JP3165262B2 - Binder composition for casting, composition for casting, and method for producing casting mold - Google Patents
Binder composition for casting, composition for casting, and method for producing casting moldInfo
- Publication number
- JP3165262B2 JP3165262B2 JP28356592A JP28356592A JP3165262B2 JP 3165262 B2 JP3165262 B2 JP 3165262B2 JP 28356592 A JP28356592 A JP 28356592A JP 28356592 A JP28356592 A JP 28356592A JP 3165262 B2 JP3165262 B2 JP 3165262B2
- Authority
- JP
- Japan
- Prior art keywords
- casting
- mold
- composition
- polyvinyl alcohol
- binder composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【0001】[0001]
【産業上の利用分野】本発明は、強度、表面安定性等の
性能に優れた鋳造用の鋳型、中子(本明細書の全てにわ
たって鋳型と略称する。)の製造、及びそのために使用
する組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of a casting mold and a core (hereinafter abbreviated as a mold throughout the present specification) which are excellent in performance such as strength and surface stability, and to be used therefor. Composition.
【従来の技術】従来、鋳込みの際に刺激性の酸ガスを発
生しない鋳造用鋳型を迅速かつ能率よく製造するための
組成物としては、例えば、液体状エステル系硬化剤で硬
化可能なカリウムアルカリ性フェノール・ホルムアルデ
ヒド樹脂及びシラン化合物を含む樹脂組成物が知られて
いる(特開平1−40136号公報参照)。2. Description of the Related Art Heretofore, as a composition for rapidly and efficiently producing a casting mold which does not generate irritating acid gas at the time of casting, for example, potassium alkali which can be hardened with a liquid ester hardener is used. A resin composition containing a phenol / formaldehyde resin and a silane compound is known (see JP-A-1-40136).
【0002】[0002]
【発明が解決しようとする課題】しかしながら、このよ
うな従来公知の樹脂組成物を使用して製造した鋳型は、
強度が低い。更に、鋳込み完了後の鋳型の崩壊性も悪
い。そのため、鋳物の品質低下の原因となっている。本
発明は、著しく高い鋳型強度及び鋳型の表面安定性を有
し、かつ鋳込み完了後の鋳型崩壊性にも優れた鋳造用鋳
型の製造方法、及びそれに使用する鋳造成形用粘結剤組
成物及び鋳造成形用組成物を提供することを目的とす
る。However, a mold produced by using such a conventionally known resin composition,
Low strength. Further, the disintegration of the mold after the completion of the casting is poor. For this reason, the quality of the casting is deteriorated. The present invention has a remarkably high mold strength and mold surface stability, and a method for producing a casting mold excellent in mold disintegration after completion of casting, and a binder composition for casting used in the method and An object of the present invention is to provide a composition for casting.
【0003】[0003]
【課題を解決するための手段】前記の目的を達成するた
めに、本発明の液体状有機酸エステル硬化性鋳造成形用
粘結剤組成物は、水溶性フェノール樹脂、ポリビニルア
ルコール、シラン化合物及び必要により溶媒を含有する
ことを特徴とする。本発明の鋳造成形用組成物は、水溶
性フェノール樹脂、ポリビニルアルコール、シラン化合
物、液体状有機酸エステル系硬化剤、粒状耐火性骨材及
び必要により溶媒を含有することを特徴とする。本発明
の鋳造用鋳型の製造方法は、水溶性フェノール樹脂、ポ
リビニルアルコール、シラン化合物及び溶媒を含有する
粘結剤組成物の溶液と液体状有機酸エステル系硬化剤と
粒状耐火性骨材とを混合し、この混合物を鋳型枠内に収
納して成形し硬化させることを特徴とする。In order to achieve the above object, a binder composition for liquid organic acid ester curable casting molding of the present invention comprises a water-soluble phenol resin, polyvinyl alcohol, a silane compound and Wherein the solvent is contained. The composition for casting and molding of the present invention is characterized by containing a water-soluble phenol resin, polyvinyl alcohol, a silane compound, a liquid organic acid ester-based curing agent, a granular refractory aggregate, and, if necessary, a solvent. The method for producing a casting mold of the present invention comprises a solution of a binder composition containing a water-soluble phenolic resin, polyvinyl alcohol, a silane compound and a solvent, a liquid organic acid ester-based curing agent, and a granular refractory aggregate. It is characterized by mixing, storing the mixture in a mold frame, molding and curing.
