JP3215945B2 - Ester curing type hardener composition for foundry sand - Google Patents
Ester curing type hardener composition for foundry sandInfo
- Publication number
- JP3215945B2 JP3215945B2 JP20380197A JP20380197A JP3215945B2 JP 3215945 B2 JP3215945 B2 JP 3215945B2 JP 20380197 A JP20380197 A JP 20380197A JP 20380197 A JP20380197 A JP 20380197A JP 3215945 B2 JP3215945 B2 JP 3215945B2
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- weight
- sand
- mold
- curing agent
- agent composition
- Prior art date
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- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の属する技術分野】本発明は、アルカリ性水溶性
フェノール樹脂を鋳型用粘結剤として用いる場合におい
て、そのアルカリ性水溶性フェノール樹脂を硬化させる
ために使用する有機エステル型の硬化剤組成物に関す
る。The present invention relates to an organic ester-type curing agent composition used for curing an alkaline water-soluble phenol resin when the alkaline water-soluble phenol resin is used as a binder for a mold.
【従来の技術】鋳型の造型方法には種々の方法があり、
これに使われる粘結剤も多岐にわたるが、大別して無機
粘結剤と有機粘結剤になる。特に、有機粘結剤を使用す
る有機自硬性鋳型造型法が近年主流となりつつある。有
機自硬性鋳型造型法は鋳物砂と有機粘結剤とその粘結剤
を硬化させるための硬化剤組成物が必要であり、三者を
混練し、抜型するというものである。このような有機自
硬性鋳型造型法に使用する有機粘結剤としては、フェノ
ール樹脂、フラン樹脂を酸で硬化させる酸硬化型粘結
剤、イソシアネートとポリオールをアミン類を触媒とし
て硬化させるウレタン硬化型粘結剤があるが、近年では
環境問題や鋳物品質を改善することを目的としてアルカ
リ性水溶性フェノール樹脂を有機エステルで硬化させる
エステル硬化型フェノール樹脂粘結剤が広く使用される
ようになった。この硬化剤組成物としては、γ−ブチロ
ラクトン、トリアセチン、グリコールジアセテート、ア
ジピン酸メチル及びそれらの混合物の有機エステルが広
く用いられる（特公昭６１−４３１３２号公報、特公平
０３−６８０６２号公報等）。しかし、アルカリ性水溶
性フェノール樹脂と有機エステルとの硬化反応の際に、
ホルムアルデヒドが発生するため、その混練工程から造
型、抜型工程、注湯、及び型ばらしにおいてホルムアル
デヒドの臭気が作業環境の悪化、作業員の皮膚のカブレ
発生などが新たな問題となっている（文献：皮膚・第３
０巻・増刊第４号・昭和６３年６月）。このため、アル
カリ性水溶性フェノール樹脂に尿素やアミン類の有機窒
素化合物をホルムアルデヒド捕捉剤として添加すること
が提案されている（特開平５−１９２７３７号公報）。
これによれば、有機窒素化合物が発生したホルムアルデ
ヒドと反応し、鋳型の外へ飛散するホルムアルデヒド量
を抑えることができるが、フェノール樹脂と有機エステ
ルとの硬化反応を阻害し、鋳型強度の低下という欠点が
生じる。また、前記有機窒素化合物とホルムアルデヒド
との反応は結合力が弱く、発生するホルムアルデヒドを
捕捉し鋳型の外へ飛散する量を抑えるのには限界があ
る。2. Description of the Related Art There are various methods for molding a mold.
