JP6916582B2 - Method for manufacturing hydraulic composition for addition manufacturing equipment and mold - Google Patents
Method for manufacturing hydraulic composition for addition manufacturing equipment and mold Download PDFInfo
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- JP6916582B2 JP6916582B2 JP2017148518A JP2017148518A JP6916582B2 JP 6916582 B2 JP6916582 B2 JP 6916582B2 JP 2017148518 A JP2017148518 A JP 2017148518A JP 2017148518 A JP2017148518 A JP 2017148518A JP 6916582 B2 JP6916582 B2 JP 6916582B2
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00939—Uses not provided for elsewhere in C04B2111/00 for the fabrication of moulds or cores
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Description
本発明は、付加製造装置（３Ｄプリンタ）を用いて造形物を製造するための付加製造装置用水硬性組成物と、該組成物を用いた鋳型の製造方法に関する。 The present invention relates to a water-hardening composition for an additional manufacturing apparatus for producing a modeled product using an additional manufacturing apparatus (3D printer), and a method for producing a mold using the composition.
鋳造は、溶融した金属を鋳型に注入して鋳物を製造する伝統的な金属加工法である。この鋳造に用いる自硬性鋳型は、使用する粘結材（結合材）に応じて有機系と無機系があり、このうち無機系は、主に水ガラス系とセメント系がある。ただし、セメント系自硬性鋳型は、鋳込み温度によっては、含まれる石膏が熱分解してガスが発生して、鋳物に欠陥が生じ、美観や機能が損なわれる。また、この鋳型の製造は、模型や木型の作製が前工程として必須であるが、この前工程には時間とコストがかかる。
そこで、鋳物の美観等が損なわれず、該前工程が不要な鋳型の製造手段が望まれる。
Casting is a traditional metalworking method in which molten metal is injected into a mold to produce a casting. The self-hardening mold used for this casting has an organic type and an inorganic type depending on the binder (bonding material) used, and among them, the inorganic type is mainly a water glass type and a cement type. However, depending on the casting temperature, the cement-based self-hardening mold thermally decomposes the gypsum contained in the cement-based self-hardening mold to generate gas, which causes defects in the casting and impairs the appearance and function. Further, in the production of this mold, the production of a model or a wooden mold is indispensable as a pre-process, but this pre-process requires time and cost.
Therefore, a mold manufacturing means that does not impair the aesthetic appearance of the casting and does not require the pre-process is desired.
ところで、最近、付加製造装置が、迅速かつ精密な造形手段として注目されている。この付加製造装置のうち、例えば、粉末積層成形装置は、粉末を平面の上に敷き詰めた後、該粉末に水性バインダを噴射して固化した固化物を、垂直方向に順次積層して造形する装置である。この装置の特徴は、３次元ＣＡＤ等で作成した立体造形のデータを多数の水平面に分割し、これらの水平面の形状を順次積層して、造形物を製造する点にある。
そこで、前記装置を用いて鋳型を製造できれば、前記の前工程は不要になり、作業時間とコストを削減できると期待される。
By the way, recently, an addition manufacturing apparatus has been attracting attention as a quick and precise modeling means. Among these additional manufacturing devices, for example, a powder laminating molding device is a device in which powder is spread on a flat surface, and then solidified solidified products are sequentially laminated in the vertical direction by injecting an aqueous binder onto the powder to form a model. Is. The feature of this device is that the three-dimensional modeling data created by three-dimensional CAD or the like is divided into a large number of horizontal planes, and the shapes of these horizontal planes are sequentially laminated to manufacture a modeled object.
Therefore, if a mold can be manufactured using the apparatus, it is expected that the above-mentioned pre-process becomes unnecessary and the working time and cost can be reduced.
例えば、特許文献１は、結合材噴射法（粉末積層成形法）に適した粉末材料を提案している。該材料は、珪砂、オリビン砂、人工砂等の耐火砂に速硬性セメントを粘結材として所定の量を配合して混練したもので、これに水性バインダを加えて固化および積層して造形物を製造する。
この結合材噴射法を用いて製造した造形物は、製造直後の運搬時の破損を防止して、製造量や良品を確保するためには、早期強度発現性が高く、かつ鋳物の製造時においても高い強度が求められる。
また、特許文献２に記載の造形用材料は、骨材と、該骨材を結着させるバインダである粉状前駆体とを混合した粉末固着積層法用の造形用材料であって、前記骨材の含有率は７０重量％以上であり、前記粉状前駆体はセメント等である。
For example, Patent Document 1 proposes a powder material suitable for a binder injection method (powder additive manufacturing method). The material is a refractory sand such as silica sand, olivine sand, artificial sand, etc. mixed with a predetermined amount of quick-hardening cement as a binder and kneaded. To manufacture.
The modeled product manufactured by using this binder injection method has a high early strength development in order to prevent damage during transportation immediately after manufacturing and to secure a manufacturing amount and a good product, and at the time of manufacturing a casting. Is also required to have high strength.
Further, the modeling material described in Patent Document 2 is a modeling material for a powder fixing lamination method in which an aggregate and a powdery precursor which is a binder for binding the aggregate are mixed, and the bone is described above. The content of the material is 70% by weight or more, and the powdery precursor is cement or the like.
しかし、石膏を比較的多く含む前記造形用材料を鋳型に用いると、高温下で硫黄酸化物等のガスが発生してブローホール等の欠陥が生じ易く、また黒鉛の球状化阻害による欠陥が生じる場合がある。一方、石膏を多く含まないセメントでは、充分な早期強度発現性が得られ難い。
このように、セメント系材料を付加製造装置用の鋳型製造用材料として用いた場合、硫黄酸化物等のガスや、黒鉛球状化不良による鋳造欠陥の発生防止と、早期強度発現性を両立することは困難であった。
However, when the molding material containing a relatively large amount of gypsum is used as a mold, gas such as sulfur oxide is generated at a high temperature and defects such as blow holes are likely to occur, and defects due to inhibition of spheroidization of graphite occur. In some cases. On the other hand, it is difficult to obtain sufficient early strength development with cement that does not contain a large amount of gypsum.
