９－３：２０１０」（モルタル及びコンクリートの長さ変化測定方法－第３部：ダイヤルゲージ方法）に準拠して、温度が２０℃でかつ相対湿度が６０％の雰囲気下で、材齢２８日まで気中養生した場合の長さ変化率が、５００×１０－６以下のものである前記［１］～［３］のいずれかに記載の付加製造装置用水硬性組成物。
［５］ 上記付加製造装置用水硬性組成物は、水を含む前記［１］～［４］のいずれかに記載の付加製造装置用水硬性組成物。
［６］ 上記付加製造装置用水硬性組成物は、上記セメント１００質量部に対して２５質量部以下の量で、起泡剤を含む前記［５］に記載の付加製造装置用水硬性組成物。
［７］ 前記［５］又は［６］に記載の付加製造装置用水硬性組成物を付加製造装置に供給する供給工程と、上記付加製造装置において、上記付加製造装置用水硬性組成物を用いて、上記付加製造装置用水硬性組成物からなる造形物を形成させる積層工程、を含むことを特徴とする造形物の製造方法。
[4] The above-mentioned hydraulic composition for additive manufacturing equipment has a temperature of 20°C in accordance with "JIS A 1129-3:2010" (Length change measurement method for mortar and concrete - Part 3: Dial gauge method). Any one of [1] to [3] above, which has a length change rate of 500 × 10 -6 or less when cured in air until the age of 28 days in an atmosphere with a relative humidity of 60%. A hydraulic composition for additive manufacturing equipment as described in .
[5] The hydraulic composition for an additive manufacturing device according to any one of [1] to [4] above, which contains water.
[6] The hydraulic composition for an additive manufacturing device according to the above [5], wherein the hydraulic composition for an additive manufacturing device contains a foaming agent in an amount of 25 parts by mass or less based on 100 parts by mass of the cement.
[7] A supply step of supplying the hydraulic composition for an additive manufacturing device according to [5] or [6] above to the additive manufacturing device, and using the hydraulic composition for an additive manufacturing device in the additive manufacturing device, A method for producing a shaped object, comprising a laminating step of forming a shaped article made of the hydraulic composition for additive manufacturing equipment.
本発明の付加製造装置用水硬性組成物によれば、付加製造装置用水硬性組成物が硬化するまでの自立性を確保することができ、かつ、収縮の小さい造形物を製造することができる。 According to the hydraulic composition for an additive manufacturing device of the present invention, it is possible to ensure self-reliance until the hydraulic composition for an additive manufacturing device is cured, and it is possible to manufacture a shaped object with small shrinkage.
本発明の付加製造装置用水硬性組成物（以下、単に「水硬性組成物」ともいう。）は、セメント及び軽量骨材を含む付加製造装置用水硬性組成物であって、セメント１００質量部に対する軽量骨材の量が、８０～１，１００質量部であるものである。
なお、本明細書中、「付加製造装置用水硬性組成物」の語は、水を含まない組成物（例えば、プレミックス材）、水を含む硬化前の組成物、および、水を含む組成物が硬化してなる硬化体を包含するものである。
セメントとしては、付加製造装置を用いて造形物を造形する際に、該造形物の材料として使用可能な物性を有するセメントを用いることができる。このようなセメントの例としては、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント、白色ポルトランドセメント、超早強ポルトランドセメント等の各種ポルトランドセメント、超速硬セメント、高炉セメント、フライアッシュセメント、アルミナセメント、エコセメント等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The hydraulic composition for additive manufacturing equipment of the present invention (hereinafter also simply referred to as "hydraulic composition") is a hydraulic composition for additive manufacturing equipment containing cement and lightweight aggregate, and has a light weight relative to 100 parts by mass of cement. The amount of aggregate is 80 to 1,100 parts by mass.
In this specification, the term "hydraulic composition for additive manufacturing equipment" refers to compositions that do not contain water (for example, premix materials), compositions that contain water before curing, and compositions that contain water. This includes a cured product obtained by curing.
