JP2003170244A - Phenol resin composition for shell molding and resin coated sand for shell molding mold - Google Patents
Phenol resin composition for shell molding and resin coated sand for shell molding moldInfo
- Publication number
- JP2003170244A JP2003170244A JP2001371245A JP2001371245A JP2003170244A JP 2003170244 A JP2003170244 A JP 2003170244A JP 2001371245 A JP2001371245 A JP 2001371245A JP 2001371245 A JP2001371245 A JP 2001371245A JP 2003170244 A JP2003170244 A JP 2003170244A
- Authority
- JP
- Japan
- Prior art keywords
- phenol resin
- alkali metal
- coated sand
- shell mold
- resin 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.)
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Links
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- Compositions Of Macromolecular Compounds (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は鋳造用の主型及び中
子（以下、単に鋳型という）の製造に用いられる硬化
性、造型性に優れたシェルモールド用フェノール樹脂組
成物及びシェルモールド鋳型用レジンコーテッドサンド
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol resin composition for a shell mold and a shell resin mold, which are used in the production of a casting main mold and a core (hereinafter, simply referred to as a mold) and have excellent curability and moldability. It is about resin coated sand.
【０００２】[0002]
【従来の技術】鋳型の製造に用いられるシェルモールド
用鋳型材料としては耐火性粒状材料の表面に熱硬化性フ
ェノール樹脂を被覆したレジンコーテッドサンドが主に
使用されている。この熱硬化性フェノール樹脂にはフェ
ノール類とホルムアルデヒド類とを塩基性触媒を用いて
反応させたレゾール型フェノール樹脂とフェノール類と
ホルムアルデヒド類とを酸性触媒を用いて反応させたノ
ボラック型フェノール樹脂があり、ノボラック型フェノ
ール樹脂は硬化剤にヘキサメチレンテトラミン（以下ヘ
キサミンという）を使用している。2. Description of the Related Art As a mold material for a shell mold used for manufacturing a mold, a resin coated sand having a surface of a refractory granular material coated with a thermosetting phenol resin is mainly used. This thermosetting phenol resin includes a resol type phenol resin obtained by reacting phenols and formaldehyde with a basic catalyst and a novolac type phenol resin obtained by reacting phenols with formaldehyde with an acidic catalyst. The novolak type phenol resin uses hexamethylenetetramine (hereinafter referred to as hexamine) as a curing agent.
【０００３】[0003]
【発明が解決しようとする課題】ノボラック型フェノー
ル樹脂を用いたシェルモールド用レジンコーテッドサン
ドは硬化剤にヘキサミンを使用しているため、鋳型造型
の加熱硬化時、ヘキサミンの分解によりアンモニアガス
が発生し、これらのガスが悪臭の原因となり作業環境を
悪化させる一原因となっている。硬化剤のヘキサミン添
加量を低減すればアンモニアガスも低減するが、鋳型造
型を満足する硬化速度が得られない。そのため速硬化タ
イプのノボラック型フェノール樹脂いわゆるハイオルソ
ノボラックやサリチル酸、安息香酸等の硬化促進剤を用
いる方法がある。しかしこれらの方法では十分な硬化速
度は得られず、かつハイオルソノボラックは鋳型強度が
低くまた価格的に不利であり、一方、サリチル酸、安息
香酸等の硬化促進剤はレジンコーテッドサンドの融着点
が低下し、ブロッキングの問題がある。本発明はこのよ
うな事情のもとで、ヘキサミンを低減しても鋳型造型が
可能な硬化性を有し、造型性に優れたシェルモールド用
フェノール樹脂組成物及びシェルモールド鋳型用レジン
コーテッドサンドを提供することを目的とする。[Problems to be Solved by the Invention] Since resin coated sand for shell molds using a novolac type phenolic resin uses hexamine as a curing agent, ammonia gas is generated due to decomposition of hexamine during heat curing during mold making. However, these gases cause a bad odor, which is one of the causes of deteriorating the working environment. If the amount of hexamine added to the curing agent is reduced, the amount of ammonia gas is also reduced, but the curing rate that satisfies the molding of the mold cannot be obtained. Therefore, there is a method of using a fast-curing type novolac-type phenol resin, a so-called high ortho novolac, or a curing accelerator such as salicylic acid or benzoic acid. However, these methods do not provide a sufficient curing rate, and high ortho novolac has a low mold strength and is disadvantageous in terms of price.On the other hand, curing accelerators such as salicylic acid and benzoic acid have a fusion point of resin coated sand. And there is a blocking problem. Under such circumstances, the present invention has a curability capable of molding a mold even if hexamine is reduced, and a phenol resin composition for a shell mold and a resin coated sand for a shell mold having excellent moldability. The purpose is to provide.
