JP2018052766A - Cement-based material for three-dimensional printer - Google Patents
Cement-based material for three-dimensional printer Download PDFInfo
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- JP2018052766A JP2018052766A JP2016189141A JP2016189141A JP2018052766A JP 2018052766 A JP2018052766 A JP 2018052766A JP 2016189141 A JP2016189141 A JP 2016189141A JP 2016189141 A JP2016189141 A JP 2016189141A JP 2018052766 A JP2018052766 A JP 2018052766A
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- catechol
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- alkali metal
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- 239000004568 cement Substances 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 37
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- -1 alkali metal salt Chemical class 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 12
- 239000011398 Portland cement Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 6
- NUWHYWYSMAPBHK-UHFFFAOYSA-N 3,4-dihydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C=C1O NUWHYWYSMAPBHK-UHFFFAOYSA-N 0.000 claims description 4
- XJNPNXSISMKQEX-UHFFFAOYSA-N 4-nitrocatechol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1O XJNPNXSISMKQEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052609 olivine Inorganic materials 0.000 claims description 4
- 239000010450 olivine Substances 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000000843 powder Substances 0.000 abstract description 14
- 238000000465 moulding Methods 0.000 abstract description 12
- 238000005452 bending Methods 0.000 abstract description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 30
- 238000003475 lamination Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、早期の強度発現性に優れ、付加製造装置（以下「３Ｄプリンタ」という。）での使用に適したセメント系材料に関する。 The present invention relates to a cement-based material that is excellent in early strength development and suitable for use in an additive manufacturing apparatus (hereinafter referred to as “3D printer”).
特許文献１には、粉末積層成形法に適した３Ｄプリンタ用のセメント系材料として、珪砂、オリビン砂、および人工砂等の耐火砂に、速硬性セメントを粘結材として１５〜５０％配合して混練（混合）した材料に、水性バインダを加えて固化・積層してセメント系硬化体（成形体）を得る技術が開示されている。
ここで、粉末積層成形法とは、積載台（台座）の上に置いた粉体材料の所定の範囲に、インクジェット等のノズルを通して造形液を滴下または噴霧して固化し、逐次、固化した層を積層して所望の形状を造形（成形）する方法である。
Patent Document 1 includes 15-50% of fast-hardening cement as a caking additive in refractory sand such as silica sand, olivine sand, and artificial sand as a cement-based material for 3D printers suitable for the powder lamination molding method. A technique is disclosed in which an aqueous binder is added to a kneaded (mixed) material to solidify and laminate to obtain a cement-based cured body (molded body).
Here, the powder lamination molding method is a layer in which a modeling liquid is dropped or sprayed through a nozzle such as an ink jet into a predetermined range of a powder material placed on a loading table (pedestal) and solidified sequentially. Is a method of forming (forming) a desired shape by laminating the layers.
しかし、特許文献１に記載の材料を用いて３Ｄプリンタにより作製した成形体は、早期の強度発現性、特に曲げ強度が十分でないため欠損が生じ易く製品の安定供給性に欠き、３Ｄプリンタによる成形技術の特徴である微細形状品の製造が困難な場合がある。 However, a molded body produced by a 3D printer using the material described in Patent Document 1 has an early strength development property, in particular, bending strength is insufficient, so that it is liable to be damaged and lacks a stable supply of products. In some cases, it is difficult to manufacture a finely shaped product that is a feature of the technology.
したがって、本発明は、早期の曲げ強度発現性に優れ、粉末積層成形法等を用いた３Ｄプリンタ用のセメント系材料を提供することを課題とする。 Therefore, an object of the present invention is to provide a cement-based material for a 3D printer that is excellent in early flexural strength and uses a powder lamination molding method or the like.