As the cement, it is possible to use a cement that has physical properties that can be used as a material for a modeled object when the modeled object is modeled using an additive manufacturing device. Examples of such cements include ordinary Portland cement, early-strength Portland cement, medium-heat Portland cement, low-heat Portland cement, white Portland cement, various types of Portland cement such as ultra-early-strength Portland cement, ultra-rapid hardening cement, blast furnace cement, and fried cement. Examples include ash cement, alumina cement, and ecocement. These may be used alone or in combination of two or more.
軽量骨材の絶乾密度は、水硬性組成物の自立性をより向上させる観点からは、好ましくは２．０ｇ／ｃｍ３以下、より好ましくは１．９ｇ／ｃｍ３以下、さらに好ましくは１．８ｇ／ｃｍ３以下、特に好ましくは１．７ｇ／ｃｍ３以下である。
また、入手の容易性や、水硬性組成物の強度発現性の向上等の観点からは、上記絶乾密度は、好ましくは０．８ｇ／ｃｍ３以上、より好ましくは１．０ｇ／ｃｍ３以上、さらに好ましくは１．２ｇ／ｃｍ３以上、特に好ましくは１．４ｇ／ｃｍ３以上である。
The bone dry density of the lightweight aggregate is preferably 2.0 g/cm 3 or less, more preferably 1.9 g/cm 3 or less, still more preferably 1. It is 8 g/cm 3 or less, particularly preferably 1.7 g/cm 3 or less.
In addition, from the viewpoint of ease of availability and improvement of strength development of the hydraulic composition, the absolute dry density is preferably 0.8 g/cm 3 or more, more preferably 1.0 g/cm 3 or more. , more preferably 1.2 g/cm 3 or more, particularly preferably 1.4 g/cm 3 or more.
軽量骨材の吸水率は、好ましくは１０～２０％、より好ましくは１１～１９％、特に好ましくは１２～１８％である。上記吸水率が１０％以上であれば、水硬性組成物の自立性をより向上させることができる。上記吸水率が２０％以下であれば、水硬性組成物の流動性をより向上させることができ、造形物を製造する際の作業性がより向上する。 The water absorption rate of the lightweight aggregate is preferably 10-20%, more preferably 11-19%, particularly preferably 12-18%. If the water absorption rate is 10% or more, the self-supporting properties of the hydraulic composition can be further improved. When the water absorption rate is 20% or less, the fluidity of the hydraulic composition can be further improved, and the workability when manufacturing a shaped object is further improved.
軽量骨材は、品質管理の容易性、及び、軽量骨材を構成する各粒子の粒度及び吸水率のばらつきが少なく、付加製造装置を用いて造形物を製造する際の作業性が向上する等の観点から、人工軽量骨材が好ましい。
軽量骨材は、例えば、膨張粘土、膨張スレート、フライアッシュ、膨張頁岩、ガラス、及び火山灰等から選ばれる一種以上を原料とし、これらを焼成、発泡することで得ることができる
軽量骨材としては、軽量細骨材のみ、または、軽量細骨材と軽量粗骨材の組み合わせを用いることができる。中でも、付加製造装置を用いて造形物を製造する際の作業性の観点から、通常、軽量細骨材のみが用いられる。すなわち、付加製造装置用水硬性組成物はモルタルが好ましい。
Lightweight aggregates are easy to control quality, and there is less variation in the particle size and water absorption rate of each particle that makes up the lightweight aggregates, which improves workability when manufacturing shaped objects using additive manufacturing equipment. From this point of view, artificial lightweight aggregates are preferred.
Lightweight aggregate can be obtained by firing and foaming one or more raw materials selected from expanded clay, expanded slate, fly ash, expanded shale, glass, volcanic ash, etc. , lightweight fine aggregate alone or a combination of lightweight fine aggregate and lightweight coarse aggregate can be used. Among these, from the viewpoint of workability when manufacturing a shaped object using additive manufacturing equipment, only lightweight fine aggregate is usually used. That is, the hydraulic composition for additive manufacturing equipment is preferably mortar.
