JP2003225736A - Self-hardening binder composition for mold - Google Patents
Self-hardening binder composition for moldInfo
- Publication number
- JP2003225736A JP2003225736A JP2002023628A JP2002023628A JP2003225736A JP 2003225736 A JP2003225736 A JP 2003225736A JP 2002023628 A JP2002023628 A JP 2002023628A JP 2002023628 A JP2002023628 A JP 2002023628A JP 2003225736 A JP2003225736 A JP 2003225736A
- Authority
- JP
- Japan
- Prior art keywords
- earth metal
- alkaline earth
- sand
- binder composition
- mold
- 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.)
- Granted
Links
Landscapes
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鋳型の製造に好適
な鋳型用自硬化性粘結剤組成物に関する。TECHNICAL FIELD The present invention relates to a self-curing binder composition for a mold, which is suitable for manufacturing a mold.
【０００２】[0002]
【従来の技術】一般的なレゾール型フェノール樹脂は、
自硬化型鋳型用粘結剤として使用される際には、酸硬
化、アルカリ硬化、或いはエステル硬化等によって実用
化されている。これらは酸、アルカリやエステル等の化
合物を液状として添加配合し、硬化させるるシステム、
又は、これらをガスの形で、砂と粘結剤を混練して型枠
の中に投入したその砂粒間に、吹き込むなどの装置を組
み込んだシステムが既存する。しかし、鋳型は、溶融さ
れた液状鉄を注ぎ込み（注湯）使用されるために、以下
の欠点が存在する。すなわち、鋳型は、瞬間的な高温に
曝され、この際の溶融鉄との接触による高温により、前
記の酸類、例えば硫酸スルホン酸類を添加した場合はガ
ス化して亜硫酸ガスを多量に発生する。また、これらの
酸類では自然には最も多く存在するアルカリ系の砂で
は、酸が砂に消費されてしまい、樹脂を硬化させるのに
は必要な理論値より多くの酸を添加する必要がある。2. Description of the Related Art A general resol type phenolic resin is
When it is used as a self-curing mold binder, it is put into practical use by acid curing, alkali curing, ester curing or the like. These are systems in which compounds such as acids, alkalis and esters are added and compounded in a liquid state and cured,
Alternatively, there is an existing system in which a device such as a blowing device is incorporated in the form of gas between the sand grains that are kneaded with sand and a binder and put into a mold. However, since the mold is used by pouring (melting) molten liquid iron, it has the following drawbacks. That is, the mold is exposed to a momentary high temperature, and due to the high temperature caused by the contact with the molten iron at this time, when the above-mentioned acids, for example, sulfuric acid sulfonic acids are added, they are gasified to generate a large amount of sulfurous acid gas. In addition, in the case of alkaline sand, which naturally exists most in these acids, the acid is consumed by the sand, and it is necessary to add more acid than the theoretical value required to cure the resin.
【０００３】又、アルカリ硬化の場合は、直接アミンガ
ス等が発生し、これらが毒性を有して、またエステル硬
化では、蟻酸等が発生し、その作業場における環境への
毒性に対応する対策には大規模な設備上の措置、処理が
必要となっている。Further, in the case of alkali curing, amine gas or the like is directly generated, and these are toxic, and in ester curing, formic acid or the like is generated, which is a countermeasure against environmental toxicity in the workplace. Large-scale equipment measures and treatments are required.
【０００４】[0004]
【発明が解決しようとする課題】本発明の課題は、注湯
時においても、有害なガスが発生せずに、且つ、鋳物砂
の種類に影響されない鋳型用自硬化性粘結剤組成物を提
供することにある。An object of the present invention is to provide a self-curing binder composition for a mold that does not generate harmful gas even when pouring molten metal and is not affected by the type of molding sand. To provide.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の課
題を鋭意検討した結果、レゾール型フェノール樹脂を自
硬化させるに有効な硬化方法として、各種の砂と共に混
練される際に、特定の弱塩基性の化合物であるアルカリ
土類金属酸化物及び／又はアルカリ土類金属水酸化物
と、チオ硫酸アンモニウム等の硫黄原子含有オキソ酸と
窒素原子含有塩基との塩とを少量の硬化促進剤として配
合することで、前記の欠点を解決することを見出し、発
明を完成させた。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have identified a specific method when kneading with various sands as an effective curing method for self-curing a resol type phenol resin. Of a weakly basic compound of alkaline earth metal oxide and / or alkaline earth metal hydroxide and a salt of a sulfur atom-containing oxo acid such as ammonium thiosulfate and a nitrogen atom-containing base with a small amount of a curing accelerator. It was found that the above-mentioned drawbacks can be solved by blending as the above, and the invention was completed.