There are a wide variety of binders used for this purpose, but they are roughly divided into inorganic binders and organic binders. In particular, an organic self-hardening mold molding method using an organic binder is becoming mainstream in recent years. The organic self-hardening mold molding method requires molding sand, an organic binder and a hardener composition for hardening the binder, and the three are kneaded and the mold is removed. Examples of the organic binder used in such an organic self-hardening mold molding method include a phenol resin, an acid-curable binder that cures a furan resin with an acid, and a urethane-curable binder that cures isocyanate and polyol with an amine as a catalyst. There is a binder, but in recent years, an ester-curable phenol resin binder which cures an alkaline water-soluble phenol resin with an organic ester has been widely used for the purpose of improving environmental problems and casting quality. As the curing agent composition, organic esters of γ-butyrolactone, triacetin, glycol diacetate, methyl adipate and mixtures thereof are widely used (JP-B-61-43132, JP-B-03-68062, etc.). . However, during the curing reaction between the alkaline water-soluble phenolic resin and the organic ester,
Since formaldehyde is generated, odors of formaldehyde in the molding process, the molding process, the pouring process, and the mold release process from the kneading process deteriorate the working environment, and there are new problems such as generation of rash on worker's skin (Reference: Skin 3
0, extra number 4, June 1988). For this reason, it has been proposed to add an organic nitrogen compound such as urea or an amine as a formaldehyde scavenger to an alkaline water-soluble phenol resin (Japanese Patent Laid-Open No. 5-192737).
According to this, an organic nitrogen compound reacts with the generated formaldehyde, and the amount of formaldehyde scattered outside the mold can be suppressed, but the curing reaction between the phenol resin and the organic ester is inhibited, and the mold strength is reduced. Occurs. Further, the reaction between the organic nitrogen compound and formaldehyde has a weak bonding force, and there is a limit in suppressing the amount of generated formaldehyde to be captured and scattered out of the mold.
【発明が解決しようとする課題】本発明は、前記従来の
実情に鑑み開発されたものであり、前記従来の問題を解
決するために、ホルムアルデヒドと反応するエステル化
合物を使用することにより、高い鋳型強度を保持しなが
ら、しかも、混練工程から造型、抜型工程、注湯、更に
は型ばらし時に発生するホルムアルデヒドを効果的に捕
捉し得る硬化剤組成物を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention has been developed in view of the above-mentioned conventional circumstances. In order to solve the above-mentioned conventional problems, the use of an ester compound which reacts with formaldehyde makes it possible to obtain a high template. It is an object of the present invention to provide a curing agent composition capable of effectively capturing formaldehyde generated during a kneading process, a molding process, a molding process, a pouring process, and a mold release process while maintaining strength.