【0004】本発明における粒状耐火性骨材としては、
けい砂、クロム鉄鉱砂、ジルコン砂、かんらん石砂等の
従来鋳型鋳造用に使用される耐火性の粒状砂のほか、粘
土質の砂、再生砂も使用することができる。本発明に用
いられる水溶性フェノール樹脂とは液体状有機酸エステ
ル系硬化剤で硬化可能な樹脂であり、例えばフェノー
ル、クレゾール、レゾルシノール、キシレノール、ビス
フェノールA、クミルフェノール、ノニルフェノール、
ブチルフェノール、フェニルフェノール、エチルフェノ
ール、オクチルフェノール、アミルフェノール、ナフト
ール、ビスフェノールF、ビスフェノールC、カテコー
ル、ハイドロキノン、ピロガロール、フロログルシン、
リグニン、ビスフェノールA残渣、クレゾール残渣、ク
ロロフェノール、ジクロロフェノール、その他の置換フ
ェノールを含めたフェノール類とホルムアルデヒド、ア
セトアルデヒド、フルフラールアルデヒド及びアルデヒ
ドの混合物等との反応によって得られるフェノール樹脂
が挙げられる。これらのフェノール樹脂の縮合に用いら
れる適当なアルカリ性物質は水酸化ナトリウム、水酸化
カリウム、水酸化リチウム及びこれらの混合物である
が、水酸化カリウムが最も好ましい。この水溶性フェノ
ール樹脂の重量平均分子量は800〜2000の範囲が
好ましい。本発明における水溶性フェノール樹脂として
はカリウムアルカリ性フェノール・ホルムアルデヒド樹
脂が好ましく、通常、固形分50〜75重量%の溶液、
特に水溶液として使用される。[0004] As the granular refractory aggregate in the present invention,
Silica sand, chromite sand, zircon sand, olivine sand, and other refractory granular sands conventionally used for mold casting, as well as clay sand and recycled sand, can also be used. The water-soluble phenolic resin used in the present invention is a resin curable with a liquid organic acid ester-based curing agent, such as phenol, cresol, resorcinol, xylenol, bisphenol A, cumylphenol, nonylphenol,
Butylphenol, phenylphenol, ethylphenol, octylphenol, amylphenol, naphthol, bisphenol F, bisphenol C, catechol, hydroquinone, pyrogallol, phloroglucin,
Phenol resins obtained by reacting phenols including lignin, bisphenol A residue, cresol residue, chlorophenol, dichlorophenol, and other substituted phenols with formaldehyde, acetaldehyde, furfural aldehyde, and a mixture of aldehydes, and the like. Suitable alkaline substances used for the condensation of these phenolic resins are sodium hydroxide, potassium hydroxide, lithium hydroxide and mixtures thereof, with potassium hydroxide being most preferred. The weight average molecular weight of this water-soluble phenol resin is preferably in the range of 800 to 2,000. As the water-soluble phenol resin in the present invention, a potassium alkaline phenol-formaldehyde resin is preferable, and usually, a solution having a solid content of 50 to 75% by weight,
In particular, it is used as an aqueous solution.
【0005】本発明におけるポリビニルアルコールは、
その重合度、ケン化度に限定はなく、公知のものはいず
れも使用することができるが、ケン化度はその溶剤に対
する溶解性、ゲル化性の点から、80〜99%の範囲で
あることが好ましく、重合度はその溶液の粘度の点から
2500以下であることが好ましい。更にポリビニルア
ルコールの配合量は、粘結剤組成物溶液とした場合の粘
度及び鋳型の強度の点から、水溶性フェノール樹脂10
0重量部(固形分として)に対して、0.1〜10重量
部の範囲が好ましく、0.5〜5重量部の範囲が特に好
ましい。ポリビニルアルコールは、製造した水溶性フェ
ノール樹脂に配合してもよく、水溶性フェノール樹脂の
製造の際にあらかじめ配合しておいてもよい。本発明に
おけるシラン化合物は、形成鋳型の強度を改善するため
に、樹脂溶液に対して0.05〜3重量%の範囲で使用
するのが好ましく、その例としては、γ−グリシドキシ
プロピルトリメトキシシラン、γ−アミノプロピルトリ
エトキシシラン等を挙げることができる。[0005] The polyvinyl alcohol in the present invention is
The degree of polymerization and the degree of saponification are not limited, and any known one can be used, but the degree of saponification is in the range of 80 to 99% from the viewpoint of solubility in the solvent and gelation. The polymerization degree is preferably 2500 or less from the viewpoint of the viscosity of the solution. Furthermore, the blending amount of polyvinyl alcohol is determined based on the viscosity of the binder composition solution and the strength of the mold.