【０００６】即ち、本発明は、鋳物砂（Ａ）、レゾール
型フェノール樹脂（Ｂ）、アルカリ土類金属酸化物及び
／又はアルカリ土類金属水酸化物（Ｃ）と、硫黄原子含
有オキソ酸と窒素原子含有塩基との塩（Ｄ）とを含有し
てなることを特徴とする鋳型用粘結剤組成物を提供す
る。That is, according to the present invention, a molding sand (A), a resol type phenol resin (B), an alkaline earth metal oxide and / or an alkaline earth metal hydroxide (C), and a sulfur atom-containing oxo acid are used. Provided is a binder composition for a template, which comprises a salt (D) with a nitrogen atom-containing base.
【０００７】[0007]
【発明の実施の形態】本発明の鋳型用自硬化性粘結剤組
成物に用いる鋳物砂（Ａ）としては、鋳物用のものであ
れば、特に限定されないが、フラタリーサンド（シリカ
含有率９９重量％型砂）、遠州珪砂（アルミナ１０重量
％、それ以外に酸化鉄、CaＯ、MgＯを含有するシリカ含
有率８０重量％の砂）、ハイアルミナサンド（アルミナ
４５重量％及び酸化鉄３重量％を含有するシリカ含有率
５０重量％の砂）、オリビンサンド（MgＯを４５重量％
含有するシリカ含有率４０重量％の砂）、ジルコンサン
ド（酸化ジルコンを６５重量％含有するシリカ含有率３
０重量％の砂）、クロマイトサンド（酸化鉄を２５重量
％、アルミナを１５重量％、MgＯを１０重量％含有する
酸化クロム含有率４６重量％の砂）、砂等が挙げられ
る。BEST MODE FOR CARRYING OUT THE INVENTION The casting sand (A) used in the self-curing binder composition for molds of the present invention is not particularly limited as long as it is for castings, but it is not limited to the flat sand (silica content rate). 99% by weight type sand), Enshu quartz sand (10% by weight alumina, sand with a silica content of 80% by weight containing iron oxide, CaO, MgO in addition to that), high alumina sand (45% by weight alumina and 3% by weight iron oxide). Silica containing 50% by weight of silica), olivine sand (45% by weight of MgO)
Containing 40% by weight silica content sand, Zircon sand (containing 65% by weight zircon oxide silica content 3
0 wt% sand), chromite sand (25 wt% iron oxide, 15 wt% alumina, 10 wt% MgO, chromium oxide content 46 wt% sand), sand and the like.
【０００８】本発明の鋳型用自硬化性粘結剤組成物に用
いるレゾール型フェノール樹脂（Ｂ）としては、フェノ
ール、クレゾール、ビスフェノールＡ等のようなフェノ
ール類と、ホルムアルデヒド、パラホルムアルデヒド、
グリオキザール等のようなアルデヒド類とを、アルカリ
触媒存在下で反応させて得られるものが挙げられる。ま
た、前述の様にして得られたレゾール樹脂を中和して酸
硬化型樹脂としたものであってもよい。また、使用する
形態としては、メタノールやグリコール等のレゾール樹
脂の有機溶剤溶液でも有効であるが、この際は環境を考
慮するとして、レゾール樹脂水溶液が好ましい。The resol type phenolic resin (B) used in the self-curing binder composition for a mold of the present invention includes phenols such as phenol, cresol and bisphenol A, formaldehyde, paraformaldehyde,
Examples thereof include those obtained by reacting with aldehydes such as glyoxal in the presence of an alkali catalyst. Alternatively, the resol resin obtained as described above may be neutralized into an acid-curable resin. Further, as a form to be used, an organic solvent solution of a resole resin such as methanol or glycol is also effective, but in this case, an aqueous resole resin solution is preferable in consideration of the environment.