【課題を解決するための手段】本発明は、アルカリ性水
溶性フェノール樹脂を硬化させるための有機エステルの
構造中に活性炭素を有する有機エステルである硬化剤組
成物を提供することである。これらの活性炭素を有する
エステルは、その活性部位においてホルムアルデヒドと
反応し、強固な結合を形成する。このため、混練時、造
型時、抜型時、注湯時、更に型ばらし時に至るまで発生
するホルムアルデヒドと即座に反応し、鋳型の外部に飛
散することを抑えることができる。また、これら活性炭
素を有するエステルも有機エステルであるので、アルカ
リ性水溶性フェノール樹脂の硬化剤となり得る。このた
め、鋳型強度の低下といった弊害もない。本発明におい
ては、活性炭素を有する有機エステル類の１種又は２種
以上を５重量％以上含有することを特徴とする硬化剤組
成物を提供する。含有量が５重量％未満であると、混練
工程から造型、抜型工程、注湯時、更に型ばらし時に発
生するホルムアルデヒドを充分捕捉することができな
い。活性炭素を有する有機エステルとは、例えば、アセ
ト酢酸エチル、マロン酸ジエチル、マロン酸ジメチル、
マロン酸ジ−ｔ−ブチル、マロン酸ジベンジル、グリコ
ール酸エチル、メトキシ酢酸メチルエステル、メトキシ
酢酸エチルエステル、シアノ酢酸メチル、シアノ酢酸エ
チル等が挙げられる（但し、化学大事典 東京化学同人
に定義されている活性メチレン及び活性メチルに含まれ
る炭素を有するエステルであれば、上記列記した限りで
はない）。また、本発明における硬化剤組成物は、上述
の有機エステルとともにフェノール化合物単量体の１種
又は２種以上を含有せしめることによって、鋳型強度の
低下、特に最終の鋳型強度を低下させることなく、可使
時間を延長させることができる。硬化剤組成物中のフェ
ノール化合物単量体の含有量としては１〜３０重量％が
適当である。フェノール化合物単量体の含有量が１重量
％未満の場合、可使時間が実質的に変わらず、また鋳型
強度の向上が認められない。一方、フェノール化合物単
量体の含有量が３０重量％を越えてしまうと、アルカリ
性水溶性フェノール樹脂と有機エステルとの硬化反応を
遅らせてしまい、立ち上がりの鋳型強度が低く、十分な
抜型強度が得られない。このため、造型の生産性が落ち
るといった欠点が生じる。本発明に使用されるフェノー
ル化合物単量体としては、例えばレゾルシノール、ビス
フェノールＡ、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、フェノー
ル、クレゾール、キシレノール、ブチルフェノール、ノ
ニルフェノール、フェニルフェノール、ナフトール、そ
の他の置換フェノールを含めたフェノール類を使用する
ことができる。本発明の硬化剤組成物は、活性炭素を有
する有機エステル及びフェノール化合物単量体の他に、
アルカリ性水溶性フェノール樹脂を硬化させるための有
機エステルを含有する。このような有機エステルとして
は、従来よりアルカリ性水溶性フェノール樹脂の硬化剤
として使用されてきたものを使用することが可能であ
り、γ−ブチロラクトン、プロピオラクトン、ξ−カプ
ロラクトンのような環状ラクトン類、Ｃ1〜Ｃ10アルキ
ル一価又は多価のアルコール類とＣ1〜Ｃ10一価又は多
価カルボン酸とのエステル、及びアルキレンカーボネー
トを挙げることができる。Ｃ1〜Ｃ10アルキル一価又は
多価のアルコール類とＣ1〜Ｃ10一価又は多価カルボン
酸とのエステル、及びアルキレンカーボネートの例とし
ては、ギ酸エチル、エチレングリコールジアセテート、
トリアセチン、アジピン酸メチルを挙げることができ
る。これらのエステルは、目的とする可使時間、抜型時
間など作業に適合させるようにして混合使用されるの
が、一般的である。本発明の硬化剤組成物により硬化さ
せるアルカリ性水溶性フェノール樹脂としては、例えば
フェノール、クレゾール、レゾルシノール、ビスフェノ
ールＡ、その他置換フェノールを含めたフェノール類を
原料として、アルカリ性触媒のもとアルデヒド化合物等
と反応させることによって得られるフェノール樹脂が挙
げられる。例として特許第１５５４０３０号等に示され
る樹脂があり、その他特に限定されるものではなく、公
知となっている樹脂であれば本発明に適応できる。例え
ば前記特開平５−１９２７３７号公報に記載されている
ような窒素化合物を含んだフェノール樹脂を用いれば、
飛散するホルムアルデヒドの量を抑えるのには効果的で
ある。SUMMARY OF THE INVENTION The present invention provides a curing agent composition which is an organic ester having an activated carbon in the structure of the organic ester for curing an alkaline water-soluble phenolic resin. Esters having these activated carbons react with formaldehyde at their active sites to form strong bonds. For this reason, it can react with formaldehyde generated at the time of kneading, molding, demolding, pouring, and even at the time of mold release, and can suppress scattering to the outside of the mold. Further, since these esters having activated carbon are also organic esters, they can serve as curing agents for alkaline water-soluble phenolic resins. Therefore, there is no adverse effect such as a decrease in mold strength. In the present invention, there is provided a curing agent composition containing one or more organic esters having activated carbon in an amount of 5% by weight or more. If the content is less than 5% by weight, it is not possible to sufficiently capture formaldehyde generated during the kneading step, the molding, the demolding step, the pouring, and the unmolding. The organic ester having an activated carbon includes, for example, ethyl acetoacetate, diethyl malonate, dimethyl malonate,