In this way, when a cement-based material is used as a material for manufacturing a mold for an additional manufacturing apparatus, it is necessary to achieve both prevention of casting defects due to gas such as sulfur oxides and poor graphite spheroidization and early strength development. Was difficult.
したがって、本発明は、強度発現性、とくに早期強度発現性が高く、鋳物の製造においてガスや黒鉛球状化不良による欠陥の発生が少ない付加製造装置用水硬性組成物等を提供することを目的とする。 Therefore, an object of the present invention is to provide a hydraulic composition for an additional manufacturing apparatus, which has high strength development, particularly early strength development, and less generation of defects due to gas or graphite spheroidization failure in the production of castings. ..
本発明者は、前記課題を解決するために鋭意検討した結果、カルシウムアルミネートを、特定割合含む結合材１００質量部に対し、ポリマーを特定割合含有する水硬性組成物は、前記目的を達成できることを見い出し、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付加製造装置用水硬性組成物等である。
As a result of diligent studies to solve the above problems, the present inventor has found that a water-hard composition containing a specific ratio of a polymer with respect to 100 parts by mass of a binder containing a specific ratio of calcium aluminate can achieve the above object. We found and completed the present invention.
That is, the present invention is a water-hardening composition for an addition manufacturing apparatus having the following constitution.
［１］ＣａＯ／Ａｌ ２ Ｏ ３ のモル比が１．７〜２．４、ブレーン比表面積が１０００〜２５００ｃｍ ２ ／ｇ、およびガラス化率が９０％以上の非晶質カルシウムアルミネートを８０〜１００質量％、および、速硬性セメント、超速硬セメント、または止水セメントから選ばれるセメントを０〜２０質量％含む無機結合材１００質量部に対し、
ケン化度が８５〜９０モル％のポリビニルアルコールを２〜１２質量部含有する、付加製造装置用水硬性組成物。
［２］前記ポリビニルアルコールの粒度が、目開き９０μｍふるいの残分で１０質量％以下である、前記［１］に記載の付加製造装置用水硬性組成物。
［３］前記無機結合材が、無機結合材全体を１００質量％として、石膏を無水石膏換算で５０質量％以下含む、前記［１］または［２］に記載の付加製造装置用水硬性組成物。
［４］付加製造装置と前記［１］〜［３］のいずれかに記載の付加製造装置用水硬性組成物を用いて鋳型を造形する、鋳型の製造方法。
[1] Amorphous calcium aluminate having a mass ratio of CaO / Al 2 O 3 of 1.7 to 2.4, a specific surface area of 1000 to 2500 cm 2 / g, and a vitrification rate of 90% or more is 80 to 2. With respect to 100 parts by mass of an inorganic binder containing 100% by mass and 0 to 20% by mass of cement selected from fast-hardening cement, ultrafast-hardening cement, and water-stopping cement.
A water-hard composition for an addition manufacturing apparatus containing 2 to 12 parts by mass of polyvinyl alcohol having a saponification degree of 85 to 90 mol%.
[2] The water-hard composition for an additional manufacturing apparatus according to the above [1] , wherein the particle size of the polyvinyl alcohol is 10% by mass or less with the remainder of the sieve having a mesh size of 90 μm.
[3] The hydraulic composition for an additional manufacturing apparatus according to the above [1] or [2] , wherein the inorganic binder contains 50% by mass or less of gypsum in terms of anhydrous gypsum, with the entire inorganic binder as 100% by mass.
[4] A method for producing a mold, which comprises molding a mold using the addition manufacturing apparatus and the water-hardening composition for the addition manufacturing apparatus according to any one of the above [1] to [ 3].
本発明の付加製造装置用水硬性組成物は、強度発現性と耐熱性が高いため、鋳型に用いた場合、鋳造時のガスの発生が少なく、欠陥のない鋳物を製造できる。 Since the water-hardening composition for an additional manufacturing apparatus of the present invention has high strength development and heat resistance, when it is used as a mold, less gas is generated during casting, and a defect-free casting can be produced.
本発明は、前記のとおり、カルシウムアルミネートを５０〜１００質量％含む結合材１００質量部に対し、ポリマーを２〜１２質量部含有する、付加製造装置用水硬性組成物（以下「水硬性組成物」と略すこともある。）等である。
以下、本発明について、結合材の必須の成分であるカルシウムアルミネートと、任意の成分であるセメント等に分けて詳細に説明する。
As described above, the present invention is a water-hard composition for an addition manufacturing apparatus containing 2 to 12 parts by mass of a polymer with respect to 100 parts by mass of a binder containing 50 to 100% by mass of calcium aluminate (hereinafter, “water-hard composition”). It may be abbreviated as ".) Etc.
Hereinafter, the present invention will be described in detail separately for calcium aluminate, which is an essential component of the binder, and cement, which is an arbitrary component.