そこで、本発明者は３Ｄプリンタ用のセメント系材料の早期の曲げ強度を高める方法について鋭意検討した結果、速硬性セメントを主な成分とするセメント組成物と特定の硬化促進剤を組み合わせあれば、前記課題を達成できることを見出し、本発明を完成させた。
すなわち、本発明は下記の構成を有する３Ｄプリンタ用セメント系材料である。
Then, as a result of earnestly examining the method for increasing the early bending strength of the cement-based material for 3D printer, the present inventor has combined a cement composition mainly composed of a fast-curing cement with a specific curing accelerator, The inventors have found that the above problems can be achieved, and have completed the present invention.
That is, the present invention is a cement-based material for 3D printers having the following configuration.
［１］速硬性セメントを６０〜１００質量％含むセメント組成物１００質量部に対し、カテコール、および下記一般式（１）で表わされる置換カテコールから選ばれる１種以上のカテコール系硬化促進剤を、０．０３〜２質量部含有する、３Ｄプリンタ用セメント系材料。
［２］前記置換カテコールが、４−シアノカテコールおよび／または４−ニトロカテコールである、前記［１］に記載の３Ｄプリンタ用セメント系材料。
［３］さらに、セメント組成物を１００質量％として、早強ポルトランドセメントを４０質量％以下含む、前記［１］または［２］に記載の３Ｄプリンタ用セメント系材料。
［４］さらに、炭酸アルカリ金属塩、乳酸アルカリ金属塩、およびケイ酸アルカリ金属塩から選ばれる１種以上のアルカリ金属塩系硬化促進剤を含む、前記［１］〜［３］のいずれかに記載の３Ｄプリンタ用セメント系材料。
［５］珪砂、オリビン砂、および人工砂等から選ばれる１種以上の細骨材を含む、前記［１］〜［４］のいずれかに記載の３Ｄプリンタ用セメント系材料。
[1] With respect to 100 parts by mass of a cement composition containing 60 to 100% by mass of a fast-curing cement, one or more catechol-based curing accelerators selected from catechol and a substituted catechol represented by the following general formula (1): A cement-based material for 3D printers containing 0.03 to 2 parts by mass.
[2] The cement-based material for 3D printer according to [1], wherein the substituted catechol is 4-cyanocatechol and / or 4-nitrocatechol.
[3] The cement-based material for 3D printer according to [1] or [2], further including 100% by mass of the cement composition and 40% by mass or less of early strong Portland cement.
[4] In any one of the above [1] to [3], further comprising one or more alkali metal salt curing accelerators selected from alkali metal carbonates, alkali metal lactates, and alkali metal silicates. The cementitious material for 3D printers as described.
[5] The cement-based material for 3D printer according to any one of [1] to [4], including one or more fine aggregates selected from quartz sand, olivine sand, artificial sand, and the like.
本発明の３Ｄプリンタ用セメント系材料は、曲げ強度の早期発現性に優れているため、粉末積層成形法等による成形品の欠損が生じ難く、微細形状を有する成形品の製作に好適に用いることができる。 Since the cement-based material for 3D printer of the present invention is excellent in the early manifestation of bending strength, it is difficult to cause defects in the molded product by the powder lamination molding method and the like, and should be suitably used for producing a molded product having a fine shape. Can do.
本発明の３Ｄプリンタ用セメント系材料は、前記のとおり、速硬性セメントを６０〜１００質量％含むセメント組成物１００質量部に対し、カテコール、および前記一般式（１）で表わされる置換カテコールから選ばれる１種以上のカテコール系硬化促進剤を、０．０３〜２質量部含有する材料である。
以下、本発明の３Ｄプリンタ用セメント系材料について、詳細に説明する。
As described above, the cement-based material for a 3D printer of the present invention is selected from catechol and substituted catechol represented by the general formula (1) with respect to 100 parts by mass of the cement composition containing 60 to 100% by mass of fast-setting cement. It is a material containing 0.03 to 2 parts by mass of one or more catechol-based curing accelerators.
Hereinafter, the cementitious material for 3D printer of the present invention will be described in detail.