【０００４】[0004]
【課題を解決するための手段】本発明者等は前記の目的
を達成するため鋭意研究を重ねた結果、硬化促進剤にア
ルカリ金属弱酸塩又はアルカリ金属水酸化物を用いると
ノボラック型フェノール樹脂とヘキサミンの硬化反応が
促進され、シェルモールド鋳型用レジンコーテッドサン
ドの造型性が良好になることを見出し、本発明を完成す
るに至った。本発明は、ノボラック型フェノール樹脂
と、アルカリ金属弱酸塩又はアルカリ金属水酸化物を含
有することを特徴とするシェルモールド用フェノール樹
脂組成物に関する。本発明は、また、耐火性粒状材料
と、アルカリ金属弱酸塩又はアルカリ金属水酸化物と、
ノボラック型フェノール樹脂と、ヘキサメチレンテトラ
ミンとを混練してなることを特徴とするシェルモールド
鋳型用レジンコーテッドサンドに関する。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, when an alkali metal weak acid salt or alkali metal hydroxide was used as a curing accelerator, novolak type phenol resin was obtained. The inventors have found that the curing reaction of hexamine is promoted and the moldability of the resin coated sand for shell mold is improved, and the present invention has been completed. The present invention relates to a phenol resin composition for a shell mold, which comprises a novolac type phenol resin and a weak alkali metal salt or an alkali metal hydroxide. The present invention also comprises a refractory particulate material, a weak alkali metal salt or alkali metal hydroxide,
The present invention relates to a resin coated sand for shell mold casting, which is obtained by kneading a novolac type phenol resin and hexamethylenetetramine.
【０００５】[0005]
【発明の実施の形態】本発明のシェルモールド用フェノ
ール樹脂組成物に用いられるノボラック型フェノール樹
脂としては、フェノール類とアルデヒド類とを酸性触媒
を使用して反応させて得たノボラック型シェルモールド
用フェノール樹脂が好ましく用いられる。フェノール類
とホルムアルデヒド類のモル比（Ｆ／Ｐ）は好ましくは
０．４０〜０．９０であり、このような混合物を酸性触
媒により通常の方法で合成させることにより得られる。
フェノール類としてはフェノールの他、クレゾール、キ
シレノール等のアルキルフェノール、カテコール、ハイ
ドロキノン等の多価フェノール、ビスフェノールＡなど
の通常のノボラック合成に用いられるフェノール類なら
びにこれらの混合物が使用される。ホルムアルデヒド類
としてはホルマリンの他パラホルムアルデヒド、トリオ
キサンなどのホルムアルデヒド重合体、ならびにこれら
の混合物が使用される。酸性触媒としては、塩酸、硫酸
等の無機酸、しゅう酸、パラトルエンスルホン酸などの
有機酸が単独で又は２種以上の混合物として使用され
る。また一般にハイオルソノボラックの合成に用いられ
る酢酸亜鉛等の金属触媒も使用可能である。BEST MODE FOR CARRYING OUT THE INVENTION The novolak-type phenol resin used in the phenol resin composition for shell mold of the present invention is a novolak-type shell mold obtained by reacting phenols and aldehydes using an acidic catalyst. Phenolic resins are preferably used. The molar ratio (F / P) of phenols and formaldehydes is preferably 0.40 to 0.90, and it can be obtained by synthesizing such a mixture by an ordinary method using an acidic catalyst.
As phenols, in addition to phenol, alkylphenols such as cresol and xylenol, polyhydric phenols such as catechol and hydroquinone, phenols such as bisphenol A which are used in ordinary novolak synthesis, and mixtures thereof are used. As the formaldehydes, formalin, paraformaldehyde, formaldehyde polymers such as trioxane, and mixtures thereof are used. As the acidic catalyst, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as oxalic acid and paratoluenesulfonic acid are used alone or as a mixture of two or more kinds. Further, a metal catalyst such as zinc acetate generally used for the synthesis of high ortho novolac can also be used.