１．カルシウムアルミネート
該カルシウムアルミネートは、１２ＣａＯ・７Ａｌ２Ｏ３、３ＣａＯ・Ａｌ2Ｏ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、Ｎａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3、および非晶質カルシウムアルミネート等から選ばれる１種以上が挙げられる。これらの中でも、好ましくは、早期強度発現性がより高いため、非晶質カルシウムアルミネートである。また、前記非晶質カルシウムアルミネートは、ＣａＯとＡｌ２Ｏ３を主成分とし、さらに、Ｎａ、Ｋ、ＳまたはＦｅから選ばれる１種以上を含むことができる。
非晶質カルシウムアルミネートは、原料を溶融した後、急冷して製造するから、実質的に結晶構造を有せず、通常、そのガラス化率は８０％以上であり、ガラス化率が高い程、早期強度発現性は高いため、ガラス化率は好ましくは９０％以上である。
本発明で用いるカルシウムアルミネートのＣａＯ／Ａｌ２Ｏ３のモル比は、好ましくは１．５〜３．０、より好ましくは１．７〜２．４である。該モル比が１．５以上で水硬性組成物の早期強度発現性が高く、３．０以下で水硬性組成物の耐熱性が高い。
また、カルシウムアルミネートと、任意の成分であるセメントおよび石膏等を含む結合材の合計を１００質量％として、カルシウムアルミネートの含有率は５０〜１００質量％である。該値が５０質量％以上であれば、水硬性組成物の早期強度発現性と耐熱性が高い。なお、該値は、好ましくは６０〜１００質量％、より好ましくは７０〜１００質量％、さらに好ましくは８０〜９５質量％である。
また、カルシウムアルミネートのブレーン比表面積は、充分な早期強度発現性を得るとともに粉塵の発生を抑制するために、好ましくは１０００〜６０００ｃｍ２／ｇ、より好ましくは１５００〜５０００ｃｍ２／ｇである。なお、カルシウムアルミネートのブレーン比表面積は、付加製造装置での敷きならしが均一で、かつ、鋳型の強度が低下しないためには、さらに好ましくは１０００〜２５００ｃｍ２／ｇ、特に好ましくは１５００〜２０００ｃｍ２／ｇである。
1. 1. Calcium aluminate the calcium aluminate, 12CaO · 7Al 2 O 3, 3CaO · Al 2 O 3, 11CaO · 7Al 2 O 3 · CaF 2, Na 2 O · 8CaO · 3Al 2 O 3, and amorphous calcium aluminate One or more kinds selected from nate and the like can be mentioned. Among these, amorphous calcium aluminate is preferable because it has a higher early strength development. Also, the amorphous calcium aluminate is mainly composed of CaO and Al 2 O 3, can further comprise one or more selected Na, K, from S or Fe.
Amorphous calcium aluminate is produced by melting the raw material and then quenching it. Therefore, it has substantially no crystal structure, and its vitrification rate is usually 80% or more, and the higher the vitrification rate, the higher the vitrification rate. Since the early strength development is high, the vitrification rate is preferably 90% or more.
The molar ratio of CaO / Al 2 O 3 of the calcium aluminate used in the present invention is preferably 1.5 to 3.0, more preferably 1.7 to 2.4. When the molar ratio is 1.5 or more, the early strength development of the hydraulic composition is high, and when the molar ratio is 3.0 or less, the heat resistance of the hydraulic composition is high.
Further, the content of calcium aluminate is 50 to 100% by mass, where the total of the binder containing calcium aluminate and an arbitrary component such as cement and gypsum is 100% by mass. When the value is 50% by mass or more, the hydraulic composition has high early strength development and heat resistance. The value is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 95% by mass.
Also, the Blaine specific surface area of the calcium aluminate, in order to suppress the generation of dust with obtaining sufficient early strength development, preferably 1000~6000cm 2 / g, more preferably 1500~5000cm 2 / g. The specific surface area of the brain of calcium aluminate is more preferably 1000 to 2500 cm 2 / g, particularly preferably 1500 to 100, so that the spread in the addition manufacturing apparatus is uniform and the strength of the mold does not decrease. It is 2000 cm 2 / g.
２．セメント
セメントは結合材の任意の成分であり、JIS R ５２１０に準拠して測定した凝結（始発）が３時間３０分以内であれば、鋳型の製造時から３時間後の早期の強度発現性が高いため好ましく、該凝結（始発）は１時間以内がより好ましい。
結合材中のセメントの含有率は、早期強度発現性の向上のため、結合材全体を１００質量％として、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１０質量％以下である。
また、セメント中の珪酸カルシウムの含有率は、好ましくは２５質量％以上である。該含有率が２５質量％以上あれば、材齢１日以後の強度発現性が高く、また長期強度発現性が必要な場合、該含有率は、好ましくは４５質量％以上である。
本発明で用いるセメントは、速硬セメント、超速硬セメント、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、エコセメント、高炉セメント、フライアッシュセメント、およびセメントクリンカー粉末から選ばれる１種以上が挙げられる。なお、本発明では、セメントクリンカー粉末もセメントに含める。
これらの中でも、早期強度発現性が高いため、好ましくは、凝結（始発）が３０分以内である速硬性セメント、超速硬セメント、または止水セメントである。なお、速硬性セメント等の市販品は、スーパージェットセメント（太平洋セメント社製）、ジェットセメント（住友大阪セメント社製）、ライオンシスイ（登録商標、住友大阪セメント社製）、またはデンカスーパーセメント（デンカ社製）が挙げられる。
2. Cement Cement is an arbitrary component of the binder, and if the condensation (starting) measured in accordance with JIS R 5210 is within 3 hours and 30 minutes, the early strength development after 3 hours from the time of mold production is achieved. It is preferable because it is high, and the condensation (first onset) is more preferably within 1 hour.
The content of cement in the binder is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, with the entire binder as 100% by mass in order to improve the early strength development. , Particularly preferably 10% by mass or less.
The content of calcium silicate in the cement is preferably 25% by mass or more. When the content is 25% by mass or more, the strength development after 1 day of age is high, and when long-term strength development is required, the content is preferably 45% by mass or more.