セメント１００質量部に対する軽量骨材の量は、８０～１，１００質量部、好ましくは１２０～１，０８０質量部、より好ましくは１８０～１，０５０質量部、さらに好ましくは２５０～１，０００質量部、さらに好ましくは３５０～１，０００質量部、さらに好ましくは５００～１，０００質量部、さらに好ましくは８００～１，０００質量部である。上記量が８０質量部未満であると、水硬性組成物の自立性が低下し、積層された造形物の高さが小さくなる。また、造形物の収縮が大きくなる。上記量が１，１００質量部を超えると、水硬性組成物の質量が過大となり、造形物が自重によってつぶれて、水硬性組成物を積層することが困難となる。 The amount of lightweight aggregate relative to 100 parts by mass of cement is 80 to 1,100 parts by mass, preferably 120 to 1,080 parts by mass, more preferably 180 to 1,050 parts by mass, and even more preferably 250 to 1,000 parts by mass. parts, more preferably 350 to 1,000 parts by weight, still more preferably 500 to 1,000 parts by weight, even more preferably 800 to 1,000 parts by weight. If the amount is less than 80 parts by mass, the self-supporting properties of the hydraulic composition will decrease, and the height of the laminated object will become smaller. Moreover, the shrinkage of the shaped object increases. When the amount exceeds 1,100 parts by mass, the mass of the hydraulic composition becomes excessive, the shaped object collapses under its own weight, and it becomes difficult to laminate the hydraulic composition.
付加製造装置用水硬性組成物は、上述した軽量骨材以外の骨材を含まない、または、軽量骨材１００質量部に対して５０質量部以下（好ましくは５～４０質量部、特に好ましくは１０～３５質量部）の量で、軽量骨材以外の骨材を含んでいてもよい。軽量骨材以外の骨材を含むことによって、得られる造形物の強度をより大きくすることができる。
軽量骨材以外の骨材としては、細骨材のみ、または、細骨材と粗骨材の組み合わせが挙げられる。中でも、付加製造装置を用いて造形物を製造する際の作業性の観点から、通常、細骨材のみが好ましい。
細骨材としては、特に限定されず、例えば、川砂、山砂、陸砂、海砂、砕砂、珪砂、及びスラグ細骨材等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
粗骨材としては、特に限定されず、例えば、川砂利、山砂利、陸砂利、海砂利、砕石、及びスラグ粗骨材等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The hydraulic composition for additive manufacturing equipment does not contain aggregates other than the above-mentioned lightweight aggregates, or contains 50 parts by mass or less (preferably 5 to 40 parts by mass, particularly preferably 10 parts by mass) based on 100 parts by mass of lightweight aggregates. 35 parts by mass) may contain aggregates other than lightweight aggregates. By including aggregates other than lightweight aggregates, the strength of the resulting model can be further increased.
Examples of aggregates other than lightweight aggregates include only fine aggregates or a combination of fine aggregates and coarse aggregates. Among these, only fine aggregate is usually preferred from the viewpoint of workability when manufacturing a shaped object using an additive manufacturing device.
The fine aggregate is not particularly limited, and examples thereof include river sand, mountain sand, land sand, sea sand, crushed sand, silica sand, and slag fine aggregate. These may be used alone or in combination of two or more.
The coarse aggregate is not particularly limited, and examples thereof include river gravel, mountain gravel, land gravel, sea gravel, crushed stone, and slag coarse aggregate. These may be used alone or in combination of two or more.
本発明の付加製造装置用水硬性組成物を付加製造装置に供給する際には、付加製造装置用水硬性組成物は水を含み、該組成物を構成する材料は混錬された未硬化の混練物の形態で供給される。
水としては、特に限定されるものではなく、水道水、「ＪＩＳ Ａ ５３０８：２０１９（レディーミクストコンクリート）」に規定される回収水等が挙げられる。
水の量は、水結合材比が、好ましくは２５～５０％、より好ましくは３０～４５％、特に好ましくは３５～４２％になる量に定められる。上記比が２５％以上であれば、造形物の強度をより大きくすることができる。上記比が５０％以下であれば、水硬性組成物を積層させる過程で、造形物をより変形しにくくすることができる。
なお、水結合材比とは、水と結合材の質量比（水／結合材）を百分率（％）で表したものである。また、結合材とは、セメントと、セメント以外の無機粉末を含むものである。
When the hydraulic composition for additive manufacturing equipment of the present invention is supplied to the additive manufacturing equipment, the hydraulic composition for additive manufacturing equipment contains water, and the material constituting the composition is a kneaded, uncured kneaded product. Supplied in the form of
Water is not particularly limited, and examples include tap water, recovered water specified in "JIS A 5308:2019 (Ready Mixed Concrete)", and the like.
