JP3457188B2 - Hardener composition for mold production - Google Patents
Hardener composition for mold productionInfo
- Publication number
- JP3457188B2 JP3457188B2 JP22419398A JP22419398A JP3457188B2 JP 3457188 B2 JP3457188 B2 JP 3457188B2 JP 22419398 A JP22419398 A JP 22419398A JP 22419398 A JP22419398 A JP 22419398A JP 3457188 B2 JP3457188 B2 JP 3457188B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- curing agent
- benzenesulfonic acid
- agent 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸硬化性樹脂の硬
化のための鋳型製造用硬化剤組成物、及びこれを用いた
鋳型製造方法に関する。TECHNICAL FIELD The present invention relates to a curing agent composition for producing a mold for curing an acid-curable resin, and a method for producing a mold using the same.
【０００２】[0002]
【従来の技術】酸硬化性樹脂の硬化剤として、ベンゼン
スルホン酸、トルエンスルホン酸、キシレンスルホン酸
等の芳香族スルホン酸が使用されており、その改良につ
いても検討されている（特開平９−47840号公報）。し
かし、鋳型の硬化速度を上げるには、これらの芳香族ス
ルホン酸を多量に添加する必要があり、これらは注湯時
の熱により分解して、硫黄含有ガス等の有害な分解物を
放出するため、作業環境が悪化する。2. Description of the Related Art Aromatic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid and xylenesulfonic acid are used as a curing agent for acid-curable resins, and their improvement has also been studied (JP-A-9- 47840 bulletin). However, in order to increase the mold curing speed, it is necessary to add a large amount of these aromatic sulfonic acids, and these are decomposed by the heat during pouring to release harmful decomposition products such as sulfur-containing gas. Therefore, the working environment deteriorates.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、硬化速度を
低下させずに、鋳込み時の硫黄含有ガスの発生量を低減
させることのできる、鋳型製造用硬化剤組成物の提供を
課題とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a curing agent composition for producing a mold, which can reduce the amount of sulfur-containing gas generated during casting without lowering the curing rate. .
【０００４】[0004]
【課題を解決するための手段】本発明は、１分子中に１
以上のカルボキシル基を有するベンゼンスルホン酸誘導
体、１分子中に２以上の水酸基を有するベンゼンスルホ
ン酸誘導体、及び１分子中に１以上のカルボキシル基と
１以上の水酸基を有するベンゼンスルホン酸誘導体より
なる群から選ばれるベンゼンスルホン酸誘導体の１種以
上を含有する鋳型製造用酸硬化剤組成物を提供する。The present invention provides 1 in 1 molecule.
A group consisting of the above-mentioned benzenesulfonic acid derivative having a carboxyl group, one benzenesulfonic acid derivative having two or more hydroxyl groups in one molecule, and benzenesulfonic acid derivative having one or more carboxyl groups and one or more hydroxyl groups in one molecule Provided is an acid curing agent composition for producing a mold, which comprises at least one benzenesulfonic acid derivative selected from
【０００５】本発明に用いられるベンゼンスルホン酸誘
導体としては、2-スルホ安息香酸、4-,又は5-スルホフ
タル酸、5-スルホイソフタル酸、2,5-ジヒドロキシベン
ゼンスルホン酸、4-ヒドロキシ-5-スルホ安息香酸など
が挙げられる。また上記カルボキシル基及び／又は水酸
基に加え、アルキル基、ハロゲン基、ニトロ基等他の置
換基を有していても良い。好ましくは、１分子中にカル
ボキシル基及び／又は水酸基を合わせて２有するベンゼ
ンスルホン酸誘導体が用いられ、更に好ましくはスルホ
フタル酸、スルホイソフタル酸、ジヒドロキシベンゼン
スルホン酸、ヒドロキシスルホ安息香酸である。The benzenesulfonic acid derivatives used in the present invention include 2-sulfobenzoic acid, 4-, or 5-sulfophthalic acid, 5-sulfoisophthalic acid, 2,5-dihydroxybenzenesulfonic acid, and 4-hydroxy-5. -Sulfobenzoic acid and the like. Further, in addition to the above-mentioned carboxyl group and / or hydroxyl group, it may have another substituent such as an alkyl group, a halogen group and a nitro group. A benzenesulfonic acid derivative having two carboxyl groups and / or hydroxyl groups in a molecule is preferably used, and more preferably sulfophthalic acid, sulfoisophthalic acid, dihydroxybenzenesulfonic acid, or hydroxysulfobenzoic acid.