１．セメント
本発明に用いるセメントは、速硬性セメントであり、さらに速硬性セメント以外のセメントを一部含んでもよい。かかる速硬性セメントは、ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」に規定する凝結の終結時間が３０分以内、好ましくは２０分以内、より好ましくは１０分以内のセメントである。具体的な商品では、例えば、スーパージェットセメント（小野田ケミコ社製）、ジェットセメント（住友大阪セメント社製）、およびデンカスーパーセメント（デンカ社製）等が挙げられる。
1. Cement The cement used in the present invention is a fast-setting cement, and may further include a part of cement other than the fast-setting cement. Such a fast-hardening cement is a cement having a setting time of 30 minutes or less, preferably 20 minutes or less, more preferably 10 minutes or less as defined in JIS R 5201 “Physical Test Method for Cement”. Specific products include, for example, super jet cement (manufactured by Onoda Chemico), jet cement (manufactured by Sumitomo Osaka Cement), and denka super cement (manufactured by Denka).
前記セメント組成物（速硬性セメント単独、または速硬性セメントと速硬性セメント以外のセメントの混合物）中の速硬性セメントの含有率は、セメント組成物を１００質量％として、６０〜１００質量％、好ましくは７０〜１００質量％、より好ましくは８０〜１００質量％である。速硬性セメントの含有率が、６０〜１００質量％の範囲内にあれば、粉末積層成形法等による成形品は、速硬性と共に取扱い可能な曲げ強度を早期に確保できる。 The content of fast-setting cement in the cement composition (fast-setting cement alone or a mixture of fast-setting cement and cement other than fast-setting cement) is preferably 60 to 100% by weight, based on 100% by weight of the cement composition. Is 70 to 100% by mass, more preferably 80 to 100% by mass. If the content rate of a quick-hardening cement exists in the range of 60-100 mass%, the molded article by a powder lamination molding method etc. can ensure the bending strength which can be handled with quick-hardness at an early stage.
前記速硬性セメント以外のセメントは、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、普通エコセメント、高炉セメント、フライアッシュセメント、シリカセメント、およびシリカフュームプレミックスセメント等から選ばれる１種以上が挙げられる。また、粉末積層成形法等による成形品の曲げ強度を早期に確保する観点等から、早強ポルトランドセメントが特に好ましい。
前記セメント組成物中の速硬性セメント以外のセメントの含有率は、セメント組成物を１００質量％として、０〜４０質量％、好ましくは０〜３０質量％、より好ましくは０〜２０質量％である。
The cements other than the fast-curing cements are ordinary Portland cement, early-strength Portland cement, medium heat Portland cement, low heat Portland cement, white Portland cement, ordinary ecocement, blast furnace cement, fly ash cement, silica cement, and silica fume premix cement. 1 type or more chosen from etc. is mentioned. Further, from the viewpoint of ensuring early the bending strength of a molded product by a powder lamination molding method or the like, early strength Portland cement is particularly preferable.
The content of the cement other than the quick-hardening cement in the cement composition is 0 to 40% by mass, preferably 0 to 30% by mass, more preferably 0 to 20% by mass, with the cement composition being 100% by mass. .
２．硬化促進剤
本発明に用いる硬化促進剤は、本発明の３Ｄプリンタ用セメント系材料において必須の成分であるカテコール系硬化促進剤と、任意の成分であるアルカリ金属塩系硬化促進剤がある。
カテコール系硬化促進剤は、カテコール、および前記一般式（１）で表わされる置換カテコールから選ばれる１種以上の化合物であり、これらの中でも、硬化促進がより高いため、好ましくは４−シアノカテコールおよび／または４−ニトロカテコールである。本発明で云うカテコール系硬化促進剤は、カテコールおよび置換カテコールのアルカリ金属塩、およびアルカリ土類金属塩等の塩類も含む。
前記カテコール系硬化促進剤の含有率は、前記セメント組成物１００質量部に対し、０．０３〜２質量部、好ましくは０．１〜１．０質量部、より好ましくは０．１〜０．５質量部である。
また、前記カテコール系硬化促進剤とセメント組成物の混合手段は、ヘンシェルミキサ、ホバートミキサ、リボンミキサ、およびパグミキサー等の通常の粉粒体混合装置を用いることができる。
2. Curing accelerator The curing accelerator used in the present invention includes a catechol-based curing accelerator that is an essential component in the cement-based material for a 3D printer of the present invention and an alkali metal salt-based curing accelerator that is an optional component.