【０００９】本発明の鋳型用自硬化性粘結剤組成物に用
いるアルカリ土類金属酸化物及び／又はアルカリ土類金
属水酸化物（Ｃ）としては、後述するの硫黄原子含有オ
キソ酸と窒素原子含有塩基との塩（Ｃ）の硬化促進剤と
しての働きを活性化する目的で使用されるものである。
例えば、酸化マグネシウム、酸化カルシウム、酸化バリ
ウム、水酸化マグネシウム、水酸化カルシウム、水酸化
バリウムが挙げられる。中でも、酸化マグネシウム、水
酸化カルシウム、水酸化バリウムが好ましく、更に酸化
マグネシウム（ＭｇＯ）が特に好ましい。前記MgＯとし
ては、例えば、骨材と呼ばれる範囲の成形用MgＯ（数mm
から数μｍ粒径）が好ましい。中でも、活性MgＯといわ
れる、粒径数μｍ以下の微粒子のものが特に好ましい。Examples of the alkaline earth metal oxide and / or the alkaline earth metal hydroxide (C) used in the self-curing binder composition for a mold of the present invention include sulfur atom-containing oxo acid and nitrogen described below. It is used for the purpose of activating the function of the salt (C) with an atom-containing base as a curing accelerator.
Examples thereof include magnesium oxide, calcium oxide, barium oxide, magnesium hydroxide, calcium hydroxide and barium hydroxide. Among them, magnesium oxide, calcium hydroxide and barium hydroxide are preferable, and magnesium oxide (MgO) is particularly preferable. As the MgO, for example, MgO for molding in a range called aggregate (several mm
To several μm particle size) is preferred. Among them, fine particles having a particle diameter of several μm or less, which is called active MgO, are particularly preferable.
【００１０】本発明の鋳型用自硬化性粘結剤組成物に用
いる硫黄原子含有オキソ酸と窒素原子含有塩基との塩
（Ｄ）としては、硫黄原子含有オキソ酸と窒素原子含有
塩基との塩であれば、特に限定されないが、例えば硫黄
原子含有オキソ酸成分としては、例えば、チオ硫酸、亜
ジチオン酸、二亜硫酸、または、二チオン酸、三チオン
酸、四チオン酸等のポリチオン酸類が挙げられ、中でも
チオ硫酸が、硬化物中に該酸成分残留した場合に硬化物
の物性の低下が少ない点から、特に好ましい。また、前
記の硫黄原子含有オキソ酸と窒素原子含有塩基との塩
（Ｄ）中の窒素原子含有塩基としては、例えば、アンモ
ニア、ヒドロキシルアミン、ヒドラジン、フェニルヒド
ラジン、セミカルバジド等のアンモニア誘導体類、メチ
ルアミン、ジメチルアミン、トリメチルアミン、エチル
アミン、n-プロピルアミン、n-ジプロピルアミン、n-ト
リプロピルアミン、イソプロピルアミン、ジイソプロピ
ルアミントリイソプロピルアミン、n-ブチルアミン、ジ
-n-ブチルアミンブチルアミン、トリ-n-ブチルアミン等
の脂肪族アミン類、アニリン、ジエチルアニリン、ジフ
ェニルアミン等の芳香族アミンが挙げられ、中でも、低
温での硬化促進効果が高い点から、アンモニアが好まし
い。これら硫黄原子含有オキソ酸と窒素原子含有塩基と
の塩（Ｄ）を具体的に例示すると、チオ硫酸アンモニウ
ム、亜ジチオン酸アンモニウム、二亜硫酸アンモニウ
ム、または、二チオン酸アンモニウム、三チオン酸アン
モニウム、四チオン酸アンモニウムなどが挙げられる。
これらの中でも、チオ硫酸アンモニウム〔（ＮＨ３）２
Ｓ２Ｏ３〕が特に好ましい。The salt (D) of a sulfur atom-containing oxo acid and a nitrogen atom-containing base used in the self-curing binder composition for a template of the present invention is a salt of a sulfur atom-containing oxo acid and a nitrogen atom-containing base. If so, it is not particularly limited, and examples of the sulfur atom-containing oxo acid component include, for example, thiosulfuric acid, dithionous acid, disulfurous acid, or polythionic acids such as dithionic acid, trithionic acid, and tetrathionic acid. Among them, thiosulfuric acid is particularly preferable, because the physical properties of the cured product are not significantly deteriorated when the acid component remains in the cured product. Examples