Examples include di-t-butyl malonate, dibenzyl malonate, ethyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methyl cyanoacetate, and ethyl cyanoacetate. This is not the case as long as it is an ester having a carbon contained in active methylene and active methyl.) Further, the curing agent composition in the present invention, by incorporating one or more phenolic compound monomers together with the organic ester described above, without reducing the mold strength, particularly without decreasing the final mold strength, Pot life can be extended. The content of the phenol compound monomer in the curing agent composition is suitably from 1 to 30% by weight. When the content of the phenol compound monomer is less than 1% by weight, the pot life is not substantially changed and no improvement in the mold strength is observed. On the other hand, if the content of the phenolic compound monomer exceeds 30% by weight, the curing reaction between the alkaline water-soluble phenolic resin and the organic ester is delayed, so that the rising mold strength is low and sufficient punching strength is obtained. I can't. For this reason, there is a disadvantage that the productivity of molding decreases. Examples of the phenol compound monomer used in the present invention include resorcinol, bisphenol A, bisphenol F, bisphenol C,
Phenols including catechol, hydroquinone, pyrogallol, phenol, cresol, xylenol, butylphenol, nonylphenol, phenylphenol, naphthol, and other substituted phenols can be used. The curing agent composition of the present invention, in addition to an organic ester having an activated carbon and a phenol compound monomer,
Contains an organic ester for curing the alkaline water-soluble phenolic resin. As such organic esters, those which have been conventionally used as a curing agent for an alkaline water-soluble phenol resin can be used, and cyclic lactones such as γ-butyrolactone, propiolactone, and ξ-caprolactone can be used. And esters of C 1 -C 10 alkyl mono- or polyhydric alcohols with C 1 -C 10 mono- or polycarboxylic acids, and alkylene carbonates. Examples of esters of C 1 -C 10 alkyl mono- or polyhydric alcohols with C 1 -C 10 mono- or polycarboxylic acids and alkylene carbonates include ethyl formate, ethylene glycol diacetate,