The amount of water is determined such that the water binder ratio is preferably 25-50%, more preferably 30-45%, particularly preferably 35-42%. If the above ratio is 25% or more, the strength of the shaped object can be further increased. If the above ratio is 50% or less, the shaped object can be made more difficult to deform during the process of laminating the hydraulic composition.
Note that the water-binder ratio is the mass ratio of water and binder (water/binder) expressed as a percentage (%). Furthermore, the binding material includes cement and inorganic powder other than cement.
セメント組成物は、得られる造形物の体積をより大きくすることができる観点から、起泡剤を含んでいてもよい。
起泡剤の例としては、陰イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤、非イオン界面活性剤等の界面活性剤系起泡剤、蛋白質系起泡剤等が挙げられる。
起泡剤の量は、セメント１００質量部に対して、好ましくは２５質量部以下、より好ましくは０．５～２３質量部、さらに好ましくは５～２２質量部、特に好ましくは１０～２１質量部である。上記量が２５質量部以下であれば、造形物の強度をより大きくすることができる。また、上記量が０．５質量部以上であれば、得られる造形物の体積をより大きくすることができる。特に、上記量が５質量部以上であれば、得られる造形物の体積を大きくするとともに、水硬性組成物の自立性をより向上させることができる。
なお、通常、起泡剤は、水と共に、他の材料に添加される。
The cement composition may contain a foaming agent from the viewpoint of increasing the volume of the obtained shaped object.
Examples of foaming agents include surfactant foaming agents such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, protein foaming agents, and the like.
The amount of foaming agent is preferably 25 parts by mass or less, more preferably 0.5 to 23 parts by mass, even more preferably 5 to 22 parts by mass, particularly preferably 10 to 21 parts by mass, based on 100 parts by mass of cement. It is. If the amount is 25 parts by mass or less, the strength of the shaped object can be further increased. Further, if the above amount is 0.5 parts by mass or more, the volume of the obtained shaped object can be made larger. In particular, when the amount is 5 parts by mass or more, the volume of the obtained shaped object can be increased and the self-supporting properties of the hydraulic composition can be further improved.
Note that the foaming agent is usually added to other materials together with water.
付加製造装置用水硬性組成物は、任意に配合可能な他の材料を含むことができる。
他の材料の例としては、シリカフューム、高炉スラグ微粉末、フライアッシュ、石灰石微粉末、及び珪石微粉末等の無機粉末、セメント分散剤、凝結遅延剤、及び凝結促進剤等の混和剤等が挙げられる。
無機粉末の量（無機粉末が２種以上である場合、その合計量）は、付加製造装置内の閉塞を防ぐ等の観点から、セメント１００質量部に対して、好ましくは２～１５０質量部、より好ましくは３～１２０質量部である。
セメント分散剤の例としては、減水剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤等が挙げられる。
The hydraulic composition for additive manufacturing equipment can optionally contain other materials that can be blended.
Examples of other materials include inorganic powders such as silica fume, pulverized blast furnace slag, fly ash, pulverized limestone, and silica powder, admixtures such as cement dispersants, set retarders, and set accelerators. It will be done.
The amount of inorganic powder (if there are two or more types of inorganic powder, the total amount) is preferably 2 to 150 parts by mass, based on 100 parts by mass of cement, from the viewpoint of preventing clogging in the additive manufacturing equipment. More preferably, it is 3 to 120 parts by mass.
Examples of cement dispersants include water reducing agents, AE water reducing agents, high performance water reducing agents, high performance AE water reducing agents, and the like.