【０００６】本発明のシェルモールド用フェノール樹脂
組成物は、アルカリ金属弱酸塩又はアルカリ金属水酸化
物を含有する。このアルカリ金属弱酸塩又はアルカリ金
属水酸化物は硬化促進剤として作用する。前記アルカリ
金属弱酸塩としては、アルカリ金属と弱酸の塩であれ
ば、制限なく使用でき、該弱酸としては、例えば、炭
酸、カルボン酸又はフェノール化合物などが挙げられ
る。硬化速度、取り扱い性、コストなどを考慮すると、
アルカリ金属炭酸塩又はアルカリ金属炭酸水素塩が好ま
しい。アルカリ金属炭酸塩又はアルカリ金属炭酸水素塩
としては、具体的には、炭酸リチウム、炭酸ナトリウ
ム、炭酸カリウム、炭酸水素リチウム、炭酸水素ナトリ
ウム、炭酸水素カリウム等が挙げられる。前記アルカリ
金属水酸化物としては、水酸化リチウム、水酸化ナトリ
ウム、水酸化カリウム等が挙げられる。前記アルカリ金
属弱酸塩又はアルカリ金属水酸化物は単独で用いてもよ
く、また２種以上を用いてもよい。アルカリ金属弱酸塩
又はアルカリ金属水酸化物の総量は、ノボラック型フェ
ノール樹脂１００重量部に対して、好ましくは０．５〜
２０重量部、より好ましくは１〜１０重量部である。
０．５重量部未満では硬化促進の効果が少なく、２０重
量部を超えると鋳型の強度が低下する。アルカリ金属弱
酸塩又はアルカリ金属水酸化物の添加は、ノボラック型
フェノール樹脂の合成終了時点又はシェルモールド鋳型
用レジンコーテッドサンド製造時のどちらでも良い。The phenol resin composition for shell molds of the present invention contains a weak alkali metal acid salt or an alkali metal hydroxide. This weak alkali metal salt or alkali metal hydroxide acts as a curing accelerator. The alkali metal weak acid salt can be used without limitation as long as it is a salt of an alkali metal and a weak acid, and examples of the weak acid include carbonic acid, carboxylic acid, and phenol compounds. Considering the curing speed, handleability, cost, etc.,
Alkali metal carbonates or hydrogen carbonates are preferred. Specific examples of the alkali metal carbonate or the alkali metal hydrogen carbonate include lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide and potassium hydroxide. The weak alkali metal salt or alkali metal hydroxide may be used alone or in combination of two or more kinds. The total amount of weak alkali metal salt or alkali metal hydroxide is preferably 0.5 to 100 parts by weight of the novolac type phenol resin.
20 parts by weight, more preferably 1 to 10 parts by weight.
If it is less than 0.5 part by weight, the effect of promoting the curing is small, and if it exceeds 20 parts by weight, the strength of the mold is lowered. The alkali metal weak acid salt or alkali metal hydroxide may be added either at the time when the synthesis of the novolac type phenol resin is completed or when the resin coated sand for shell mold mold is manufactured.
【０００７】本発明のシェルモールド鋳型用レジンコー
テッドサンドに使用される耐火性粒状材料としては、石
英質を主成分とする珪砂、クロマイト砂、ジルコン砂、
オリビン砂、ムライト砂、合成ムライト砂、マグネシア
及びこれらの回収砂、再生砂等が挙げられる。本発明に
おいては、これらの耐火性粒状材料は、新砂、回収砂、
再生砂、あるいはこれらの混合砂が使用可能である。The refractory granular material used in the resin coated sand for the shell mold of the present invention includes silica sand containing quarts as a main component, chromite sand, zircon sand,
Examples include olivine sand, mullite sand, synthetic mullite sand, magnesia, and recovered sand and recycled sand thereof. In the present invention, these refractory granular materials include fresh sand, recovered sand,
Reclaimed sand or mixed sand of these can be used.