【０００６】硬化剤組成物中には、上記ベンゼンスルホ
ン酸誘導体が単独で若しくは混合して含有される。さら
に、メタンスルホン酸、エタンスルホン酸等の炭素数１
〜10の脂肪族スルホン酸、ベンゼンスルホン酸、トルエ
ンスルホン酸、キシレンスルホン酸等の芳香族スルホン
酸、酒石酸、クエン酸等のカルボン酸等の有機酸、硫
酸、燐酸、塩酸、硝酸等の無機酸が単独で若しくは混合
して含有されていてもよい。The above-mentioned benzenesulfonic acid derivative is contained alone or in a mixture in the curing agent composition. Furthermore, carbon number 1 such as methanesulfonic acid and ethanesulfonic acid
~ 10 aromatic sulfonic acids such as aliphatic sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, organic acids such as carboxylic acid such as tartaric acid and citric acid, inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid May be contained alone or in a mixture.
【０００７】上記ベンゼンスルホン酸誘導体の好ましい
硬化剤組成物中の濃度は砂温によって異なるが、硬化剤
組成物中の硫黄濃度が好ましくは0.1〜30重量％、さら
に好ましくは１〜20重量％となる量である。The preferred concentration of the benzenesulfonic acid derivative in the hardener composition varies depending on the sand temperature, but the sulfur concentration in the hardener composition is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. It is an amount.
【０００８】硬化剤組成物が上記ベンゼンスルホン酸誘
導体に加えて、他のスルホン酸や無機酸を含有する場
合、硬化剤組成物中の全硫黄濃度の40％以上、好ましく
は60％以上が上記ベンゼンスルホン酸に由来するもので
あることが望ましい。When the curing agent composition contains other sulfonic acid or inorganic acid in addition to the above benzenesulfonic acid derivative, 40% or more, preferably 60% or more of the total sulfur concentration in the curing agent composition is described above. It is preferably derived from benzenesulfonic acid.
【０００９】本発明の硬化剤組成物は、耐火性粒状材料
100重量部に対して好ましくは0.05〜５重量部、好まし
くは0.2〜３重量部用いられる。硬化剤組成物の使用に
際しては、界面活性剤などの硬化を促進するための従来
公知の添加剤を使用できる。The hardener composition of the present invention comprises a refractory granular material.
It is preferably used in an amount of 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight. When the curing agent composition is used, conventionally known additives such as a surfactant for promoting curing can be used.
【００１０】耐火性粒状材料としては、石英質を主成分
とする硅砂の他、クロマイト砂、ジルコン砂、オリビン
砂、アルミナサンドや人工ムライトサンド等の新砂若し
くは機械的摩耗式或は焙焼式で得られる再生砂が使用さ
れる。As the refractory granular material, in addition to silica sand containing silica as a main component, new sand such as chromite sand, zircon sand, olivine sand, alumina sand and artificial mullite sand, or mechanical abrasion type or roasting type is used. The resulting recycled sand is used.