The catechol-based curing accelerator is one or more compounds selected from catechol and the substituted catechol represented by the general formula (1). Among these, since the curing acceleration is higher, 4-cyanocatechol and preferably / Or 4-nitrocatechol. The catechol-based curing accelerator referred to in the present invention includes salts such as alkali metal salts of catechol and substituted catechol, and alkaline earth metal salts.
The content of the catechol curing accelerator is 0.03 to 2 parts by weight, preferably 0.1 to 1.0 parts by weight, more preferably 0.1 to 0. 0 parts by weight with respect to 100 parts by weight of the cement composition. 5 parts by mass.
Moreover, the mixing means of the said catechol type | system | group hardening accelerator and cement composition can use normal granule mixing apparatuses, such as a Henschel mixer, a Hobart mixer, a ribbon mixer, and a pug mixer.
また、アルカリ金属塩系硬化促進剤は、炭酸アルカリ金属塩、乳酸アルカリ金属塩、およびケイ酸アルカリ金属塩から選ばれる１種以上であり、具体的には、炭酸リチウム、炭酸ナトリウム、乳酸ナトリウム、ケイ酸ナトリウム、およびケイ酸カリウム等が挙げられる。
前記アルカリ金属塩系硬化促進剤の含有率は、前記セメント組成物１００質量部に対し、好ましくは０．５〜１０質量部、より好ましくは１〜８質量部、さらに好ましくは３〜６質量部である。硬化促進剤の含有率が０．５〜１０質量部であれば、粉末積層成形法等を用いて成形した成形品の速硬性と曲げ強度発現性がさらに向上する。
The alkali metal salt curing accelerator is at least one selected from alkali metal carbonates, alkali metal lactates, and alkali metal silicates. Specifically, lithium carbonate, sodium carbonate, sodium lactate, Examples thereof include sodium silicate and potassium silicate.
The content of the alkali metal salt curing accelerator is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 3 to 6 parts by mass with respect to 100 parts by mass of the cement composition. It is. If the content rate of a hardening accelerator is 0.5-10 mass parts, the quick-hardness and bending strength expression property of the molded article shape | molded using the powder lamination molding method etc. will further improve.
３．細骨材
本発明の３Ｄプリンタ用セメント系材料は、細骨材を含むこともできる。該細骨材は特に限定されないが、製品の安定供給性の観点から、好ましくは、珪砂、オリビン砂、および人工砂等から選ばれる１種以上である。また、該細骨材の最大粒径は、微細な形状が成形し易いことから、好ましくは１．０ｍｍ以下、より好ましくは０．６ｍｍ以下、さらに好ましくは０．４ｍｍ以下である。
また、細骨材の含有率は、前記セメント組成物１００質量部に対し、好ましくは１００〜４００質量部、より好ましくは１５０〜３５０質量部、さらに好ましくは２００〜３００質量部である。
3. Fine Aggregate The cementitious material for a 3D printer of the present invention can also contain fine aggregate. The fine aggregate is not particularly limited, but is preferably at least one selected from quartz sand, olivine sand, artificial sand and the like from the viewpoint of stable supply of the product. The maximum particle size of the fine aggregate is preferably 1.0 mm or less, more preferably 0.6 mm or less, and further preferably 0.4 mm or less because a fine shape can be easily formed.