Triacetin and methyl adipate can be mentioned. These esters are generally mixed and used in such a manner as to be compatible with the intended working time, demolding time and the like. As the alkaline water-soluble phenol resin to be cured by the curing agent composition of the present invention, for example, phenols including phenol, cresol, resorcinol, bisphenol A, and other substituted phenols as raw materials are reacted with aldehyde compounds and the like under an alkaline catalyst. And a phenolic resin obtained by the reaction. Examples thereof include a resin disclosed in Japanese Patent No. 1554030 and the like, and the present invention is not particularly limited. Any known resin can be applied to the present invention. For example, if a phenol resin containing a nitrogen compound as described in JP-A-5-192737 is used,
It is effective in reducing the amount of formaldehyde scattered.
【実施例】以下、実施例をあげて本発明に係わる鋳物砂
用硬化剤組成物について更に詳しく説明する。但し、本
発明は、下記実施例に限定されるものでなく、その要旨
の範囲内で種々の変形実施が可能である。 ［実施例１］先ず、トリアセチンを８５重量％、アセト
酢酸エチルを１０重量％及びレゾルシノールを５重量％
含有する硬化剤組成物を得た。次に、恒温恒湿室内（２
５℃、６０％）において骨材としての珪砂（フラタリー
サンド）１００重量部に対してアルカリ性水溶性フェノ
ール樹脂（群栄ボーデン株式会社製 ＴＰＡ−３６）
２．０重量部、及び前述の硬化剤組成物０．４重量部添
加し、混練機にて各々６０秒間混練し、混練砂を得た。
混練砂を５０ｍｍｈ（高さ）×５０ｍｍφ（直径）のテ
ストピース木型（１２個取り）に手込めにて充填し、３
０分間放置後抜型を行い、２４Ｈｒ後に鋳型の圧縮強さ
を測定した。並行して可使時間の測定をＪＡＣＴ法に従
って行った。なお、骨材としては、本実施例で用いた珪
砂（フラタリーサンド）の他、珪砂、ジルコン砂、オリ
ビン砂、クロマイト砂、アルミナ砂、ムライト砂の１種
又は２種以上を用いることができる。また、前記混練直
後の混練砂を５０ｇ取り、図１の参考図に示すホルムア
ルデヒド捕集装置にて発生するホルムアルデヒドを純水
５００ミリリットルにて捕集し、捕集した水溶液をアセ
チルアセトン法にてホルムアルデヒドの定量を行った
（『ホルムアルデヒド』井本稔、垣内弘、黄慶雲編集を
参照）。図１中、１は混練砂、２は純水、３は捕集瓶、
４はアスピレーターである。強度測定値及びホルムアル
デヒド定量結果を表１に示す。 ［実施例２］先ず、トリアセチンを７５重量％、アセト
酢酸エチルを２０重量％及びレゾルシノールを５重量％
含有する硬化剤組成物を得た。実施例１と同様の方法に
て鋳型強度測定、可使時間の測定及び発生ホルムアルデ
ヒドの定量を行った。結果を表１に示す。 ［実施例３］先ず、トリアセチンを４５重量％、アセト
酢酸エチルを５０重量％及びレゾルシノールを５重量％
含有する硬化剤組成物を得た。実施例１と同様の方法に
て鋳型強度測定、可使時間の測定及び発生ホルムアルデ
ヒドの定量を行った。結果を表１に示す。 ［実施例４］先ず、トリアセチンを８５重量％、マロン
酸ジエチルを１０重量％及びレゾルシノールを５重量％
含有する硬化剤組成物を得た。実施例１と同様の方法に
て鋳型強度測定、可使時間の測定、及び発生ホルムアル
デヒドの定量を行った。結果を表１に示す。 ［比較例１］硬化剤組成物をトリアセチン１００重量部
とした。実施例１と同様の方法にて鋳型強度測定、可使
時間の測定及び発生ホルムアルデヒドの定量を行った。
結果を表１に示す。 ［比較例２］先ず、トリアセチンを９３重量％、アセト
酢酸エチルを２重量％及びレゾルシノールを５重量％含
有する硬化剤組成物を得た。実施例１と同様の方法にて
鋳型強度測定、可使時間の測定、及び発生ホルムアルデ
ヒドの定量を行った。結果を表１に示す。 ［比較例３］恒温恒湿室内（２５℃、６０％）において
珪砂（フラタリーサンド）１００重量部に対してアルカ
リ性水溶性フェノール樹脂（群栄ボーデン株式会社製／
ＴＰＡ−３６）２．０重量部、５０ｗｔ％の尿素水溶
液を０．０８重量部、及びトリアセチンを０．４重量部
添加し、混練機にて各々６０秒間混練し、混練砂を得
た。そして、実施例１と同様の方法にて鋳型強度測定、
可使時間の測定、及び発生ホルムアルデヒドの定量を行
った。結果を表１に示す。 ［実施例５］先ず、トリアセチンを８５重量％、アセト
酢酸エチルを１０重量％及びビスフェノールＡ５重量％
を含有する硬化剤組成物を得た。実施例１と同様の方法
にて鋳型強度測定、可使時間の測定及び発生ホルムアル
デヒドの定量を行った。結果を表２に示す。 ［実施例６］先ず、トリアセチンを８０重量％、アセト
酢酸エチルを１０重量％及びビスフェノールＡ１０重量
％を含有する硬化剤組成物を得た。実施例１と同様の方
法にて鋳型強度測定、可使時間の測定及び発生ホルムア
ルデヒドの定量を行った。結果を表２に示す。 ［実施例７］先ず、トリアセチンを７５重量％、アセト
酢酸エチルを１０重量％及びビスフェノールＡ１５重量
％を含有する硬化剤組成物を得た。実施例１と同様の方
法にて鋳型強度測定、可使時間の測定及び発生ホルムア
ルデヒドの定量を行った。結果を表２に示す。 ［実施例８］先ず、トリアセチンを８５重量％、アセト
酢酸エチルを１０重量％及びフェノール５重量％を含有
する硬化剤組成物を得た。実施例１と同様の方法にて鋳
型強度測定、可使時間の測定及び発生ホルムアルデヒド
の定量を行った。結果を表２に示す。 ［比較例４］先ず、トリアセチンを８９．５重量％、ア
セト酢酸エチルを１０重量％及びビスフェノールＡ０．
５重量％を含有する硬化剤組成物を得た。実施例１と同
様の方法にて鋳型強度測定、可使時間の測定及び発生ホ
ルムアルデヒドの定量を行った。結果を表２に示す。 ［比較例５］先ず、トリアセチンを５５重量％、アセト
酢酸エチルを１０重量％及びビスフェノールＡ３５重量
％を含有する硬化剤組成物を得た。実施例１と同様の方
法にて鋳型強度測定、可使時間の測定及び発生ホルムア
ルデヒドの定量を行った。結果を表２に示す。The hardening composition for foundry sand according to the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention. [Example 1] First, 85% by weight of triacetin, 10% by weight of ethyl acetoacetate, and 5% by weight of resorcinol.