【００１１】本発明の硬化剤組成物は、結合剤である酸
硬化性樹脂の硬化を促進させる。酸硬化性樹脂として
は、フルフリルアルコール、フルフリルアルコールポリ
マー、フルフリルアルコール・尿素重縮合物、フルフリ
ルアルコール・アルデヒド類重縮合物、フルフリルアル
コール・アルデヒド類・尿素重縮合物、フルフリルアル
コール・メラミン重縮合物、フルフリルアルコール・ア
ルデヒド類・メラミン重縮合物、フルフリルアルコール
・フェノール類重縮合物等のフラン樹脂の１種以上が好
ましく、またその添加量は、耐火性粒状材料100重量部
に対して0.1〜５重量部であるのが好ましい。アルデヒ
ド類としては、ホルムアルデヒド、グリオキザール、フ
ルフラールなどが使用でき、フェノール類としてはフェ
ノール、レゾルシノール、ビスフェノールＡなどが使用
できる。The hardener composition of the present invention accelerates the hardening of the acid-curable resin as the binder. As the acid-curable resin, furfuryl alcohol, furfuryl alcohol polymer, furfuryl alcohol / urea polycondensate, furfuryl alcohol / aldehyde polycondensate, furfuryl alcohol / aldehyde / urea polycondensate, furfuryl alcohol One or more furan resins such as melamine polycondensate, furfuryl alcohol / aldehydes / melamine polycondensate, furfuryl alcohol / phenol polycondensate are preferable, and the addition amount thereof is 100 weight% of the refractory granular material. It is preferably 0.1 to 5 parts by weight with respect to parts. Formaldehyde, glyoxal, furfural, etc. can be used as the aldehydes, and phenol, resorcinol, bisphenol A, etc. can be used as the phenols.
【００１２】さらに、鋳型強度をより向上させる目的
で、Ｎ−β（アミノエチル）γ−アミノプロピルメチル
ジメトキシシラン、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を加えることもできる。Further, a silane coupling agent such as N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane or γ-aminopropyltrimethoxysilane may be added for the purpose of further improving the template strength.
【００１３】本発明に係る硬化剤組成物を使用して鋳型
を製造する場合、まず上記した耐火性粒状材料に、本発
明に係る硬化剤組成物及び酸硬化性樹脂を添加混練す
る。硬化剤組成物の添加後に酸硬化性フラン樹脂を添加
するのが一般的であるが、逆であっても、同時に添加し
てもよい。また、従来公知の各種変性剤等が酸硬化性樹
脂中に配合されていてもよく、2,5-ビスヒドロキシメチ
ルフランなどの硬化促進剤を含有することが好ましい。When a mold is produced using the curing agent composition according to the present invention, first, the curing agent composition according to the present invention and an acid-curable resin are added and kneaded to the above-mentioned refractory granular material. The acid-curable furan resin is generally added after the addition of the curing agent composition, but the reverse order or the simultaneous addition may be performed. Further, various conventionally known modifiers and the like may be blended in the acid-curable resin, and it is preferable to contain a curing accelerator such as 2,5-bishydroxymethylfuran.
【００１４】上記のようにして、耐火性粒状材料に硬化
剤組成物及び酸硬化性樹脂等を添加混練して混練砂を得
る。この混練砂を型枠に充填した後、酸硬化性樹脂を硬
化させることによって、鋳型が製造される。As described above, the hardener composition, the acid-curable resin and the like are added and kneaded to the refractory granular material to obtain kneaded sand. A mold is manufactured by filling the kneading sand in a mold and then curing the acid-curable resin.
【００１５】[0015]
【実施例】実施例及び比較例中の％は重量％を示す。EXAMPLES In the examples and comparative examples,% means% by weight.
【００１６】実施例１〜６及び比較例１〜４
25℃、55％ＲＨの条件下で、フリーマントル珪砂の新砂
100重量部に対し、表２記載のスルホン酸種を所定の硫
黄濃度（Ｓ％）で含有する硬化剤組成物水溶液を0.4重
量部、次いで表１に示す酸硬化性樹脂Ａ0.8重量部を添
加混合し、枠に充填して、直径50mm、高さ50mmの円柱形
テストピースを作成した。JIS Z 2604-1976に記載され
た方法で、30分後のテストピースの圧縮強度（kg／c
m2）を測定した。また、５人のパネラーにより鋳込み時
の臭気を判定した。 Examples 1 to 6 and Comparative Examples 1 to 4 Fresh mantle quartz sand under the conditions of 25 ° C. and 55% RH
With respect to 100 parts by weight, 0.4 part by weight of an aqueous solution of a curing agent composition containing the sulfonic acid species shown in Table 2 at a predetermined sulfur concentration (S%), and then 0.8 part by weight of the acid-curable resin A shown in Table 1 were used. The mixture was added and mixed, and filled in a frame to prepare a cylindrical test piece having a diameter of 50 mm and a height of 50 mm. According to the method described in JIS Z 2604-1976, the compressive strength of the test piece after 30 minutes (kg / c
m 2 ) was measured. Also, the odor during casting was judged by five panelists.