The content of fine aggregate is preferably 100 to 400 parts by mass, more preferably 150 to 350 parts by mass, and still more preferably 200 to 300 parts by mass with respect to 100 parts by mass of the cement composition.
また、本発明の３Ｄプリンタ用セメント系材料と、前記アルカ金属塩系硬化促進剤および／または細骨材の混合手段には、前記と同様に、ヘンシェルミキサ、ホバートミキサ、リボンミキサ、およびパグミキサー等の通常の粉粒体混合装置を用いることができる。 Further, the mixing means for the cement material for 3D printer of the present invention and the alkali metal salt hardening accelerator and / or fine aggregate is the same as described above, Henschel mixer, Hobart mixer, ribbon mixer, and pug mixer. Ordinary powder mixing devices such as the above can be used.
４．水
粉末積層成形法の実施において、３Ｄプリンタ用セメント系材料に噴霧する噴霧水は、一般の水道水（上水道、工業用水）が使用できる。
噴霧水の噴霧割合は、前記３Ｄプリンタ用セメント系材料中のセメント組成物１００質量部に対し、３〜２０質量部、好ましくは５〜１５質量部、より好ましくは７〜１３質量部である。
4). In the implementation of the water powder lamination molding method, general tap water (water supply, industrial water) can be used as the spray water sprayed onto the cement-based material for the 3D printer.
The spray ratio of spray water is 3 to 20 parts by mass, preferably 5 to 15 parts by mass, and more preferably 7 to 13 parts by mass with respect to 100 parts by mass of the cement composition in the cementitious material for 3D printer.
５．養生方法
粉末積層成形法等を実施して得られた成形体（硬化体）の養生方法は、気中養生、または、気中養生後に続けて水中養生する方法が採用できる。気中および水中の温度は、特に制限されないが、養生のし易さから、好ましくは１０〜５０℃でよい。
気中養生時間は、十分な強度発現と生産効率の観点から、好ましくは１〜４時間、より好ましくは１．５〜３時間、さらに好ましくは２〜３時間である。また、水中養生時間は、前記気中養生した後に、好ましくは３時間以上、より好ましくは５時間以上、さらに好ましくは８時間以上である。
5. Curing Method As a curing method for a molded body (cured body) obtained by carrying out a powder lamination molding method or the like, an air curing method or a method of underwater curing after air curing can be adopted. The temperature in the air and water is not particularly limited, but is preferably 10 to 50 ° C. for ease of curing.
The air curing time is preferably 1 to 4 hours, more preferably 1.5 to 3 hours, and further preferably 2 to 3 hours from the viewpoint of sufficient strength expression and production efficiency. The underwater curing time is preferably 3 hours or more, more preferably 5 hours or more, and further preferably 8 hours or more after the air curing.
以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されない。
１．使用材料
（１）速硬性セメント：スーパージェットセメント（小野田ケミコ社製、終結時間；１０分以内）
（２）速硬性セメント以外のセメント：早強ポルトランドセメント（太平洋セメント社製）
（３）カテコール系硬化促進剤：カテコール（試薬、和光純薬工業社製）、４−シアノカテコール（試薬、東京化成工業社製）、および４−ニトロカテコール（試薬、和光純薬工業社製）
（４）アルカリ金属塩系硬化促進剤：炭酸リチウム（試薬１級、和光純薬工業社製）
（５）非アルカリ金属塩系硬化促進剤：亜硝酸カルシウム（試薬１級、和光純薬工業社製）
（６）砂：珪砂８号（粒径０．３ｍｍ以下、東北硅砂社製）
（７）水：水道水
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
1. Materials used (1) Fast-curing cement: Super Jet Cement (manufactured by Onoda Chemico, closing time: within 10 minutes)
(2) Cement other than fast-curing cement: Early strong Portland cement (manufactured by Taiheiyo Cement)
(3) Catechol-based curing accelerator: Catechol (reagent, manufactured by Wako Pure Chemical Industries), 4-cyanocatechol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-nitrocatechol (reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
(4) Alkali metal salt curing accelerator: lithium carbonate (reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Non-alkali metal salt hardening accelerator: Calcium nitrite (reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.)