of the nitrogen atom-containing base in the salt (D) of the sulfur atom-containing oxo acid and the nitrogen atom-containing base include ammonia, hydroxylamine, hydrazine, phenylhydrazine, semicarbazide and other ammonia derivatives, and methylamine. , Dimethylamine, trimethylamine, ethylamine, n-propylamine, n-dipropylamine, n-tripropylamine, isopropylamine, diisopropylamine triisopropylamine, n-butylamine, di
Examples thereof include aliphatic amines such as -n-butylamine butylamine and tri-n-butylamine, and aromatic amines such as aniline, diethylaniline and diphenylamine. Among them, ammonia is preferable because it has a high curing acceleration effect at low temperatures. Specific examples of the salt (D) of the sulfur atom-containing oxo acid and the nitrogen atom-containing base include ammonium thiosulfate, ammonium dithionite, ammonium disulfite, or ammonium dithionate, ammonium trithionate, and tetrathione. Ammonium acid etc. are mentioned.
Among these, ammonium thiosulfate [(NH 3 ) 2
S 2 O 3 ] is particularly preferable.
【００１１】本発明において、鋳物砂（Ａ）とレゾール
型フェノール樹脂（Ｂ）との配合比率は、鋳物砂（Ａ）
１００重量部に対して、レゾール型フェノール樹脂
（Ｂ）を０．３〜１０重量部配合して混練することが好
ましい。In the present invention, the mixing ratio of the foundry sand (A) and the resole type phenolic resin (B) is such that the foundry sand (A)
It is preferable to mix 0.3 to 10 parts by weight of the resol type phenol resin (B) with 100 parts by weight and knead.
【００１２】また、硫黄原子含有オキソ酸と窒素原子含
有塩基との塩（Ｄ）の配合量は、前記の鋳物砂（Ａ）と
レゾール型フェノール樹脂（Ｂ）とを、鋳物砂（Ａ）１
００重量部に対して、レゾール型フェノール樹脂（Ｂ）
を０．３〜１０重量部配合した配合物（Ｘ）において、
（［配合物（Ｘ）］／［（Ｄ）］）＝（１００／０．０
１）〜（１００／５）（重量比）となることが好まし
い。Further, the compounding amount of the salt (D) of the sulfur atom-containing oxo acid and the nitrogen atom-containing base is such that the molding sand (A) and the resole type phenolic resin (B) are mixed in the molding sand (A) 1
Resol type phenolic resin (B) based on 00 parts by weight
In the compound (X) containing 0.3 to 10 parts by weight of
([Compound (X)] / [(D)]) = (100 / 0.0
It is preferably 1) to (100/5) (weight ratio).
【００１３】また、アルカリ土類金属酸化物および／又
はアルカリ土類金属水酸化物（Ｃ）の配合量は、前記配
合物（Ｘ）と硫黄原子含有オキソ酸と窒素原子含有塩基
との塩（Ｄ）との配合物を配合物（Ｙ）としたとき、配
合物（Ｙ）１００重量部に対して、アルカリ土類金属酸
化物および／又はアルカリ土類金属水酸化物（Ｃ）を
０．１重量部〜１０重量部添加することが好ましい。Further, the blending amount of the alkaline earth metal oxide and / or the alkaline earth metal hydroxide (C) is such that the blend (X) is a salt of a sulfur atom-containing oxo acid and a nitrogen atom-containing base ( When the compound with (D) is used as the compound (Y), the alkaline earth metal oxide and / or the alkaline earth metal hydroxide (C) is added to 100 parts by weight of the compound (Y). It is preferable to add 1 to 10 parts by weight.