【００１７】実施例７〜10
酸硬化性樹脂を表１に示す酸硬化性樹脂Ｂにした以外は
実施例１と同様に鋳型を製造し、測定を行った。以上の
結果を表２に示す。 Examples 7 to 10 Molds were prepared and measured in the same manner as in Example 1 except that the acid-curable resin B shown in Table 1 was used instead of the acid-curable resin. The above results are shown in Table 2.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【発明の効果】本発明によるベンゼンスルホン酸誘導体
を含有する鋳型製造用硬化剤組成物は、鋳型の硬化速度
を低下させずに、硫黄含有ガスなどによる作業環境の問
題を解決できる。EFFECTS OF THE INVENTION The curing agent composition for producing a mold containing the benzenesulfonic acid derivative according to the present invention can solve the problem of working environment due to sulfur-containing gas without lowering the curing rate of the mold.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−90246（ＪＰ，Ａ) 特開 平１−31542（ＪＰ，Ａ) 特開 昭55−86642（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B22C 1/00 - 1/26 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-3-90246 (JP, A) JP-A-1-31542 (JP, A) JP-A-55-86642 (JP, A) (58) Field (Int.Cl. 7 , DB name) B22C 1/00-1/26
Claims (4)
するベンゼンスルホン酸誘導体、１分子中に２以上の水
酸基を有するベンゼンスルホン酸誘導体、及び１分子中
に１以上のカルボキシル基と１以上の水酸基を有するベ
ンゼンスルホン酸誘導体よりなる群から選ばれるベンゼ
ンスルホン酸誘導体の１種以上を含有する鋳型製造用酸
硬化剤組成物。1. A benzenesulfonic acid derivative having one or more carboxyl groups in one molecule, a benzenesulfonic acid derivative having two or more hydroxyl groups in one molecule, and one or more carboxyl groups and one or more in one molecule. An acid curing agent composition for producing a mold, comprising at least one benzenesulfonic acid derivative selected from the group consisting of benzenesulfonic acid derivatives having a hydroxyl group.
中にカルボキシル基及び／又は水酸基を合わせて２有す
るベンゼンスルホン酸である請求項１の鋳型製造用硬化
剤組成物。2. The curing agent composition for producing a mold according to claim 1, wherein the benzenesulfonic acid derivative is benzenesulfonic acid having a total of two carboxyl groups and / or hydroxyl groups in one molecule.
組成物中に、硬化剤組成物中の硫黄濃度が0.1〜30重量
％となる量で含有される請求項１又は２の鋳型製造用硬
化剤組成物。3. The curing agent for producing a mold according to claim 1, wherein the benzenesulfonic acid derivative is contained in the curing agent composition in an amount such that the concentration of sulfur in the curing agent composition is 0.1 to 30% by weight. Composition.
求項１から３のいずれかの鋳型製造用硬化剤組成物とを
混合し、酸硬化性樹脂を硬化させる鋳型製造方法。4. A method for producing a mold, wherein a refractory granular material, an acid-curable resin, and the curing agent composition for producing a mold according to claim 1 are mixed to cure the acid-curable resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22419398A JP3457188B2 (en) | 1998-08-07 | 1998-08-07 | Hardener composition for mold production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22419398A JP3457188B2 (en) | 1998-08-07 | 1998-08-07 | Hardener composition for mold production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000051992A JP2000051992A (en) | 2000-02-22 |
| JP3457188B2 true JP3457188B2 (en) | 2003-10-14 |
Family
ID=16809987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22419398A Expired - Fee Related JP3457188B2 (en) | 1998-08-07 | 1998-08-07 | Hardener composition for mold production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3457188B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6069047B2 (en) * | 2012-04-27 | 2017-01-25 | 花王株式会社 | Hardener composition for mold making |
-
1998
- 1998-08-07 JP JP22419398A patent/JP3457188B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000051992A (en) | 2000-02-22 |
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