(6) Sand: Silica sand No. 8 (particle size 0.3 mm or less, manufactured by Tohoku Sosuna Co., Ltd.)
(7) Water: Tap water
２．セメント系材料による硬化体の作製
表１の配合に従い、前記材料をホバートミキサで乾式混合して３Ｄプリンタ用セメント系材料を作製した。次に、３Ｄプリンタ（粉末積層造形装置、商品名：ZPrinter310、Ｚコーポレーション社製）と前記３Ｄプリンタ用セメント系材料を用いて、粉末積層成形法により、寸法が縦１０ｍｍ、横１６ｍｍ、および長さ８０ｍｍの供試体（硬化体）を成形した。
なお、前記供試体の成形で用いた噴霧水の噴霧割合は、前記３Ｄプリンタ用セメント系材料中のセメント組成物１００質量部に対し、１０質量部であった。
2. Preparation of hardened body with cement-based material According to the composition shown in Table 1, the material was dry-mixed with a Hobart mixer to prepare a cement-based material for 3D printer. Next, using a 3D printer (powder additive manufacturing apparatus, trade name: ZPrinter310, manufactured by Z Corporation) and the 3D printer cement material, the dimensions are 10 mm in length, 16 mm in width, and length by the powder laminate molding method. An 80 mm specimen (cured body) was molded.
In addition, the spraying ratio of the spray water used in the molding of the specimen was 10 parts by mass with respect to 100 parts by mass of the cement composition in the cement material for the 3D printer.
３．セメント硬化体の曲げ強度の測定
次に、前記供試体を、２０℃の気中で２時間養生した後、曲げ強度試験機（型番：MODEL-2257、アイコーエンジニアリング社製）を用いて３点曲げ試験を行った。その結果を表１に示す。
3. Measurement of bending strength of hardened cement body Next, the specimen was cured in the air at 20 ° C for 2 hours, and then bent at three points using a bending strength tester (model number: MODEL-2257, manufactured by Aiko Engineering Co., Ltd.). A test was conducted. The results are shown in Table 1.
表１に示すように、材齢２時間における曲げ強度比は、比較例１〜４で０．７９（比較例３）〜１．０４（比較例４）であるのに対し、実施例１〜２６では１．１０（実施例１、２、６、２１）〜１．７７（実施例１４）であるから、本発明の３Ｄプリンタ用セメント系材料は、材齢２時間という極めて早期における曲げ強度発現性が高いと云える。
As shown in Table 1, the bending strength ratio at the age of 2 hours is 0.79 (Comparative Example 3) to 1.04 (Comparative Example 4) in Comparative Examples 1 to 4, whereas Examples 1 to 4 are used. 26, from 1.10 (Examples 1, 2, 6, 21) to 1.77 (Example 14), the cementitious material for 3D printers of the present invention has an extremely early bending strength of 2 hours of age. It can be said that expression is high.
Claims (5)
The cementitious material for 3D printers according to any one of claims 1 to 4, comprising one or more fine aggregates selected from quartz sand, olivine sand, artificial sand and the like.
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| JP2020026523A (en) * | 2018-08-08 | 2020-02-20 | 花王株式会社 | Additive for inorganic particle-containing composition |
| CN113087441A (en) * | 2021-03-05 | 2021-07-09 | 山西佳维新材料股份有限公司 | Fluoride-free liquid alkali-free accelerator and preparation method and application thereof |
| US11111178B2 (en) * | 2018-06-18 | 2021-09-07 | The Board Of Trustees Of The University Of Alabama | Renewable admixtures for cementitious compositions |
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