The cement used in the present invention is fast-hardening cement, ultrafast-hardening cement, ordinary Portland cement, early-strength Portland cement, moderate heat Portland cement, low heat Portland cement, white Portland cement, eco-cement, blast furnace cement, fly ash cement, and cement clinker. One or more selected from the powder can be mentioned. In the present invention, cement clinker powder is also included in cement.
Among these, fast-hardening cements, ultrafast-hardening cements, or water-stopping cements in which the setting (starting) is within 30 minutes are preferable because the early strength development is high. Commercially available products such as quick-hardening cement include Super Jet Cement (manufactured by Taiheiyo Cement), Jet Cement (manufactured by Sumitomo Osaka Cement), Lion Sisui (registered trademark, manufactured by Sumitomo Osaka Cement), or Denka Super Cement (Denka). (Manufactured by the company).
３．石膏
石膏は結合材の任意の成分であり、無水石膏、半水石膏、および二水石膏から選ばれる１種以上が挙げられる。これらの中でも、半水石膏は早期強度発現性がより高いために好ましい。
結合材中の石膏の含有率は、強度の向上や、鋳物の製造時においてガスや黒鉛球状化不良を防止するため、結合材全体を１００質量％として、好ましくは無水石膏換算で５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは１０質量％以下、特に好ましくは５質量％以下である。また、結合材中の石膏の含有率は、早期強度発現性を向上させるため、結合材全体を１００質量％として、好ましくは無水石膏換算で０．５質量％以上、より好ましくは１質量％以上である。
3. 3. Gypsum Gypsum is an optional component of the binder, including one or more selected from anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum. Among these, hemihydrate gypsum is preferable because it has a higher early strength development.
The content of gypsum in the binder is 100% by mass, preferably 50% by mass or less in terms of anhydrous gypsum, in order to improve the strength and prevent gas and graphite spheroidization defects during the production of castings. , More preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. Further, the content of gypsum in the binder is 100% by mass, preferably 0.5% by mass or more, more preferably 1% by mass or more in terms of anhydrous gypsum, in order to improve the early strength development. Is.
また、前記石膏はセメント中に含まれる石膏でもよく、セメント中の石膏の含有率が無水石膏換算で５質量％以上含むような超速硬セメント（例えば、太平洋セメント社製スーパージェットセメント）は、カルシウムアルミネートと混合して結合材として用いることで、より早期強度発現性が向上する。 Further, the gypsum may be gypsum contained in cement, and ultrafast-hardened cement (for example, Super Jet Cement manufactured by Pacific Cement Co., Ltd.) in which the content of gypsum in cement is 5% by mass or more in terms of anhydrous gypsum is calcium. By mixing with aluminate and using it as a binder, early strength development is improved.
４．ポリマー
本発明の水硬性組成物中のポリマーの含有割合は、水硬性組成物の強度をより高めるために、結合材１００質量部に対し固形分換算で２〜１２質量部である。ポリマーの含有割合が２質量部未満では、強度の向上効果は低く、また、１２質量部を越えると、造形物の収縮により、形状によっては変形やひび割れが生じ、また形状が複雑な鋳型が製造できない場合がある。なお、ポリマーの含有割合は、結合材１００質量部に対し、より好ましくは３〜１２質量部、さらに好ましくは４〜１０質量部である。
前記ポリマーは、ポリマーの形態で示せば、ＪＩＳ Ａ ６２０３に規定するポリマーディスパージョンや再乳化粉末樹脂等であり、また、ポリマーの種類で示せば、ポリアクリル酸エステル、エチレン・酢酸ビニル共重合体、スチレン・ブタジエン共重合体、酢酸ビニル・バーサチック酸ビニルエステル共重合体、酢酸ビニル・バーサチック酸ビニル・アクリル酸エステル３元共重合体、ポリビニルアルコール、マルトデキストリン、エポキシ樹脂、およびウレタン樹脂から選ばれる１種以上が挙げられる。
これらの中でも、早期強度発現性が得られるため、好ましくはポリビニルアルコール（ポリ酢酸ビニルの部分ケン化物または完全ケン化物）であり、さらに好ましくはケン化度が８５〜９０モル％のポリビニルアルコールである。
また、早期強度発現性が得られるため、好ましくポリビニルアルコールの粒度は、目開き９０μｍふるいの残分が１０質量％以下、より好ましくは目開き７５μｍふるいの残分が１０質量％以下である。したがって、ポリビニルアルコールは、結合材のいずれかまたは複数の結合材の原料と混合粉砕して、粒度調整すると、より細粒で均質に混合でき、早期強度発現性を高めることができる。
前記ポリマーは、粉体の状態で結合材や砂と混合して用いるか、または、後述の水に溶解して用いてもよい。
4. Polymer The content ratio of the polymer in the water-hard composition of the present invention is 2 to 12 parts by mass in terms of solid content with respect to 100 parts by mass of the binder in order to further increase the strength of the water-hard composition. If the polymer content is less than 2 parts by mass, the effect of improving the strength is low, and if it exceeds 12 parts by mass, the modeled object shrinks, causing deformation or cracking depending on the shape, and a mold with a complicated shape is manufactured. It may not be possible. The content ratio of the polymer is more preferably 3 to 12 parts by mass, still more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder.
The polymer is a polymer dispersion or a re-emulsified powder resin specified in JIS A 6203 in the form of a polymer, and a polyacrylic acid ester or an ethylene / vinyl acetate copolymer in the form of a polymer. , Styrene-butadiene copolymer, vinyl acetate-versatic acid vinyl ester copolymer, vinyl acetate-versatic acid vinyl-acrylic acid ester ternary copolymer, polyvinyl alcohol, maltodextrin, epoxy resin, and urethane resin. One or more types can be mentioned.
Among these, polyvinyl alcohol (partially saponified or completely saponified product of polyvinyl acetate) is preferable because early strength development can be obtained, and polyvinyl alcohol having a saponification degree of 85 to 90 mol% is more preferable. ..
Further, since early strength development can be obtained, the particle size of polyvinyl alcohol is preferably 10% by mass or less for the residue of the 90 μm mesh sieve, and more preferably 10% by mass or less for the residue of the 75 μm sieve. Therefore, polyvinyl alcohol can be mixed and pulverized with the raw materials of one or more of the binders to adjust the particle size, so that the polyvinyl alcohol can be mixed uniformly with finer particles, and the early strength development can be enhanced.
The polymer may be used in a powder state by mixing with a binder or sand, or may be used by dissolving it in water described later.
５．砂
砂は、耐火砂であれば、特に制限されず、珪砂、オリビン砂、ジルコン砂、クロマイト砂、アルミナ砂、および人工砂等から選ばれる１種以上が挙げられる。
また、砂の配合量は、前記結合材１００質量部に対し、好ましくは１００〜４００質量部である。該値が該範囲であれば、耐火性と強度発現性を確保できる。なお、該配合量は、前記結合材１００質量部に対し、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。
5. Sand The sand is not particularly limited as long as it is fire-resistant sand, and examples thereof include one or more selected from silica sand, olivine sand, zircon sand, chromate sand, alumina sand, artificial sand and the like.
The amount of sand blended is preferably 100 to 400 parts by mass with respect to 100 parts by mass of the binder. When the value is within the range, fire resistance and strength development can be ensured. The blending amount is more preferably 150 to 350 parts by mass, still more preferably 200 to 300 parts by mass with respect to 100 parts by mass of the binder.
６．硬化促進剤
本発明の水硬性組成物は、強度発現性を向上させるため、さらに任意成分として硬化促進剤を含むことができる。該硬化促進剤は、炭酸アルカリ金属塩、乳酸アルカリ金属塩、乳酸アルカリ土類金属塩、およびケイ酸アルカリ金属塩から選ばれる１種以上である。これらの硬化促進剤は、ポリマーの含有割合が、結合材１００質量部に対し２〜６質量部である水硬性組成物において強度発現性の向上効果が高い。また、これらの硬化促進剤は、後述の養生温度が１０〜４０℃と低い場合において、強度発現性の向上効果が高い。
そして、(i）前記炭酸アルカリ金属塩は、炭酸ナトリウム、炭酸カリウム、および炭酸リチウムから選ばれる１種以上が挙げられる。また、(ii）前記乳酸アルカリ金属塩は、乳酸ナトリウム、乳酸カリウム、および乳酸リチウムから選ばれる１種以上が挙げられる。(iii）前記乳酸アルカリ土類金属塩は、乳酸カルシウム、および乳酸マグネシウムから選ばれる１種以上が挙げられる。また、(vi）前記ケイ酸アルカリ金属塩は、ケイ酸ナトリウム、ケイ酸カリウム、およびケイ酸リチウムから選ばれる１種以上が挙げられる。
前記硬化促進剤の含有割合は、結合材１００質量部に対し、好ましくは３〜１０質量部である。硬化促進剤の含有割合が該範囲内であれば、迅速な造形のための早期強度発現性と取扱い可能な強度を確保できる。なお、硬化促進剤の含有割合は、結合材１００質量部に対し、より好ましくは４〜９質量部、さらに好ましくは５〜８質量部である。硬化促進剤は、予め水硬性組成物に混合するほか、付加製造装置から供給される水に溶解して用いることもできる。
6. Curing Accelerator The hydraulic composition of the present invention may further contain a curing accelerator as an optional component in order to improve the strength development. The curing accelerator is one or more selected from alkali metal carbonate, alkali metal lactate, alkaline earth metal lactate, and alkali metal silicate. These curing accelerators have a high effect of improving the strength development in a hydraulic composition in which the content ratio of the polymer is 2 to 6 parts by mass with respect to 100 parts by mass of the binder. Further, these curing accelerators have a high effect of improving the strength development when the curing temperature described later is as low as 10 to 40 ° C.
And (i) the alkali metal carbonate includes one or more selected from sodium carbonate, potassium carbonate, and lithium carbonate. (Ii) Examples of the alkali metal lactate salt include one or more selected from sodium lactate, potassium lactate, and lithium lactate. (iii) Examples of the lactic acid alkaline earth metal salt include one or more selected from calcium lactate and magnesium lactate. In addition, (vi) the alkali metal silicate may be one or more selected from sodium silicate, potassium silicate, and lithium silicate.
The content ratio of the curing accelerator is preferably 3 to 10 parts by mass with respect to 100 parts by mass of the binder. When the content ratio of the curing accelerator is within the above range, early strength development and manageable strength for rapid modeling can be ensured. The content ratio of the curing accelerator is more preferably 4 to 9 parts by mass, still more preferably 5 to 8 parts by mass with respect to 100 parts by mass of the binder. The curing accelerator may be mixed with the hydraulic composition in advance, or may be dissolved in water supplied from the addition manufacturing apparatus and used.
７．その他
造形後に残った水硬性組成物の未硬化の粉末を、造形物から除去する作業（デパウダー）を容易にするために、本発明の水硬性組成物は、さらに、結合材の合計１００質量部に対し、任意の成分として疎水性フュームドシリカを０．１〜２質量部、より好ましくは０．５〜１．５質量部含むことができる。ここで、疎水性フュームドシリカとは、フュームドシリカの表面をシランまたはシロキサンで処理して、表面を疎水性にしたシリカ粉末である。
また、水硬性組成物の粉末の除去効率をより高めるため、疎水性フュームドシリカのＢＥＴ比表面積は、好ましくは３０〜３００ｍ２／ｇである。疎水性フュームドシリカのＢＥＴ比表面積が該範囲内であれば、粉体の流動性が向上し、付加製造装置で敷きならした面が平坦で、かつ強度が低下することなく鋳型を軽量化できる。また、造形物の透気性が向上するため鋳物の製造時にガスが発生しても欠陥が生じ難い。また、疎水性フュームドシリカは、粉体の固結の防止や混合性の向上に有効である。
7. Others In order to facilitate the work (depowder) of removing the uncured powder of the water-hard composition remaining after molding from the model, the water-hard composition of the present invention further comprises 100 parts by mass of a binder in total. On the other hand, as an arbitrary component, hydrophobic fumed silica can be contained in an amount of 0.1 to 2 parts by mass, more preferably 0.5 to 1.5 parts by mass. Here, the hydrophobic fumed silica is a silica powder in which the surface of the fumed silica is treated with silane or siloxane to make the surface hydrophobic.
Further, in order to further increase the powder removal efficiency of the hydraulic composition, the BET specific surface area of the hydrophobic fumed silica is preferably 30 to 300 m 2 / g. When the BET specific surface area of the hydrophobic fumed silica is within the range, the fluidity of the powder is improved, the surface laid by the additional manufacturing apparatus is flat, and the weight of the mold can be reduced without reducing the strength. .. In addition, since the air permeability of the modeled object is improved, defects are unlikely to occur even if gas is generated during the production of the casting. Further, the hydrophobic fumed silica is effective in preventing the solidification of the powder and improving the mixing property.
なお、本発明の水硬性組成物は、さらに、強度発現性の調整材等として、高炉スラグ、フライアッシュ、シリカフューム、珪石微粉末、および石灰石粉末等の任意の成分を含んでもよい。 The hydraulic composition of the present invention may further contain any component such as blast furnace slag, fly ash, silica fume, silica stone fine powder, and limestone powder as a strength-developing adjusting material.
８．鋳型の製造方法
該製造方法は、付加製造装置と本発明の水硬性組成物を用いて、鋳型を製造する方法である。付加製造装置は特に限定されず、粉末積層型付加製造装置等の市販品が使用できる。また、水硬性組成物は、前記の成分を市販の混合機または手作業で混合して調製する。なお、結合材として複数の材料を用いる場合、結合材を予め市販の混合機や手作業で混合したり、粉砕機で混合粉砕してもよい。
また、本発明の鋳型の製造方法において、水／結合材の質量比は、鋳型の強度を確保するために、好ましくは０．１以上、より好ましくは０．２以上、さらに好ましくは０．２５以上である。また、鋳物の製造時に発生する水蒸気を抑制するために、好ましくは０．５以下、より好ましく０．４以下、さらに好ましくは０．３５以下である。
水には、必要に応じて、増粘剤、潤滑剤、流動化剤、界面活性剤、および表面張力低減剤から選ばれる１種以上を混合してもよい。
8. Mold Manufacturing Method The manufacturing method is a method of manufacturing a mold using an additional manufacturing apparatus and the water-hard composition of the present invention. The addition manufacturing apparatus is not particularly limited, and commercially available products such as powder lamination type addition manufacturing apparatus can be used. Further, the hydraulic composition is prepared by mixing the above-mentioned components with a commercially available mixer or manually. When a plurality of materials are used as the binder, the binder may be mixed in advance with a commercially available mixer or manually, or may be mixed and crushed with a crusher.
Further, in the method for producing a mold of the present invention, the mass ratio of water / binder is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.25 in order to secure the strength of the mold. That is all. Further, in order to suppress water vapor generated during the production of the casting, the amount is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.35 or less.
If necessary, water may be mixed with one or more selected from thickeners, lubricants, fluidizers, surfactants, and surface tension reducing agents.
鋳型の養生方法は、気中養生単独、気中養生した後に続けて水中養生する方法、または、表面含浸剤養生等がある。これらの中でも、早期の強度発現と鋳物の製造時に発生する水蒸気の抑制の点から、気中養生単独が好ましい。また、カルシウムアルミネート、セメント、およびポリマーによる強度増進の点から、気中養生の温度は、好ましくは１０〜１００℃、より好ましくは３０〜６０℃である。また、気中養生の湿度は、充分な強度発現と生産効率の点から、好ましくは１０〜９０％、より好ましくは１５〜８０％、さらに好ましくは２０〜６０％である。さらに、気中養生時間は、充分な強度発現と生産効率の点から、好ましくは０．５〜１０時間、より好ましくは１〜８時間、さらに好ましくは２〜５時間である。 The mold curing method includes aerial curing alone, a method of aerial curing followed by underwater curing, a surface impregnating agent curing, and the like. Among these, aerial curing alone is preferable from the viewpoint of early strength development and suppression of water vapor generated during the production of castings. Further, the temperature of the aerial curing is preferably 10 to 100 ° C., more preferably 30 to 60 ° C. from the viewpoint of increasing the strength by calcium aluminate, cement and polymer. The humidity of the aerial curing is preferably 10 to 90%, more preferably 15 to 80%, still more preferably 20 to 60% from the viewpoint of sufficient strength development and production efficiency. Further, the aerial curing time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, still more preferably 2 to 5 hours from the viewpoint of sufficient strength development and production efficiency.
また、前記表面含浸剤養生は、造形物にケイ酸アルカリ水溶液を噴霧するか、または造形物をケイ酸アルカリ水溶液中に浸漬して、造形物の強度を増進させる養生である。
前記ケイ酸アルカリ水溶液中のケイ酸アルカリは、好ましくはケイ酸ナトリウムおよび／またはケイ酸カリウムである。そして、前記ケイ酸アルカリ水溶液中のケイ酸アルカリの含有率は、好ましくは１０〜４０質量％である。該含有率が１０質量％未満ではケイ酸アルカリの浸透量が不充分で強度増進効果は低く、４０質量％を超えるとケイ酸アルカリ水溶液の粘性が高くなり浸透性が低下するおそれがある。なお、該含有率は、より好ましくは２０〜３５質量％である。なかでも早期の強度発現と鋳物の製造時の水蒸気の発生抑制の点から、水／結合材の質量比が、好ましくは０．０２以下となるように、ケイ酸アルカリ水溶液を造形物に噴霧する。
Further, the surface impregnating agent curing is a curing that enhances the strength of the modeled object by spraying an alkaline silicate aqueous solution on the modeled object or immersing the modeled object in the alkaline silicate aqueous solution.
The alkali silicate in the alkaline aqueous solution of silicate is preferably sodium silicate and / or potassium silicate. The content of alkali silicate in the aqueous alkali silicate solution is preferably 10 to 40% by mass. If the content is less than 10% by mass, the permeation amount of the alkali silicate is insufficient and the strength enhancing effect is low, and if it exceeds 40% by mass, the viscosity of the alkaline silicate aqueous solution may increase and the permeability may decrease. The content is more preferably 20 to 35% by mass. In particular, from the viewpoint of early strength development and suppression of water vapor generation during the production of castings, an aqueous alkali silicate solution is sprayed onto the modeled object so that the mass ratio of water / binder is preferably 0.02 or less. ..
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．使用した材料
（１）カルシウムアルミネート
非晶質のカルシウムアルミネート（略号：ＣＡ、）
試製品、ＣａＯ／Ａｌ２Ｏ３のモル比は２．２、ガラス化率は９５％以上、ブレーン比表面積は２０００ｃｍ２／ｇである。
（２）セメント
スーパージェットセメント、太平洋セメント社製、ケイ酸カルシウムの含有率は４７質量％、凝結（始発）は３０分、ブレーン比表面積は４７００ｃｍ２／ｇである。ただし、無水石膏を１４質量％含む。
（３）石膏
半水石膏、試薬鹿１級、関東化学社製
（４）砂
(i）人工鋳物砂Ａ（略号：砂Ａ）
アルミナ系、商品名 エスパール♯１８０Ｌ、山川産業社製
(ii）人工鋳物砂Ｂ（略号：砂Ｂ）
アルミナ系、商品名 セラビーズ＃１４５０（登録商標）、伊藤忠セラテック社製
（５）ポリマー
（ａ）酢酸ビニル共重合体 品番 Ｄ５１００Ｐ、粒度７５μｍ以下、日本合成社製
（ｂ）ポリビニルアルコール 品番 ２２−８８Ｓ１（ＰＶＡ２１７ＳＳ）、ケン化度９０％、粒度７５μｍ以下、クラレ社製
（ｃ）ポリビニルアルコール 品番 ＫＰ１８−８８Ｓ１、ケン化度８５％、粒度６３μｍ以下、クラレ社製
（６）硬化促進剤
（i）炭酸リチウム（略号：ＬＣ）
試薬１級、関東化学社製
（ii）乳酸カルシウム（略号：ＣＬ）
試薬１級、関東化学社製
（７）疎水性フュームドシリカ（略号：ＦＳ）
商品名 ＡＥＲＯＳＩＬ ＲＸ２００（登録商標）、日本アエロジル社製
（８）水
３質量％のグリセロール水溶液（ProJet660Pro用バインダー液）、スリーディシステム社製
Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.
1. 1. Materials used (1) Calcium aluminate Amorphous calcium aluminate (abbreviation: CA,)
The sample product, CaO / Al 2 O 3, has a molar ratio of 2.2, a vitrification rate of 95% or more, and a brain specific surface area of 2000 cm 2 / g.
(2) Cement Super Jet Cement, manufactured by Taiheiyo Cement Co., Ltd., has a calcium silicate content of 47% by mass, condensation (first departure) for 30 minutes, and a brain specific surface area of 4700 cm 2 / g. However, it contains 14% by mass of anhydrous gypsum.
(3) Gypsum Semi-hydrated gypsum, reagent deer first grade, manufactured by Kanto Chemical Co., Inc. (4) Sand
(i) Artificial casting sand A (abbreviation: sand A)
Alumina type, product name Espal # 180L, manufactured by Yamakawa Sangyo Co., Ltd.
(ii) Artificial casting sand B (abbreviation: sand B)
Alumina type, trade name Cera beads # 1450 (registered trademark), manufactured by ITOCHU Ceratech (5) Polymer (a) vinyl acetate copolymer Part number D5100P, particle size 75 μm or less, manufactured by Nippon Synthetic Co., Ltd. (b) Polyvinyl alcohol Part number 22-88S1 ( PVA217SS), saponification degree 90%, particle size 75 μm or less, manufactured by Kuraray (c) Polyvinyl alcohol Part No. KP18-88S1, saponification degree 85%, particle size 63 μm or less, manufactured by Kuraray (6) Curing accelerator (i) Lithium carbonate (Abbreviation: LC)
Reagent 1st grade, manufactured by Kanto Chemical Co., Inc. (ii) Calcium lactate (abbreviation: CL)
Reagent 1st grade, manufactured by Kanto Chemical Co., Inc. (7) Hydrophobic fumed silica (abbreviation: FS)
Product name AEROSIL RX200 (registered trademark), manufactured by Nippon Aerosil Co., Ltd. (8) 3% by mass glycerol aqueous solution of water (binder solution for ProJet660Pro), manufactured by 3D System Co., Ltd.
２．水硬性組成物、鋳型、およびモルタル供試体の作製
表１に掲載の配合に従い、前記のカルシウムアルミネート、セメント、ポリマー、および砂等を混合して水硬性組成物を作製した。なお、結合材（カルシウムアルミネート、セメント、および石膏の混合物）１００質量部に対し、混合砂（砂Ａ：砂Ｂ＝１：１［質量比］）は２００質量部用いた。
次に、該水硬性組成物と、付加製造装置として結合材噴射式粉末積層造形装置（商品名： ProJet660Pro スリーディシステム社製）を用いて、結合材噴射法により、断面の寸法が縦１０ｍｍ、横１６ｍｍ、および長さ８０ｍｍのモルタル供試体を作製した。また、実施例１〜１０の水硬性組成を用いて、室温（２０℃）、相対湿度６０％の条件下で鋳型を作製した後、該鋳型は４０℃、相対湿度３０％の条件下で３時間、気中養生した。
なお、前記装置による鋳型の製造方法は、水硬性組成物の所定の位置を選択して、ノズルから一定量の水を噴出し、水硬性組成物を固化する方法であり、水／結合材の質量比は０．２９〜０．３５であった。
2. Preparation of hydraulic composition, mold, and mortar specimen According to the formulation shown in Table 1, the above-mentioned calcium aluminate, cement, polymer, sand, and the like were mixed to prepare a hydraulic composition. 200 parts by mass of mixed sand (sand A: sand B = 1: 1 [mass ratio]) was used with respect to 100 parts by mass of the binder (mixture of calcium aluminate, cement, and gypsum).
Next, using the hydraulic composition and a binder injection type powder laminating molding device (trade name: ProJet660Pro 3D System Co., Ltd.) as an additional manufacturing device, the cross-sectional dimension is 10 mm in length and width by the binder injection method. Mortar specimens having a length of 16 mm and a length of 80 mm were prepared. Further, using the hydraulic composition of Examples 1 to 10, a mold was prepared under the conditions of room temperature (20 ° C.) and a relative humidity of 60%, and then the mold was prepared under the conditions of 40 ° C. and a relative humidity of 30%. I was cured in the air for a while.
The method for producing a mold by the above device is a method of selecting a predetermined position of the water-hard composition and ejecting a certain amount of water from a nozzle to solidify the water-hard composition. The mass ratio was 0.29 to 0.35.
３．モルタル供試体の曲げ強度の測定
次に、前記モルタル供試体を気中で、４０℃、３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点曲げ試験を行い、前記モルタル供試体の曲げ強度を測定した。その結果を表１に示す。
表１に示すように、養生温度が４０℃で養生時間が３時間の曲げ強度は、比較例２では０．６４Ｎ／ｃｍ２と低いのに対し、実施例１〜１０では０．８９〜２．３０Ｎ／ｃｍ２と、比較例２に比べて１．４〜３．６倍も高い。また、硬化促進剤を含む実施例２および４の曲げ強度は、２．０６Ｎ／ｃｍ２以上とより高い。
3. 3. Measurement of bending strength of mortar specimen Next, after curing the mortar specimen in the air at 40 ° C. for 3 hours, 3 points using a bending strength tester (model number: MODEL-2257, manufactured by Aiko Engineering Co., Ltd.). A bending test was performed, and the bending strength of the mortar specimen was measured. The results are shown in Table 1.
As shown in Table 1, the bending strength at a curing temperature of 40 ° C. and a curing time of 3 hours was as low as 0.64 N / cm 2 in Comparative Example 2, whereas it was 0.89 to 2 in Examples 1 to 10. It is .30 N / cm 2 , which is 1.4 to 3.6 times higher than that of Comparative Example 2. Further, the bending strength of Examples 2 and 4 containing the curing accelerator is as high as 2.06 N / cm 2 or more.
４．鋳物の作製
さらに溶湯アルミニウムを、前記鋳型に流し込んで鋳物を作製したところ、いずれの実施例も表面が平滑な鋳物が製造できた。
4. Preparation of Casting Further, when molten aluminum was poured into the mold to prepare a casting, a casting having a smooth surface could be produced in each of the examples.
Claims (4)
ケン化度が８５〜９０モル％のポリビニルアルコールを２〜１２質量部含有する、付加製造装置用水硬性組成物。 Amorphous calcium aluminate having a molar ratio of CaO / Al 2 O 3 of 1.7 to 2.4, a specific surface area of brain of 1000 to 2500 cm 2 / g, and a vitrification rate of 90% or more is 80 to 100% by mass. , And 100 parts by mass of the inorganic binder containing 0 to 20% by mass of cement selected from fast-hardening cement, ultrafast-hardening cement, and waterproof cement.
A water-hard composition for an addition manufacturing apparatus containing 2 to 12 parts by mass of polyvinyl alcohol having a saponification degree of 85 to 90 mol%.
A method for producing a mold, which comprises molding a mold using the additional manufacturing apparatus and the water-hardening composition for the additional manufacturing apparatus according to any one of claims 1 to 3.
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| PCT/JP2018/028438 WO2019026841A1 (en) | 2017-07-31 | 2018-07-30 | Hydraulic composition for additive manufacturing device, and method for manufacturing casting mold |
| TW107126304A TWI756457B (en) | 2017-07-31 | 2018-07-30 | Hydraulic composition for lamination manufacturing apparatus and method for manufacturing casting mold |
| US16/629,764 US11173539B2 (en) | 2017-07-31 | 2018-07-30 | Hydraulic composition for additive manufacturing device and method of manufacturing casting mold |
| DE112018003889.0T DE112018003889T5 (en) | 2017-07-31 | 2018-07-30 | Hydraulic composition for a device for additive manufacturing and method for manufacturing a mold |
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