A curing agent composition was obtained. Next, in a constant temperature and humidity room (2
(5 ° C., 60%) and an alkaline water-soluble phenol resin (TPA-36 manufactured by Gunei Boden Co., Ltd.) with respect to 100 parts by weight of silica sand (flattery sand) as an aggregate.
2.0 parts by weight and 0.4 parts by weight of the above-mentioned curing agent composition were added and kneaded with a kneader for 60 seconds each to obtain kneaded sand.
The kneading sand is hand-filled into a 50 mmh (height) x 50 mmφ (diameter) test piece wooden mold (take 12 pieces),
After leaving for 0 minute, the mold was removed, and after 24 hours, the compressive strength of the mold was measured. In parallel, the pot life was measured according to the JACT method. In addition, as the aggregate, one or two or more of silica sand, zircon sand, olivine sand, chromite sand, alumina sand, and mullite sand can be used in addition to the silica sand (flat sand) used in the present embodiment. . In addition, 50 g of the kneading sand immediately after the kneading is taken, formaldehyde generated by a formaldehyde collecting apparatus shown in the reference diagram of FIG. Quantification was performed (see “Formaldehyde” edited by Minoru Imoto, Hiroshi Kakiuchi and Huang Qingyun). In FIG. 1, 1 is kneading sand, 2 is pure water, 3 is a collecting bottle,
4 is an aspirator. Table 1 shows the measured strength values and the results of formaldehyde quantification. Example 2 First, triacetin was 75% by weight, ethyl acetoacetate was 20% by weight, and resorcinol was 5% by weight.
A curing agent composition was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 1 shows the results. Example 3 First, triacetin was 45% by weight, ethyl acetoacetate was 50% by weight, and resorcinol was 5% by weight.
A curing agent composition was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 1 shows the results. Example 4 First, 85% by weight of triacetin, 10% by weight of diethyl malonate and 5% by weight of resorcinol were used.
A curing agent composition was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the generated formaldehyde was quantified. Table 1 shows the results. [Comparative Example 1] The curing agent composition was used as 100 parts by weight of triacetin. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined.
Table 1 shows the results. Comparative Example 2 First, a curing agent composition containing 93% by weight of triacetin, 2% by weight of ethyl acetoacetate, and 5% by weight of resorcinol was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the generated formaldehyde was quantified. Table 1 shows the results. [Comparative Example 3] In a constant temperature and humidity room (25 ° C, 60%), an alkaline water-soluble phenol resin (manufactured by Gunei Boden Co., Ltd.) was added to 100 parts by weight of silica sand (flatary sand).
TPA-36) 2.0 parts by weight, 0.08 parts by weight of a 50 wt% urea aqueous solution, and 0.4 parts by weight of triacetin were added and kneaded with a kneader for 60 seconds each to obtain kneaded sand. Then, the mold strength was measured in the same manner as in Example 1,
The pot life was measured and the formaldehyde generated was quantified. Table 1 shows the results. Example 5 First, triacetin was 85% by weight, ethyl acetoacetate was 10% by weight, and bisphenol A was 5% by weight.
Was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 2 shows the results. Example 6 First, a curing agent composition containing 80% by weight of triacetin, 10% by weight of ethyl acetoacetate, and 10% by weight of bisphenol A was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 2 shows the results. Example 7 First, a curing agent composition containing 75% by weight of triacetin, 10% by weight of ethyl acetoacetate, and 15% by weight of bisphenol A was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 2 shows the results. Example 8 First, a curing agent composition containing 85% by weight of triacetin, 10% by weight of ethyl acetoacetate, and 5% by weight of phenol was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 2 shows the results. Comparative Example 4 First, 89.5% by weight of triacetin, 10% by weight of ethyl acetoacetate and 0.1% of bisphenol A were added.
A curing agent composition containing 5% by weight was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was determined. Table 2 shows the results. Comparative Example 5 First, a curing agent composition containing 55% by weight of triacetin, 10% by weight of ethyl acetoacetate, and 35% by weight of bisphenol A was obtained. In the same manner as in Example 1, the mold strength was measured, the pot life was measured, and the amount of formaldehyde generated was quantified. Table 2 shows the results.
【表１】 注１．有機エステル及びフェノール化合物単量体の略記
号 トリアセチン ・・・Ｔ レゾルシノー
ル ・・・Ｒ アセト酢酸エチル・・・Ａ マロン酸エチル ・・・Ｍ 注２．可使時間の測定方法はＪＡＣＴ法に従った。 注３．尿素水溶液（５０％濃度）を０．０８重量部、砂
に添加[Table 1] Note 1. Abbreviations of organic ester and phenolic compound monomers Triacetin ... T Resorcinol ... R Ethyl acetoacetate ... A Ethyl malonate ... M Note2. The pot life was measured according to the JACT method. Note3. 0.08 parts by weight of urea aqueous solution (50% concentration) added to sand
【表２】 注１．有機エステル及びフェノール化合物単量体の略記
号 トリアセチン ・・・Ｔ フェノール
・・・Ｐ アセト酢酸エチル・・・Ａ ビスフェノールＡ・・・Ｂ 注２．可使時間の測定方法はＪＡＣＴ法に従った。表
１、表２の各実施例と各比較例との対比から明らかなよ
うに、各実施例の活性炭素を有する有機エステル、及び
フェノール化合物単量体を含有する硬化剤組成物は、各
比較例の場合よりも、比較的長い可使時間を有し、且つ
高い鋳型強度を得ながら、砂混練時等に発生するホルム
アルデヒドを効果的に捕捉して、鋳型の外部に飛散する
ことを抑え得ることがわかる。[Table 2] Note 1. Abbreviation of organic ester and phenolic compound monomer Triacetin ・ ・ ・ T phenol
... P ethyl acetoacetate ... A Bisphenol A ... B Note2. The pot life was measured according to the JACT method. As is clear from the comparison between each example and each comparative example in Tables 1 and 2, the curing agent composition containing the organic ester having activated carbon and the phenolic compound monomer in each example is different from each comparative example. Compared with the case of the example, it has a relatively long pot life, and while obtaining high mold strength, it can effectively capture formaldehyde generated at the time of sand kneading etc. and suppress scattering to the outside of the mold. You can see that.
【発明の効果】本発明の活性炭素を有する有機エステ
ル、及びフェノール化合物単量体を含有する硬化剤組成
物は、有機自硬性鋳型造型法において、長い可使時間を
有し、且つ高い鋳型強度を得ながら、混練時、造型時、
抜型時、注湯時、更に型ばらし時に発生するホルムアル
デヒドを効果的に捕捉して、鋳型の外部に飛散すること
を抑え、臭気、作業員の皮膚のカブレなどの作業環境を
改善する。The curing agent composition of the present invention containing an organic ester having activated carbon and a phenolic compound monomer has a long pot life and a high mold strength in an organic self-hardening mold molding method. At the time of kneading, molding,
Formaldehyde generated at the time of mold removal, pouring, and when the mold is released is effectively captured to prevent scattering to the outside of the mold, and to improve the working environment such as odor and rash on the worker's skin.
【図１】本発明の実施例におけるホルムアルデヒドの定
量を行うためのホルムアルデヒド捕集装置の概略を示す
参考図である。FIG. 1 is a reference diagram schematically showing a formaldehyde trapping apparatus for quantifying formaldehyde in an example of the present invention.