【０００８】ノボラック型フェノール樹脂としては通常
シェルモールド用レジンコーテッドサンドに用いられる
ランダムノボラック、ハイオルソノボラック等のノボラ
ック型フェノール樹脂が使用できる。またノボラック型
フェノール樹脂の一部をレゾール型フェノール樹脂に替
え併用しても良い。シェルモールド用レジンコーテッド
サンドには硬化剤としてヘキサミンをノボラック型フェ
ノール樹脂１００重量部に対して、好ましくは３〜２０
重量部、より好ましくは５〜１５重量部、特に好ましく
は６〜１２重量部添加する。ヘキサミンが３重量部未満
では硬化が遅く鋳型造型性が悪くなることがある。２０
重量部を超えると造型時のアンモニア発生量が多く作業
環境を悪化させたり、また鋳物のガス欠陥も発生するこ
とがある。As the novolac type phenolic resin, a novolac type phenolic resin such as a random novolac or high ortho novolac usually used for resin coated sand for shell mold can be used. Further, a part of the novolac type phenol resin may be replaced with the resol type phenol resin and used together. Hexamine as a curing agent is preferably contained in the resin coated sand for shell mold in an amount of 3 to 20 relative to 100 parts by weight of the novolac type phenol resin.
Parts by weight, more preferably 5 to 15 parts by weight, particularly preferably 6 to 12 parts by weight. If the amount of hexamine is less than 3 parts by weight, curing may be slow and moldability may deteriorate. 20
If it exceeds the weight part, a large amount of ammonia is generated at the time of molding, the working environment is deteriorated, and gas defects of the casting may occur.
【０００９】アルカリ金属弱酸塩又はアルカリ金属水酸
化物の添加量はシェルモールド用フェノール樹脂組成物
と同様ノボラック型フェノール樹脂１００重量部に対し
て、好ましくは０．５〜２０重量部、より好ましくは１
〜１０重量部が望ましい。アルカリ金属弱酸塩又はアル
カリ金属水酸化物の添加は、ノボラック型フェノール樹
脂と同時に添加してもよいし、又は硬化剤のヘキサミン
と混合して添加してもよい。The amount of the weak alkali metal salt or alkali metal hydroxide added is preferably 0.5 to 20 parts by weight, and more preferably 100 parts by weight of the novolac type phenol resin as in the case of the shell mold phenol resin composition. 1
10 to 10 parts by weight is desirable. The weak alkali metal acid salt or alkali metal hydroxide may be added at the same time as the novolac type phenol resin, or may be mixed with hexamine which is a curing agent.
【００１０】本発明のシェルモールド用フェノール樹脂
組成物及びシェルモールド用鋳型用コーッテドサンドに
は前記成分以外に所望に応じ従来シェルモールド用鋳型
材料に一般的に用いられている添加成分、例えばγ−ア
ミノプロピルトリエトキシシラン、Ｎ−β（アミノエチ
ル）−γ−アミノプロピルトリメトキシシラン等のシラ
ンカップリング剤や脂肪族アマイド等の内部滑剤、ステ
アリン酸カルシウム等の離型剤、さらには崩壊剤や消臭
剤を含有させることができる。In addition to the above-mentioned components, the phenol resin composition for shell molds and the coated sand for molds for shell molds of the present invention may optionally contain additional components generally used in conventional mold materials for shell molds, such as γ-amino. Silane coupling agents such as propyltriethoxysilane and N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, internal lubricants such as aliphatic amides, mold release agents such as calcium stearate, and further disintegrators and deodorants. Agents can be included.