付加製造装置用水硬性組成物は、「ＪＩＳ Ａ １１２９－３：２０１０」（モルタル及びコンクリートの長さ変化測定方法－第３部：ダイヤルゲージ方法）に準拠して、温度が２０℃でかつ相対湿度が６０％の雰囲気下で、材齢２８日まで気中養生した場合の長さ変化率が、好ましくは５００×１０－６以下、より好ましくは４８０×１０－６以下、さらに好ましくは４４０×１０－６以下、さらに好ましくは４１０×１０－６以下、さらに好ましくは４００×１０－６以下、さらに好ましくは３９０×１０－６以下、さらに好ましくは３５０×１０－６以下、特に好ましくは３００×１０－６以下である。なお、長さ変化率が小さい程、より収縮が低減された造形物が得られることを意味する。 Hydraulic compositions for additive manufacturing equipment must be prepared at a temperature of 20°C and relative humidity in accordance with "JIS A 1129-3:2010" (Length change measurement method for mortar and concrete - Part 3: Dial gauge method). The rate of change in length when air-cured until the material age is 28 days in an atmosphere with 60% of −6 or less, more preferably 410×10 −6 or less, even more preferably 400×10 −6 or less, even more preferably 390×10 −6 or less, even more preferably 350×10 −6 or less, particularly preferably 300×10 -6 or less. Note that the smaller the rate of change in length is, the more shrinkage can be obtained.
また、付加製造装置用水硬性組成物は、付加製造装置を用いた造形物の製造を容易に行うことができる観点から、以下の条件（ｉ）～（ｉｉ）を満たすものであることが好ましい。
（ｉ）「ＪＩＳ Ｒ ５２０１：２０１５（セメントの物理試験方法）」の「１２ フロー試験」に準拠して、１５回の落下運動を行わずに測定した場合におけるフロー値（０打ちフロー値）が１２０ｍｍ以下であること、
（ｉｉ）「ＪＩＳ Ａ １１４７：２０１９（コンクリートの凝結時間試験方法）」に準拠して測定された場合における凝結の終結時間が４時間未満であること
Further, the hydraulic composition for additive manufacturing equipment preferably satisfies the following conditions (i) to (ii) from the viewpoint of facilitating the manufacture of shaped objects using additive manufacturing equipment.
(i) In accordance with “12 Flow Test” of “JIS R 5201:2015 (Physical Test Methods for Cement)”, the flow value (0-stroke flow value) when measured without performing 15 falling movements is Must be 120mm or less,
(ii) The completion time of setting is less than 4 hours when measured in accordance with "JIS A 1147:2019 (Concrete setting time test method)"
本発明の付加製造装置用水硬性組成物を用いた造形物の製造方法の例としては、付加製造装置用水硬性組成物を付加製造装置に供給する供給工程と、付加製造装置において、付加製造装置用水硬性組成物を用いて、付加製造装置用水硬性組成物からなる造形物を形成させる積層工程を含む方法が挙げられる。
付加製造装置用水硬性組成物は、付加製造装置用水硬性組成物を構成する各材料（少なくともセメント、軽量骨材及び水を含む）を混練することで、調製することができる。各材料を混練する混練手段としては、特に限定されるものではなく、モルタルやコンクリートの練り混ぜにおいて一般的に使用されるミキサを使用することができる。
具体的には、縦型ミキサ、横型ミキサ、ナウターミキサ、傾胴ミキサ、強制ミキサ、二軸ミキサ等が挙げられる。縦型ミキサの例としては、ホバート社製の「ホバートミキサ」、ヘンシェル社製の「ヘンシェルミキサ」等が挙げられる。横型ミキサの例としては、レディゲ社製の「レディゲミキサ」等が挙げられる。
調製された付加製造装置用水硬性組成物は、供給工程において、付加製造装置に投入される。付加製造装置としては、市販されている一般的な付加製造装置（３Ｄプリンタ）を用いることができる。
積層工程では、付加製造装置のノズル等から付加製造装置用水硬性組成物を押し出して、二次元形状の層状体を形成させる。その後、この層状体の上に、二層目の層状体を形成させ、以後、同様の操作を繰り返して、最終的に所望の形状を有する積層体からなる造形物を形成することができる。
An example of the method for manufacturing a shaped object using the hydraulic composition for additive manufacturing equipment of the present invention includes a supply step of supplying the hydraulic composition for additive manufacturing equipment to the additive manufacturing equipment; Examples include a method including a lamination step of forming a shaped object made of a hydraulic composition for additive manufacturing equipment using a hard composition.