１ 混練砂 ２ 純水 ３ 捕集瓶 ４ アスピレーター DESCRIPTION OF SYMBOLS 1 Kneading sand 2 Pure water 3 Collection bottle 4 Aspirator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮下 雄次 群馬県高崎市宿大類町700番地 群栄化 学工業株式会社内 (56)参考文献 特開 平８−164439（ＪＰ，Ａ) 特開 平７−178507（ＪＰ，Ａ) 特開 昭53−46427（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B22C 1/00 - 1/26 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Miyashita 700, Shukudaidaicho, Takasaki City, Gunma Prefecture Inside Gunei Kagaku Kogyo Co., Ltd. (56) References JP-A-8-164439 (JP, A) JP-A-7 -178507 (JP, A) JP-A-53-46427 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B22C 1/00-1/26
Claims (2)
ト砂、アルミナ砂、ムライト砂の１種又は２種以上を骨
材として用い、アルカリ性水溶性フェノール樹脂を有機
エステルにより硬化させる鋳型造型法において用いるエ
ステル硬化型硬化剤組成物であって、前記有機エステル
がその構造中に活性炭素を有する有機エステル類の１種
又は２種以上を５重量％以上含有することを特徴とする
有機エステル硬化剤組成物。1. A mold molding method in which one or more of silica sand, zircon sand, olivine sand, chromite sand, alumina sand and mullite sand are used as an aggregate and an alkaline water-soluble phenol resin is cured with an organic ester. An ester-curable curing agent composition, wherein the organic ester contains at least 5% by weight of one or more of organic esters having an activated carbon in its structure. object.
単量体の１種又は２種以上を１〜３０重量％含有するこ
とを特徴とする請求項１記載の有機エステル硬化剤組成
物。2. The organic ester curing agent composition according to claim 1, wherein the organic ester contains 1 to 30% by weight of one or more phenolic compound monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20380197A JP3215945B2 (en) | 1997-07-14 | 1997-07-14 | Ester curing type hardener composition for foundry sand |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20380197A JP3215945B2 (en) | 1997-07-14 | 1997-07-14 | Ester curing type hardener composition for foundry sand |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1133670A JPH1133670A (en) | 1999-02-09 |
| JP3215945B2 true JP3215945B2 (en) | 2001-10-09 |
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ID=16479971
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20380197A Expired - Lifetime JP3215945B2 (en) | 1997-07-14 | 1997-07-14 | Ester curing type hardener composition for foundry sand |
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| JP (1) | JP3215945B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5248749B2 (en) * | 2006-03-03 | 2013-07-31 | 花王株式会社 | Curing agent composition for alkali phenol resin |
| JP5089935B2 (en) * | 2006-07-18 | 2012-12-05 | 花王株式会社 | Furan resin composition for mold production |
| US8729152B2 (en) | 2009-04-10 | 2014-05-20 | Kao Corporation | Curing agent composition |
| CN104493073A (en) * | 2014-11-26 | 2015-04-08 | 马鞍山市恒达耐磨材料有限责任公司 | High-temperature-resistant purple knar molding sand and preparation method thereof |
| US20170174813A1 (en) * | 2015-12-18 | 2017-06-22 | Ha-International, Llc | Compositions and Methods for Modified Ester-Curatives and Reduction of Formaldehyde Emission and Odor in Ester-Cured Phenolic Binder Systems |
| US20170174814A1 (en) | 2015-12-18 | 2017-06-22 | Ha-International, Llc | Compositions and Methods for Modified Ester-Curatives and Reduction of Formaldehyde Emission and Odor in Ester-Cured Phenolic Binder Systems |
| JP6895804B2 (en) * | 2017-05-29 | 2021-06-30 | 花王株式会社 | Hardener composition for molding |
| DE102018100694A1 (en) * | 2018-01-12 | 2019-07-18 | Ask Chemicals Gmbh | Formaldehyde-reduced phenolic resin binder |
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1997
- 1997-07-14 JP JP20380197A patent/JP3215945B2/en not_active Expired - Lifetime
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|---|---|
| JPH1133670A (en) | 1999-02-09 |
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