【００１１】[0011]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明は実施例に限定されるものではない。
実施例１
攪拌機、還流冷却器、温度計を備えた４つ口フラスコに
フェノール９４０ｇ、３７％ホルマリン５６０ｇ及びし
ゅう酸９．４ｇを配合し、攪拌しながら徐々に昇温し
た。還流温度に達してから３時間反応を行い、その後、
減圧下で濃縮を行い、軟化点が８５℃となったら終点と
した。その後、内部滑剤としてエチレンビスステアリン
酸アミド２０ｇ、シランカップリング剤としてγ−アミ
ノプロピルトリエトキシシラン９ｇ、さらに硬化促進剤
として炭酸ナトリウム２０ｇを添加し、シェルモールド
用フェノール樹脂組成物９５０ｇを得た。次に遠州鉄工
製ミキサーに１４０〜１６０℃に加熱した珪砂（フラタ
リーサンド）１０ｋｇと前記シェルモールド用フェノー
ル樹脂組成物２００ｇを仕込み６０秒間混練した後、硬
化剤としてヘキサミン２０ｇを含む水溶液１４０ｇを添
加し砂の塊が崩れるまで混練し、次いでステアリン酸カ
ルシウム１０ｇを添加してシェルモールド用レジンコー
テッドサンドを得た。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to the examples. Example 1 940 g of phenol, 560 g of 37% formalin and 9.4 g of oxalic acid were added to a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was gradually raised with stirring. After reaching the reflux temperature, the reaction is carried out for 3 hours, then
Concentration was performed under reduced pressure, and the end point was reached when the softening point reached 85 ° C. Thereafter, 20 g of ethylenebisstearic acid amide as an internal lubricant, 9 g of γ-aminopropyltriethoxysilane as a silane coupling agent, and 20 g of sodium carbonate as a curing accelerator were added to obtain 950 g of a phenol resin composition for shell mold. Next, 10 kg of silica sand (flattery sand) heated to 140 to 160 ° C. and 200 g of the phenol resin composition for shell mold were charged into an Enshu Iron Works mixer and kneaded for 60 seconds, then 140 g of an aqueous solution containing 20 g of hexamine as a curing agent was added. Then, the mixture was kneaded until the lump of sand collapsed, and then 10 g of calcium stearate was added to obtain a resin coated sand for shell mold.
【００１２】実施例２
硬化促進剤として炭酸ナトリウムの添加量を１０ｇとし
た以外は実施例１と同様の方法によりシェルモールド用
レジンコーテッドサンドを得た。Example 2 A resin coated sand for shell mold was obtained in the same manner as in Example 1 except that the amount of sodium carbonate added as a curing accelerator was 10 g.
【００１３】実施例３
硬化促進剤として炭酸ナトリウムの添加量を５０ｇとし
た以外は実施例１と同様の方法によりシェルモールド用
レジンコーテッドサンドを得た。Example 3 A resin coated sand for shell mold was obtained in the same manner as in Example 1 except that the amount of sodium carbonate added as a curing accelerator was 50 g.
【００１４】実施例４
硬化促進剤として炭酸ナトリウム２０ｇの替わりに炭酸
水素ナトリウム２０ｇとした以外は実施例１と同様の方
法によりシェルモールド用レジンコーテッドサンドを得
た。Example 4 A resin coated sand for shell mold was obtained in the same manner as in Example 1 except that 20 g of sodium hydrogen carbonate was used as a curing accelerator instead of 20 g of sodium carbonate.
【００１５】実施例５
硬化促進剤として炭酸ナトリウム２０ｇの替わりに水酸
化ナトリウム２０ｇとした以外は実施例１と同様の方法
によりシェルモールド用レジンコーテッドサンドを得
た。Example 5 A resin coated sand for shell mold was obtained in the same manner as in Example 1 except that 20 g of sodium hydroxide was used as a curing accelerator instead of 20 g of sodium carbonate.
【００１６】実施例６
硬化促進剤として炭酸ナトリウム２０ｇの替わりに炭酸
カリウム２０ｇとした以外は実施例１と同様の方法によ
りシェルモールド用レジンコーテッドサンドを得た。Example 6 A resin coated sand for shell mold was obtained in the same manner as in Example 1 except that 20 g of potassium carbonate was used as the curing accelerator instead of 20 g of sodium carbonate.
【００１７】実施例７
硬化促進剤として炭酸ナトリウム２０ｇの替わりに水酸
化カリウム２０ｇとした以外は実施例１と同様の方法に
よりシェルモールド用レジンコーテッドサンドを得た。Example 7 A resin coated sand for shell mold was obtained by the same method as in Example 1 except that 20 g of potassium hydroxide was used instead of 20 g of sodium carbonate as a curing accelerator.