【００１４】なお、前記のアルカリ土類金属酸化物及び
／又はアルカリ土類金属水酸化物（Ｃ）と硫黄原子含有
オキソ酸と窒素原子含有塩基との塩（Ｄ）を併用するこ
とで、アルカリ性化合物のみを硬化触媒として用いる場
合、或いは、ｐ−トルエンスルホン酸等の酸成分を単独
で用いる場合よりも使用量が少なくても硬化する。The alkaline earth metal oxide and / or the alkaline earth metal hydroxide (C) and a salt (D) of a sulfur atom-containing oxo acid and a nitrogen atom-containing base are used in combination to obtain an alkaline solution. Even when the compound is used as a curing catalyst, or when an acid component such as p-toluenesulfonic acid is used alone, the compound is cured even when used in a smaller amount.
【００１５】前記の鋳物砂（Ａ）、レゾール型フェノー
ル樹脂（Ｂ）、アルカリ土類金属酸化物及び／又はアル
カリ土類金属水酸化物（Ｃ）及び硫黄原子含有オキソ酸
と窒素原子含有塩基との塩（Ｄ）の混合、混練には、現
行の鋳型成形システムに使用のバッチ式、連続式装置を
使用することは全く支障ない。混練された鋳物砂は通常
の型枠に投入され、自硬化性により経時的に硬化し、型
枠から脱枠され鋳型としての砂型が得られる。The above molding sand (A), resol type phenol resin (B), alkaline earth metal oxide and / or alkaline earth metal hydroxide (C), sulfur atom-containing oxo acid and nitrogen atom-containing base. For the mixing and kneading of the salt (D), the use of the batch type or continuous type apparatus used in the current mold forming system does not cause any problem. The kneaded foundry sand is put into an ordinary mold, and is cured over time due to its self-hardening property, and is removed from the mold to obtain a sand mold as a mold.
【００１６】本発明の鋳型用自硬化性粘結剤組成物は、
例えば、上記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）の４成分
を単に混合するだけで得られる。このようにして得られ
た本発明のレゾール型フェノール樹脂組成物は、１０〜
１１０℃の温度、例えば、室温放置や、１００℃程度で
も低温で硬化する。特に、本発明の組成物の硬化温度と
しては、１０℃〜５０℃が好ましい。もちろん、通常の
レゾール樹脂の硬化に要する１２０〜２５０℃程度まで
の加熱も、硬化速度を速め、かつ余分の水分、揮発分等
を除去することになり、差し支えない。The self-curing binder composition for molds of the present invention comprises
For example, it can be obtained by simply mixing the above four components (A), (B), (C), and (D). The resol type phenolic resin composition of the present invention thus obtained has
It cures at a temperature of 110 ° C., for example at room temperature, or at a low temperature of about 100 ° C. Particularly, the curing temperature of the composition of the present invention is preferably 10 ° C to 50 ° C. Of course, heating up to about 120 to 250 ° C. required for usual resol resin curing also accelerates the curing rate and removes excess water, volatile matter, etc.
【００１７】[0017]
【実施例】以下に実施例および比較例を挙げて本発明を
具体的に説明する。なお、例中の部および％はすべて重
量基準である。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. All parts and% in the examples are based on weight.
【００１８】実施例１〜１４及び比較例1〜７
以下の例で用いるレゾール型フェノール樹脂（Ｂ）は、
NaＯＨ触媒で製造した水溶性のレゾール型フェノール樹
脂（大日本インキ化学製品フェノライトＤＧ−６２６）
を用いた。Examples 1 to 14 and Comparative Examples 1 to 7 The resol type phenolic resin (B) used in the following examples is
Water-soluble resol type phenolic resin manufactured with NaOH catalyst (Dainippon Ink and Chemicals Phenolite DG-626)
Was used.