The range is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 0 parts by weight (as solid content). The polyvinyl alcohol may be blended with the produced water-soluble phenol resin, or may be blended in advance at the time of producing the water-soluble phenol resin. The silane compound in the present invention is preferably used in the range of 0.05 to 3% by weight based on the resin solution in order to improve the strength of the forming template. For example, γ-glycidoxypropyl tri Methoxysilane, γ-aminopropyltriethoxysilane and the like can be mentioned.
【0006】本発明における硬化剤である有機酸エステ
ルは、蟻酸メチル、蟻酸エチル、蟻酸プロピルを除く液
体状のエステル系化合物であり、その沸点が常温で10
0℃以上のものである。具体的には、一価又は多価アル
コールとカルボン酸とのエステル化合物、特に炭素数1
〜10の一価又は多価アルコールと炭素数2〜10のカ
ルボン酸とのエステル化合物、あるいはラクトン化合
物、カーボネート化合物を挙げることができる。さらに
具体的には例えば、酢酸エチル、アジピン酸ジメチル、
コハク酸ジメチル、エチレングリコールジアセテート、
モノアセチン、ダイアセチン、トリアセチン、エチレン
カーボネート、γ−ブチロラクトン、プロピオラクト
ン、ε−カプロラクトン、あるいはこれらの混合物であ
る。使用される液体状有機酸エステル系硬化剤の量は、
粘結剤組成物の溶液に対して5〜110重量%、特に2
0〜60重量%の範囲が好ましい。The organic acid ester as the curing agent in the present invention is a liquid ester compound excluding methyl formate, ethyl formate and propyl formate, and has a boiling point of 10 at room temperature.
0 ° C or higher. Specifically, an ester compound of a monohydric or polyhydric alcohol and a carboxylic acid, particularly one having 1 carbon atom
An ester compound of a monohydric or polyhydric alcohol having 10 to 10 and a carboxylic acid having 2 to 10 carbon atoms, a lactone compound, and a carbonate compound can be given. More specifically, for example, ethyl acetate, dimethyl adipate,
Dimethyl succinate, ethylene glycol diacetate,
Monoacetin, diacetin, triacetin, ethylene carbonate, γ-butyrolactone, propiolactone, ε-caprolactone, or a mixture thereof. The amount of the liquid organic acid ester-based curing agent used is
5 to 110% by weight, especially 2%, based on the solution of the binder composition
A range of 0 to 60% by weight is preferred.
【0007】鋳造用鋳型の製造は、粒状耐火性骨材と粘
結剤組成物の溶液と液体状有機酸エステル系硬化剤とを
慣用の方法によって混合し、成形することによって行
う。中子取りと鋳型枠もまた、従来使用されている慣用
型のものを使用することができる。本発明の粒状耐火性
骨材と粘結剤組成物の有機溶剤、水等の溶液と液体状有
機酸エステル系硬化剤とを配合した組成物を成形した型
は、常温あるいはそれより若干高い温度で一定時間放置
して硬化させる。硬化時間は、型の大きさと形状及び樹
脂の種類に依存するが、1時間から24時間の範囲であ
る場合がほとんどである。本発明の粘結剤組成物溶液
は、粒状耐火性骨材に対して、0.5〜8重量%の範囲
で配合するのが好ましい。成形鋳型の強度の点からは、
1〜3重量%の範囲で配合するのが特に好ましい。The casting mold is manufactured by mixing a granular refractory aggregate, a solution of a binder composition, and a liquid organic acid ester-based curing agent by a conventional method, followed by molding. For the core removal and the mold frame, a conventional type conventionally used can also be used. An organic solvent of the granular refractory aggregate of the present invention and the binder composition, a mold formed by mixing a solution such as water and a liquid organic acid ester-based curing agent is molded at room temperature or a slightly higher temperature. And let it cure for a certain period of time. The curing time depends on the size and shape of the mold and the type of the resin, but is usually in the range of 1 hour to 24 hours. The binder composition solution of the present invention is preferably blended in the range of 0.5 to 8% by weight with respect to the granular refractory aggregate. In terms of the strength of the mold,
It is particularly preferable to mix in the range of 1 to 3% by weight.
【0008】[0008]
【実施例】以下、実施例及び比較例により、本発明を更
に詳細に説明する。実施例及び比較例において、「部」
は全て「重量部」を意味し、「%」は全て「重量%」を
意味する。実施例1〜3、比較例1、2 粘結剤組成物の調製 100%フェノール27.2部とKOH10部を含む水
溶液を混合して溶解した。この中に46.9部の37%
ホルムアルデヒド水溶液をさらに加えた(ホルムアルデ
ヒド:フェノールのモル比は2.0:1)。この混合物
溶液を還流下で3時間加熱した後に冷却して、固形分5
0%のカリウムアルカリ性フェノール・ホルムアルデヒ
ド樹脂の水溶液を製造した。このカリウムアルカリ性フ
ェノール・ホルムアルデヒド樹脂水溶液中に、この樹脂
100部(固形分として)に対し、表1に示す配合量の
10%あるいは30%ポリビニルアルコール水溶液(G
L−05:重合度500、ケン化度88%)と、γ−グ
リシドキシプロピルトリメトキシシランを1部加えて充
分に混合し、粘結剤組成物を調製した。表1において、
実施例1では10%ポリビニルアルコール水溶液を配合
し、それ以外の実施例では30%ポリビニルアルコール
水溶液を配合し、比較例1では他に何も加えず、比較例
2では実施例1におけるポリビニルアルコール水溶液の
添加量に相当する量の水を加えた。 〔物性測定方法〕固形分含量は、空気循環炉内で試料
2.0±0.1gを100℃で3時間加熱して測定し
た。The present invention will be described below in more detail with reference to Examples and Comparative Examples. In Examples and Comparative Examples,
Means "parts by weight", and "%" means "% by weight". Preparation of binder compositions in Examples 1 to 3 and Comparative Examples 1 and 2 An aqueous solution containing 27.2 parts of 100% phenol and 10 parts of KOH was mixed and dissolved. 37% of 46.9 parts in this
An aqueous formaldehyde solution was further added (formaldehyde: phenol molar ratio 2.0: 1). The mixture solution was heated under reflux for 3 hours and then cooled to obtain a solid content of 5%.
An aqueous solution of 0% potassium alkaline phenol-formaldehyde resin was prepared. In this potassium alkaline phenol / formaldehyde resin aqueous solution, 10% or 30% polyvinyl alcohol aqueous solution (G
L-05: polymerization degree 500, saponification degree 88%) and one part of γ-glycidoxypropyltrimethoxysilane were added and mixed well to prepare a binder composition. In Table 1,
In Example 1, a 10% aqueous solution of polyvinyl alcohol was added. In other examples, an aqueous solution of 30% polyvinyl alcohol was added. In Comparative Example 1, nothing else was added. In Comparative Example 2, the aqueous solution of polyvinyl alcohol in Example 1 was added. Water was added in an amount corresponding to the amount added. [Method for Measuring Physical Properties] The solid content was measured by heating 2.0 ± 0.1 g of a sample at 100 ° C. for 3 hours in an air circulation furnace.
【0009】鋳型試験片の製造 フリーマントル珪砂1000部に硬化剤としてトリアセ
チン4部を加えて1分間混練し、さらにこの中に前記の
とおり製造した粘結剤組成物の溶液を20部加えて更に
1分間混練して、鋳造成形用組成物を調製した。この鋳
造成形用組成物を木型枠内に収納して成形し、常温で2
4時間放置して、直径50mm、高さ50mmの鋳型試
験片を製造した。製造した鋳型試験片の性能を表1に示
す。 Production of mold test piece To 1000 parts of Fremantle silica sand, 4 parts of triacetin as a hardening agent was added and kneaded for 1 minute. Further, 20 parts of the solution of the binder composition produced as described above was added thereto, and further added. The mixture was kneaded for 1 minute to prepare a composition for casting and molding. The composition for casting and molding was stored in a wooden form and molded,
It was left for 4 hours to produce a mold test piece having a diameter of 50 mm and a height of 50 mm. Table 1 shows the performance of the manufactured mold test pieces.
【0010】〔性能試験方法〕 1.圧縮強度 鋳型試験片製造後、常温(20℃)、50%相対温度に
おける鋳型試験片の圧縮強度(kgf/cm2 )を測
定。 2.表面安定性 鋳型試験片を常温(20℃)で10メッシュの篩上で2
分間振とうして、篩上に残った鋳型試験片の残存率を
(重量)%で表示。 3.熱間表面安定性 鋳型試験片を700℃で20秒間加熱した後、10メッ
シュの篩上で1分間振とうして、それぞれ篩上に残った
鋳型試験片の残存率を(重量)%で表示。 4.残留強度 鋳型試験片を700℃で5分間加熱した後、常温(20
℃)で24時間放置後の鋳型試験片の圧縮強度(kgf
/cm2 )を測定。[Performance Test Method] Compressive strength After the mold test piece was manufactured, the compressive strength (kgf / cm 2 ) of the mold test piece was measured at normal temperature (20 ° C.) and 50% relative temperature. 2. Surface stability A mold specimen was placed on a 10-mesh sieve at room temperature (20 ° C.) for 2 minutes.
After shaking for a minute, the residual ratio of the mold test piece remaining on the sieve is indicated by (weight)%. 3. Hot surface stability After the mold test piece was heated at 700 ° C. for 20 seconds, it was shaken on a 10-mesh sieve for 1 minute, and the residual ratio of the mold test piece remaining on the sieve was indicated by (weight)%. . 4. Residual strength After heating the mold specimen at 700 ° C. for 5 minutes,
℃) for 24 hours, and the compressive strength (kgf
/ Cm 2 ).
【0011】[0011]
【表1】 [Table 1]
【0012】[0012]
【発明の効果】以上説明したとおり、本発明により成形
した鋳型は著しく高い圧縮強度を有し、しかも同時に残
留強度も低下させることができたので、注湯して鋳物の
製造を完了した後の鋳型の崩壊性が一段と優れているう
え、表面安定性及び熱間表面安定性も良好である。その
ため、高い圧縮強度を要しかつ鋳造後の型ばらしが容易
であることが必須の、大型の精密鋳物を高品質でかつ能
率よく製造することが可能となった。As described above, the mold molded according to the present invention has remarkably high compressive strength and, at the same time, the residual strength can be reduced. The disintegration of the mold is much better, and the surface stability and hot surface stability are also good. For this reason, it has become possible to produce a large-sized precision casting with high quality and efficiency, which requires high compressive strength and requires easy mold release after casting.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 塩川 盛雄 神奈川県横浜市鶴見区大黒町7番43号 保土谷アシュランド株式会社 技術研究 所内 (56)参考文献 特開 平6−579(JP,A) 特開 平4−284940(JP,A) (58)調査した分野(Int.Cl.7,DB名) B22C 1/00 - 1/26 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Morio Shiokawa 7-43, Oguro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture Hodogaya Ashland Co., Ltd. Technical Research Institute (56) References JP-A-6-579 (JP, A JP-A-4-284940 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B22C 1/00-1/26
Claims (3)
コール、シラン化合物及び必要により溶媒を含有するこ
とを特徴とする液体状有機酸エステル硬化性鋳造成形用
粘結剤組成物。1. A liquid organic acid ester curable binder composition for casting, which comprises a water-soluble phenol resin, polyvinyl alcohol, a silane compound and, if necessary, a solvent.
コール、シラン化合物、液体状有機酸エステル系硬化
剤、粒状耐火性骨材及び必要により溶媒を含有すること
を特徴とする鋳造成形用組成物。2. A casting composition comprising a water-soluble phenol resin, polyvinyl alcohol, a silane compound, a liquid organic acid ester-based curing agent, a granular refractory aggregate and, if necessary, a solvent.
コール、シラン化合物及び溶媒を含有する粘結剤組成物
の溶液と液体状有機酸エステル系硬化剤と粒状耐火性骨
材とを混合し、この混合物を鋳型枠内に収納して成形し
硬化させることを特徴とする鋳造用鋳型の製造方法。3. A solution of a binder composition containing a water-soluble phenolic resin, polyvinyl alcohol, a silane compound and a solvent, a liquid organic acid ester-based curing agent, and a particulate refractory aggregate are mixed. A method for producing a casting mold, wherein the mold is housed in a mold frame, molded and cured.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28356592A JP3165262B2 (en) | 1992-09-30 | 1992-09-30 | Binder composition for casting, composition for casting, and method for producing casting mold |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28356592A JP3165262B2 (en) | 1992-09-30 | 1992-09-30 | Binder composition for casting, composition for casting, and method for producing casting mold |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06114491A JPH06114491A (en) | 1994-04-26 |
JP3165262B2 true JP3165262B2 (en) | 2001-05-14 |
Family
ID=17667180
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28356592A Expired - Lifetime JP3165262B2 (en) | 1992-09-30 | 1992-09-30 | Binder composition for casting, composition for casting, and method for producing casting mold |
Country Status (1)
Country | Link |
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JP (1) | JP3165262B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7079093B2 (en) * | 2015-11-18 | 2022-06-01 | 花王株式会社 | Binder composition for mold molding |
CN109805391A (en) * | 2019-03-08 | 2019-05-28 | 上海萧雅生物科技股份有限公司 | A kind of whitening food formulation and its instructions of taking containing tablet and capsule dual dosage form |
-
1992
- 1992-09-30 JP JP28356592A patent/JP3165262B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH06114491A (en) | 1994-04-26 |
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