【００１８】実施例８
攪拌機、還流冷却器、温度計を備えた４つ口フラスコに
フェノール９４０ｇ、３７％ホルマリン５６０ｇ及びし
ゅう酸９．４ｇを配合し、攪拌しながら徐々に昇温し
た。還流温度に達してから３時間反応を行い、その後、
減圧下で濃縮を行い、軟化点が８５℃となったら終点と
した。その後、内部滑剤としてエチレンビスステアリン
酸アミド２０ｇ、シランカップリング剤としてγ−アミ
ノプロピルトリエトキシシラン９ｇを添加し、シェルモ
ールド用フェノール樹脂組成物９５０ｇを得た。次に遠
州鉄工製ミキサーに１４０〜１６０℃に加熱した珪砂
（フラタリーサンド）１０ｋｇと前記シェルモールド用
フェノール樹脂組成物２００ｇを仕込み６０秒間混練し
た後、硬化剤としてヘキサミン２０ｇ及び硬化促進剤と
して炭酸ナトリウム４ｇを含む水溶液１４５ｇを添加し
砂の塊が崩れるまで混練し、次いでステアリン酸カルシ
ウム１０ｇを添加してシェルモールド用レジンコーテッ
ドサンドを得た。Example 8 To a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 940 g of phenol, 560 g of 37% formalin and 9.4 g of oxalic acid were added and gradually heated while stirring. After reaching the reflux temperature, the reaction is carried out for 3 hours, then
Concentration was performed under reduced pressure, and the end point was reached when the softening point reached 85 ° C. Thereafter, 20 g of ethylenebisstearic acid amide as an internal lubricant and 9 g of γ-aminopropyltriethoxysilane as a silane coupling agent were added to obtain 950 g of a phenol resin composition for shell mold. Next, 10 kg of silica sand (flattery sand) heated to 140 to 160 ° C. and 200 g of the phenol resin composition for shell mold were charged into an Enshu Iron Works mixer and kneaded for 60 seconds, then 20 g of hexamine as a curing agent and carbonic acid as a curing accelerator. 145 g of an aqueous solution containing 4 g of sodium was added and kneaded until the lump of sand collapsed, and then 10 g of calcium stearate was added to obtain a resin coated sand for shell mold.
【００１９】実施例９
硬化促進剤として炭酸ナトリウム４ｇの替わりに炭酸水
素ナトリウム４ｇとした以外は実施例８と同様の方法に
よりシェルモールド用レジンコーテッドサンドを得た。Example 9 A resin coated sand for shell mold was obtained in the same manner as in Example 8 except that 4 g of sodium hydrogen carbonate was used as a curing accelerator instead of 4 g of sodium carbonate.
【００２０】実施例１０
硬化促進剤として炭酸ナトリウム４ｇの替わりに水酸化
ナトリウム４ｇとした以外は実施例８と同様の方法によ
りシェルモールド用レジンコーテッドサンドを得た。Example 10 A resin coated sand for shell mold was obtained in the same manner as in Example 8 except that 4 g of sodium hydroxide was used as a curing accelerator instead of 4 g of sodium carbonate.
【００２１】実施例１１
硬化促進剤として炭酸ナトリウム４ｇの替わりに炭酸カ
リウム４ｇとした以外は実施例８と同様の方法によりシ
ェルモールド用レジンコーテッドサンドを得た。Example 11 A resin coated sand for shell mold was obtained in the same manner as in Example 8 except that 4 g of potassium carbonate was used as the curing accelerator instead of 4 g of sodium carbonate.