【００１９】また、鋳型用自硬化性粘結剤組成物の調製
手順としては、後述する種々の鋳物砂（Ａ）にレゾール
樹脂水溶液を添加し砂粒を濡らし、配合物（Ｘ）を調製
する。次いで、配合物（Ｘ）に硫黄原子含有オキソ酸と
窒素原子含有塩基との塩（Ｄ）として、チオ硫酸アンム
ニウムを添加して再度濡らし、配合物（Ｙ）を調製す
る。次いで、配合物（Ｙ）にアルカリ土類金属酸化物及
び／又はアルカリ土類金属水酸化物（Ｃ）としてMgＯを
入れて全体を混合し、鋳型用自硬化性粘結剤組成物（以
下、混練砂と記す。）を調製する。取り出した混練砂
を、５cm径×５cm高さの木型中にて成形する。その後経
時強度を見るべく適当な時間毎に、２４時間まで追跡し
て硬化状況を確認した。下記表１及び２その実施例の結
果を、また比較例を表３に示す。As a procedure for preparing the self-curing binder composition for casting molds, an aqueous resole resin solution is added to various molding sands (A) described below to wet the sand grains to prepare the compound (X). Then, as the salt (D) of the sulfur atom-containing oxo acid and the nitrogen atom-containing base, the formulation (X) is added with ammonium thiosulfate and wetted again to prepare the formulation (Y). Then, MgO as an alkaline earth metal oxide and / or an alkaline earth metal hydroxide (C) is added to the compound (Y) and the whole is mixed to obtain a self-curing binder composition for a template (hereinafter, Prepared as kneading sand). The kneaded sand taken out is molded in a wooden mold having a diameter of 5 cm and a height of 5 cm. Then, in order to see the strength over time, the state of curing was confirmed by tracing for 24 hours at an appropriate time. Tables 1 and 2 below show the results of the examples, and Table 3 shows comparative examples.
【００２０】前記の鋳物砂（Ａ）としては、フラタリ
ーサンド（シリカ含有率９９％型砂）、遠州珪砂（ア
ルミナ１０％、それ以外に酸化鉄、CaＯ、MgＯを含有す
るシリカ含有率８０％の砂）、ハイアルミナサンド
（アルミナ４５％及び酸化鉄３％を含有するシリカ含有
率５０％の砂）、オリビンサンド（MgＯを４５％含有
するシリカ含有率４０％の砂）、ジルコンサンド（酸
化ジルコンを６５％含有するシリカ含有率３０％の
砂）、クロマイトサンド（酸化鉄を２５％、アルミナ
を１５％、MgＯを１０％含有する酸化クロム含有率４６
％の砂）、前記のフラタリーサンド１００重量部当た
り粘土２０％を添加した砂をそれぞれ用いた。As the above-mentioned foundry sand (A), flat sand (silica content 99% type sand), Enshu quartz sand (alumina 10%, silica 80% containing iron oxide, CaO, MgO in addition thereto) Sand), high alumina sand (sand containing 45% alumina and 3% iron oxide and having a silica content of 50%), olivine sand (sand containing 45% MgO and a silica content of 40%), zircon sand (zircon oxide Silica containing 65% of 30% sand), chromite sand (iron oxide 25%, alumina 15%, MgO 10% chromium oxide content 46
% Sand) and sand to which 20% of clay was added per 100 parts by weight of the above flattery sand.
【００２１】実施例１〜１４及び比較例1〜７
鋳物砂として使用されているものの中から以下の概要
で、種々の系統の砂で硬化性を確認した。Examples 1 to 14 and Comparative Examples 1 to 7 From among those used as foundry sand, the hardenability was confirmed with various types of sand according to the following outline.
【００２２】表中の各配合量は砂１００重量部に対する
重量部を示し、また、強度は 抗圧強度(Kg/cm2)を示
す。Each compounding amount in the table indicates parts by weight with respect to 100 parts by weight of sand, and the strength indicates a compressive strength (Kg / cm 2 ).