The hydraulic composition for additive manufacturing equipment can be prepared by kneading each material (including at least cement, lightweight aggregate, and water) constituting the hydraulic composition for additive manufacturing equipment. The kneading means for kneading each material is not particularly limited, and a mixer commonly used for kneading mortar and concrete can be used.
Specifically, a vertical mixer, a horizontal mixer, a Nauta mixer, a tilting mixer, a forced mixer, a biaxial mixer, etc. may be mentioned. Examples of vertical mixers include "Hobart Mixer" manufactured by Hobart, "Henschel Mixer" manufactured by Henschel, and the like. An example of a horizontal mixer is "Ledige Mixer" manufactured by Ledige.
The prepared hydraulic composition for additive manufacturing equipment is fed into the additive manufacturing equipment in the supply step. As the additive manufacturing device, a commercially available general additive manufacturing device (3D printer) can be used.
In the lamination step, the hydraulic composition for additive manufacturing equipment is extruded from a nozzle or the like of the additive manufacturing equipment to form a two-dimensionally shaped layered body. Thereafter, a second layered body is formed on this layered body, and the same operation is repeated thereafter to finally form a shaped article made of a laminate having a desired shape.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
［使用材料］
（１）セメント；太平洋セメント社製、普通ポルトランドセメント
（２）軽量骨材；人工軽量細骨材、日本メサライト工業社製、商品名「メサライト」、絶乾密度：１．６５±０．５ｇ／ｃｍ３、吸水率：１５．０±２．５％
（３）細骨材；珪砂７号、最大粒径：０．３ｍｍ以下
（４）起泡剤；陰イオン界面活性剤、小野田ケミコ社製、商品名「ＯＦＡ－２」
（５）水；上水道水
EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
[Materials used]
(1) Cement: Ordinary Portland cement, manufactured by Taiheiyo Cement Co., Ltd. (2) Lightweight aggregate: Artificial lightweight fine aggregate, manufactured by Nippon Mesalite Kogyo Co., Ltd., trade name "Mesalite", absolute dry density: 1.65 ± 0.5 g/ cm3 , water absorption rate: 15.0±2.5%
(3) Fine aggregate: Silica sand No. 7, maximum particle size: 0.3 mm or less (4) Foaming agent: Anionic surfactant, manufactured by Onoda Chemico Co., Ltd., trade name "OFA-2"
(5) Water; tap water
［実施例１～９、比較例１～３］
ホバートミキサを用いて、各材料の配合量が表１又は２に示す量となるセメント、軽量骨材、細骨材、及び起泡剤、並びに、水を混練して、水硬性組成物を調製した。なお、水は、水セメント比が４０％となる量に定めた。
得られた水硬性組成物は、上述した条件（ｉ）～（ｉｉ）を満たすものであった。
付加製造装置として、高さ１３０ｍｍ、幅１００ｍｍ、奥行き１，２００ｍｍの門型フレーム、内径１４ｍｍの押し出し用ノズル、制御用コンピュータ、及び制御盤を有するものを用いた。上記付加製造装置のカートリッジに調製した水硬性組成物を投入し、押し出しノズルから水硬性組成物を押し出して、射出幅１６ｍｍ、層厚８ｍｍ、積層速度３０ｍｍ／秒の条件で積層造形を行い、造形物を得た。
[Examples 1 to 9, Comparative Examples 1 to 3]
Using a Hobart mixer, cement, lightweight aggregate, fine aggregate, foaming agent, and water are mixed in amounts shown in Table 1 or 2 to prepare a hydraulic composition. did. Note that the amount of water was determined so that the water-cement ratio was 40%.
The obtained hydraulic composition satisfied the above-mentioned conditions (i) to (ii).
The additive manufacturing apparatus used had a gate-shaped frame with a height of 130 mm, a width of 100 mm, and a depth of 1,200 mm, an extrusion nozzle with an inner diameter of 14 mm, a control computer, and a control panel. The prepared hydraulic composition is put into the cartridge of the additive manufacturing device, and the hydraulic composition is extruded from the extrusion nozzle to perform additive manufacturing under the conditions of injection width 16 mm, layer thickness 8 mm, and lamination speed 30 mm/sec. I got something.
実施例１～９及び比較例１～３で得られた造形物の積層高さ比を、比較例１で得られた造形物を基準として算出した。具体的には、造形物の高さと比較例１で得られた造形物の高さの比（造形物の高さ／比較例１で得られた造形物の高さ）を算出した。
また、造形物の長さ変化率を、「ＪＩＳ Ａ １１２９－３：２０１０」（モルタル及びコンクリートの長さ変化測定方法－第３部：ダイヤルゲージ方法）に準拠して、温度が２０℃でかつ相対湿度が６０％の雰囲気下で、材齢２８日まで気中養生して測定した。
なお、比較例３は、積層することはできず、造形物が潰れてしまった。
結果を表３～４に示す。
The stacking height ratios of the objects obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were calculated using the object obtained in Comparative Example 1 as a reference. Specifically, the ratio of the height of the model to the height of the model obtained in Comparative Example 1 (height of the model/height of the model obtained in Comparative Example 1) was calculated.
In addition, the rate of change in length of the modeled object was measured at a temperature of 20°C and in accordance with "JIS A 1129-3:2010" (Method for measuring length change in mortar and concrete - Part 3: Dial gauge method). Measurements were made after curing in air until the age of 28 days in an atmosphere with a relative humidity of 60%.
In addition, in Comparative Example 3, it was not possible to laminate, and the modeled object was crushed.
The results are shown in Tables 3 and 4.
表３～４から、実施例１～９の積層高さ比（１．２～２．５）は、比較例１～２の積層高さ比（１．０）よりも大きく、実施例１～９の水硬性組成物は自立性に優れていることがわかる。また、実施例１～７の比較から、軽量骨材の量が大きくなるほど、造形物の自立性が優れていることがわかる。
また、実施例１～９の長さ変化率（２６５～４６１×１０－６）は、比較例１～２の長さ変化率（５４７～６２１×１０－６）よりも小さく、実施例１～９の水硬性組成物は収縮が小さいものであることがわかる。また、実施例１～７の比較から、軽量骨材の量が大きくなるほど、収縮が小さくなることがわかる。
From Tables 3 and 4, the stacking height ratios (1.2 to 2.5) of Examples 1 to 9 are larger than the stacking height ratios (1.0) of Comparative Examples 1 to 2. It can be seen that the hydraulic composition No. 9 has excellent self-supporting properties. Further, from the comparison of Examples 1 to 7, it can be seen that the greater the amount of lightweight aggregate, the better the self-supporting properties of the shaped objects.
Further, the length change rate of Examples 1 to 9 (265 to 461×10 −6 ) is smaller than the length change rate of Comparative Examples 1 to 2 (547 to 621×10 −6 ), and It can be seen that the hydraulic composition No. 9 has small shrinkage. Furthermore, from the comparison of Examples 1 to 7, it can be seen that the larger the amount of lightweight aggregate, the smaller the shrinkage.
Claims (7)
上記セメント１００質量部に対する上記軽量骨材の量が、８０～１，１００質量部であることを特徴とする付加製造装置用水硬性組成物。 A hydraulic composition for additive manufacturing equipment comprising cement and lightweight aggregate, the composition comprising:
A hydraulic composition for additive manufacturing equipment, characterized in that the amount of the lightweight aggregate is 80 to 1,100 parts by mass relative to 100 parts by mass of the cement.
上記付加製造装置において、上記付加製造装置用水硬性組成物を用いて、上記付加製造装置用水硬性組成物からなる造形物を形成させる積層工程、
を含むことを特徴とする造形物の製造方法。 A supplying step of supplying the hydraulic composition for additive manufacturing equipment according to claim 5 or 6 to the additive manufacturing equipment;
In the additive manufacturing device, a lamination step of forming a shaped object made of the hydraulic composition for additive manufacturing device using the hydraulic composition for additive manufacturing device;
A method for producing a shaped object, the method comprising:
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