【００２２】実施例１２
硬化剤としてヘキサミンを２０ｇをヘキサミン１４ｇ及
び硬化促進剤として炭酸ナトリウム４ｇの替わりに炭酸
水素ナトリウム１０ｇとした以外は実施例８と同様の方
法によりシェルモールド用レジンコーテッドサンドを得
た。Example 12 A resin coated sand for shell mold was obtained in the same manner as in Example 8 except that 20 g of hexamine was used as a curing agent and 14 g of hexamine and 10 g of sodium hydrogencarbonate was used as a curing accelerator instead of 4 g of sodium carbonate. It was
【００２３】比較例１
攪拌機、還流冷却器、温度計を備えた４つ口フラスコに
フェノール９４０ｇ、３７％ホルマリン５６０ｇ及びし
ゅう酸９．４ｇを配合し、攪拌しながら徐々に昇温し
た。還流温度に達してから３時間反応を行い、その後、
減圧下で濃縮を行い、軟化点が８５℃となったら終点と
した。その後、内部滑剤としてエチレンビスステアリン
酸アミド２０ｇ、シランカップリング剤としてγ−アミ
ノプロピルトリエトキシシラン９ｇを添加し、シェルモ
ールド用フェノール樹脂組成物９５０ｇを得た。次に遠
州鉄工製ミキサーに１４０〜１６０℃に加熱した珪砂
（フラタリーサンド）１０Ｋｇと前記シェルモールド用
フェノール樹脂組成物２００ｇを仕込み６０秒間混練し
た後、硬化剤としてヘキサミン３０ｇを含む水溶液１５
０ｇを添加し砂の塊が崩れるまで混練し、次いでステア
リン酸カルシウム１０ｇを添加してシェルモールド用レ
ジンコーテッドサンドを得た。Comparative Example 1 940 g of phenol, 560 g of 37% formalin and 9.4 g of oxalic acid were added to a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was gradually raised with stirring. After reaching the reflux temperature, the reaction is carried out for 3 hours, then
Concentration was performed under reduced pressure, and the end point was reached when the softening point reached 85 ° C. Thereafter, 20 g of ethylenebisstearic acid amide as an internal lubricant and 9 g of γ-aminopropyltriethoxysilane as a silane coupling agent were added to obtain 950 g of a phenol resin composition for shell mold. Next, 10 kg of silica sand (flattery sand) heated to 140 to 160 ° C. and 200 g of the phenol resin composition for shell mold were charged into an Enshu Iron Works mixer and kneaded for 60 seconds, and then an aqueous solution containing 30 g of hexamine as a curing agent 15
0 g was added and the mixture was kneaded until the lump of sand collapsed, and then 10 g of calcium stearate was added to obtain a resin coated sand for shell mold.
【００２４】比較例２
硬化剤としてヘキサミン３０ｇを含む水溶液１５０ｇの
替わりに、ヘキサミン２０ｇを含む水溶液１４０ｇとし
た以外は比較例１と同様の方法によりシェルモールド用
レジンコーテッドサンドを得た。Comparative Example 2 A resin coated sand for shell mold was obtained in the same manner as in Comparative Example 1 except that 140 g of an aqueous solution containing 20 g of hexamine was used instead of 150 g of an aqueous solution containing 30 g of hexamine as a curing agent.
【００２５】比較例３
硬化剤としてヘキサミン２０ｇを含む水溶液１４０ｇの
替わりに、ヘキサミン２０ｇ及び硬化促進剤としてサリ
チル酸４ｇを含む水溶液１４５ｇとした以外は比較例１
と同様の方法によりシェルモールド用レジンコーテッド
サンドを得た。Comparative Example 3 Comparative Example 1 except that instead of 140 g of an aqueous solution containing 20 g of hexamine as a curing agent, 145 g of an aqueous solution containing 20 g of hexamine and 4 g of salicylic acid as a curing accelerator was used.
A resin coated sand for shell mold was obtained by the same method as described above.
【００２６】試験例
実施例１〜１１及び比較例１〜３により得られたシェル
モールド用レジンコーテッドサンドの特性を表１に示
す。Test Examples Table 1 shows the characteristics of the resin coated sands for shell molds obtained in Examples 1 to 11 and Comparative Examples 1 to 3.
【００２７】レジンコーテッドサンド試験方法
融着点：ＪＡＣＴ法に準拠して測定した。
曲げ強度：ＪＩＳ Ｋ６９１０に準拠し、２５０℃で６
０秒間焼成後冷却して曲げ強度を測定した。
温時強度：ＪＩＳ Ｋ６９１０に準拠し、２５０℃で６
０秒間焼成、離型１０秒後に曲げ強度を測定した。
アンモニア発生量：２５０℃に加熱した金型にレジンコ
ーテッドサンド５ｇをのせ直ちに２０Ｌの容器で覆い、
発生するアンモニアガスを補足し、１分後北川式ガス検
知管を用いアンモニア発生量を測定した。Resin Coated Sand Test Method Fusion Point: Measured according to the JACT method. Bending strength: 6 at 250 ° C. according to JIS K6910
Bending strength was measured after firing for 0 seconds and cooling. Warm strength: 6 at 250 ° C according to JIS K6910
Bending strength was measured after firing for 0 seconds and releasing for 10 seconds. Ammonia generation amount: 5 g of resin coated sand is placed on a mold heated to 250 ° C. and immediately covered with a 20 L container,
The generated ammonia gas was supplemented, and 1 minute later, the amount of ammonia generated was measured using a Kitagawa gas detector tube.
【００２８】[0028]
【表１】 ％／樹脂：ノボラック型フェノール樹脂に対する重量％[Table 1] % / Resin:% by weight with respect to novolac type phenolic resin
【００２９】[0029]
【発明の効果】このように本発明より得られるシェルモ
ールド用レジンコーテッドサンドは硬化剤のヘキサミン
量が１０重量％以下でも実用上支障のない曲げ強度を有
し、しかも温時強度も高く造形性も問題ない。またヘキ
サミン量を低減することによりアンモニア発生量は低減
し、作業環境の改善が図れる。As described above, the resin coated sand for shell mold obtained according to the present invention has a flexural strength that does not hinder practical use even when the amount of hexamine as a curing agent is 10% by weight or less, and has a high strength during warming and a good moldability. Is no problem. Further, by reducing the amount of hexamine, the amount of ammonia generated is reduced, and the working environment can be improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高田 新吾 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館事業所内 (72)発明者 大和田 芳郎 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館事業所内 (72)発明者 曽根 孝明 三重県桑名市桑部1053−１ (72)発明者 池田 一市 三重県桑名市桑部1053−１ Ｆターム(参考） 4E092 AA02 AA03 AA04 AA16 AA19 AA47 BA02 BA04 BA12 CA03 4J002 CC031 DE057 DE078 DE206 DE226 DJ008 EG026 EU189 GT00 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Shingo Takada Hitachi Chemical, 1500 Ogawa, Shimodate City, Ibaraki Prefecture Shimodate Office of Industry Co., Ltd. (72) Inventor Yoshio Owada Hitachi Chemical, 1500 Ogawa, Shimodate City, Ibaraki Prefecture Shimodate Office of Industry Co., Ltd. (72) Inventor Takaaki Sone 1053-1 Kuwabe, Kuwana City, Mie Prefecture (72) Inventor, Ichiichi Ikeda 1053-1 Kuwabe, Kuwana City, Mie Prefecture F-term (reference) 4E092 AA02 AA03 AA04 AA16 AA19 AA47 BA02 BA04 BA12 CA03 4J002 CC031 DE057 DE078 DE206 DE226 DJ008 EG026 EU189 GT00
Claims (4)
リ金属弱酸塩又はアルカリ金属水酸化物を含有すること
を特徴とするシェルモールド用フェノール樹脂組成物。1. A phenol resin composition for shell mold, comprising a novolac type phenol resin and a weak alkali metal salt or alkali metal hydroxide.
酸化物の総量がノボラック型フェノール樹脂１００重量
部に対して、０．５〜２０重量部である請求項１記載の
シェルモールド用フェノール樹脂組成物。2. The phenol resin composition for shell mold according to claim 1, wherein the total amount of weak alkali metal acid salt or alkali metal hydroxide is 0.5 to 20 parts by weight with respect to 100 parts by weight of the novolac type phenol resin. .
又はアルカリ金属水酸化物と、ノボラック型フェノール
樹脂と、ヘキサメチレンテトラミンとを混練してなるこ
とを特徴とするシェルモールド鋳型用レジンコーテッド
サンド。3. A resin coated sand for a shell mold template, which is made by kneading a refractory granular material, a weak alkali metal salt or alkali metal hydroxide, a novolac type phenol resin, and hexamethylenetetramine. .
酸化物の総量がノボラック型フェノール樹脂１００重量
部に対して、０．５〜２０重量部である請求項３記載の
シェルモールド鋳型用レジンコーテッドサンド。4. The resin coated sand for a shell mold template according to claim 3, wherein the total amount of the weak alkali metal salt or alkali metal hydroxide is 0.5 to 20 parts by weight with respect to 100 parts by weight of the novolac type phenol resin. .
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|---|---|---|---|
| JP2001371245A JP4106212B2 (en) | 2001-12-05 | 2001-12-05 | Phenolic resin composition for shell mold and resin coated sand for shell mold mold |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001371245A JP4106212B2 (en) | 2001-12-05 | 2001-12-05 | Phenolic resin composition for shell mold and resin coated sand for shell mold mold |
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|---|---|
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| JP4106212B2 JP4106212B2 (en) | 2008-06-25 |
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