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】比較例については、レゾール型フェノール
樹脂（表３ではレゾール樹脂と記す。）は実施例に使用
したフェノール樹脂に同じで、その硬化剤としては最も
汎用な酸硬化剤であるパラトルエンスルホン酸（ＰＴＳ
Ａ）を使用して、実施例と同じ砂について比較した。な
お、前記のＰＴＳＡを実施例１と同量添加して成形した
ものは、下記の比較例４と同様に、成形物の強度が極め
て抗圧強度が低かった。In the comparative example, the resol type phenol resin (referred to as a resol resin in Table 3) is the same as the phenol resin used in the examples, and its curing agent is paratoluene sulfone which is the most general-purpose acid curing agent. Acid (PTS
A) was used to compare the same sands as the example. In addition, in the same manner as in Comparative Example 4 below, a molded article obtained by adding the above-mentioned PTSA in the same amount as in Example 1 had a significantly low strength of the molded product.
【表３】 [Table 3]
【００２５】[0025]
【発明の効果】本発明の組成物は、少量の硬化触媒で、
充分な強度の硬化物を得ることができ、そのため、硬化
触媒の分解時に発生する有害なガスの発生が大幅に軽減
された硬化システムを提供できる。The composition of the present invention contains a small amount of a curing catalyst,
It is possible to obtain a cured product having sufficient strength, and thus it is possible to provide a curing system in which the generation of harmful gas generated when the curing catalyst is decomposed is significantly reduced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 61/06 Ｃ０８Ｌ 61/06 Ｆターム(参考） 4E092 AA02 AA03 AA06 AA14 AA19 AA46 BA12 4J002 CC041 CC061 DE067 DG038 DJ006 FD147 FD148 FD206 GT00 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 61/06 C08L 61/06 F term (reference) 4E092 AA02 AA03 AA06 AA14 AA19 AA46 BA12 4J002 CC041 CC061 DE067 DG038 DJ006 FD147 FD148 FD206 GT00
Claims (5)
脂（Ｂ）、アルカリ土類金属酸化物及び／又はアルカリ
土類金属水酸化物（Ｃ）と、硫黄原子含有オキソ酸と窒
素原子含有塩基との塩（Ｄ）とを含有してなることを特
徴とする鋳型用粘結剤組成物。1. A molding sand (A), a resol type phenol resin (B), an alkaline earth metal oxide and / or an alkaline earth metal hydroxide (C), a sulfur atom-containing oxo acid and a nitrogen atom-containing base. And a salt (D) thereof with a binder composition for a mold.
ルカリ土類金属水酸化物（Ｃ）が、マグネシウム、カル
シウム又はバリウムの酸化物および／又はマグネシウ
ム、カルシウム又はバリウムの水酸化物である請求項１
記載の鋳型用粘結剤組成物。2. The alkaline earth metal oxide and / or alkaline earth metal hydroxide (C) is an oxide of magnesium, calcium or barium and / or a hydroxide of magnesium, calcium or barium. 1
The binder composition for a mold as described.
基との塩（Ｄ）が、チオ硫酸アンモニウムである、請求
項２記載の鋳型用粘結剤組成物。3. The binder composition for a template according to claim 2, wherein the salt (D) of a sulfur atom-containing oxo acid and a nitrogen atom-containing base is ammonium thiosulfate.
フェノール樹脂（Ｂ）を０．３〜１０重量部混練した配
合物（Ｘ）と、硫黄原子含有オキソ酸と窒素原子含有塩
基との塩（Ｄ）との配合比率が、（［配合物（Ｘ）］／
［（Ｄ）］）＝（１００／０．０１）〜（１００／５）
（重量比）である請求項１、２又は３記載の鋳型用粘結
剤組成物。4. A compound (X) prepared by kneading 100 parts by weight of molding sand (A) with 0.3 to 10 parts by weight of a resol type phenol resin (B), a sulfur atom-containing oxo acid and a nitrogen atom-containing base. The blending ratio with the salt (D) is ([blend (X)] /
[(D)]) = (100 / 0.01) to (100/5)
(Weight ratio) The binder composition for a mold according to claim 1, 2 or 3.
窒素原子含有塩基との塩（Ｄ）との混合物（Ｙ）１００
重量部に対して、アルカリ土類金属酸化物および／又は
アルカリ土類金属水酸化物（Ｃ）が０．１〜１０重量部
添加されてなる請求項４記載の鋳型用粘結剤組成物。5. A mixture (Y) 100 of the compound (X) and a salt (D) of a sulfur atom-containing oxo acid and a nitrogen atom-containing base.
The binder composition for a mold according to claim 4, wherein 0.1 to 10 parts by weight of the alkaline earth metal oxide and / or the alkaline earth metal hydroxide (C) is added to the parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002023628A JP4114000B2 (en) | 2002-01-31 | 2002-01-31 | Self-curing binder composition for mold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002023628A JP4114000B2 (en) | 2002-01-31 | 2002-01-31 | Self-curing binder composition for mold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003225736A true JP2003225736A (en) | 2003-08-12 |
| JP4114000B2 JP4114000B2 (en) | 2008-07-09 |
Family
ID=27746289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002023628A Expired - Fee Related JP4114000B2 (en) | 2002-01-31 | 2002-01-31 | Self-curing binder composition for mold |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4114000B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015039720A (en) * | 2013-08-23 | 2015-03-02 | 見得行股▲ふん▼有限公司 | Stabilizer |
| JP2020082132A (en) * | 2018-11-26 | 2020-06-04 | 花王株式会社 | Binder composition for cast molding |
| JP2020089915A (en) * | 2018-11-26 | 2020-06-11 | 花王株式会社 | Phenol odor inhibitory cast molding composition |
-
2002
- 2002-01-31 JP JP2002023628A patent/JP4114000B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015039720A (en) * | 2013-08-23 | 2015-03-02 | 見得行股▲ふん▼有限公司 | Stabilizer |
| JP2020082132A (en) * | 2018-11-26 | 2020-06-04 | 花王株式会社 | Binder composition for cast molding |
| JP2020089915A (en) * | 2018-11-26 | 2020-06-11 | 花王株式会社 | Phenol odor inhibitory cast molding composition |
| JP7341609B2 (en) | 2018-11-26 | 2023-09-11 | 花王株式会社 | Molding composition for suppressing phenol odor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4114000B2 (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20080207796A1 (en) | Furanic resin aggregate binders and method | |
| BR112019024317B1 (en) | METHOD FOR PRODUCING THREE-DIMENSIONAL BODIES MOLDED IN LAYERS | |
| JP2003225736A (en) | Self-hardening binder composition for mold | |
| JP2009269062A (en) | Binder composition for casting mold making, sand composition for casting mold making, and manufacturing method of casting mold | |
| JP2017070967A (en) | Phenolic resin composition for shell mold, resin coated sand for shell mold, and mold for shell mold prepared therewith | |
| JPH11244991A (en) | Manufacture of resin coated sand | |
| JP3203257B2 (en) | Acid-curable refractory granular material composition for mold molding | |
| JP2001314939A (en) | Component of binding agent for gas hardening mold | |
| WO1997018913A1 (en) | Cold-box process for preparing foundry shapes | |
| JP3933794B2 (en) | Binder composition for carbon dioxide gas curing | |
| KR100947964B1 (en) | Binder composition of carbon dioxide gas hardening type and molding method thereof | |
| JP7337659B2 (en) | Curing agent composition for mold making | |
| JP2005095932A (en) | Phenolic resin composition for shell mold, and resin-coated sand | |
| JP7303680B2 (en) | Binder composition for mold making | |
| EP1167428B1 (en) | Resol-type phenol resin composition and method for curing the same | |
| JP3200644B2 (en) | Binder composition for mold and method for producing mold | |
| JP4440017B2 (en) | Acid curable refractory granular material composition | |
| JPH02299741A (en) | Improvement of fluidity of resin-coated sand | |
| JPH04147743A (en) | Manufacture of mold or core | |
| JP3457188B2 (en) | Hardener composition for mold production | |
| JP6584919B2 (en) | Mold manufacturing method | |
| JP3197973B2 (en) | Composition for foundry sand | |
| JPH0623475A (en) | Hardener composition for thermosetting casting hold | |
| JP3170928B2 (en) | Binder composition for mold and method for producing mold | |
| JP2001219242A (en) | Binder composition for molding sand and casting mold composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050120 |
|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20050628 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080205 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080226 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080318 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080331 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110425 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4114000 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110425 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110425 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120425 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120425 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120425 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130425 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130425 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140425 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |