JPH0325255B2 - - Google Patents

Info

Publication number
JPH0325255B2
JPH0325255B2 JP58229356A JP22935683A JPH0325255B2 JP H0325255 B2 JPH0325255 B2 JP H0325255B2 JP 58229356 A JP58229356 A JP 58229356A JP 22935683 A JP22935683 A JP 22935683A JP H0325255 B2 JPH0325255 B2 JP H0325255B2
Authority
JP
Japan
Prior art keywords
mold
weight
composition
peroxide
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP58229356A
Other languages
Japanese (ja)
Other versions
JPS60121036A (en
Inventor
Yasuyuki Kawakatsu
Mitsuru Sakai
Kazuhiko Kiuchi
Yoshihiro Ejiri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KAO KUEEKAA KK
Original Assignee
KAO KUEEKAA KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by KAO KUEEKAA KK filed Critical KAO KUEEKAA KK
Priority to JP22935683A priority Critical patent/JPS60121036A/en
Publication of JPS60121036A publication Critical patent/JPS60121036A/en
Publication of JPH0325255B2 publication Critical patent/JPH0325255B2/ja
Granted legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/224Furan polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mold Materials And Core Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は耐火性粒状骨材に酸硬化性樹脂と過酸
化物を添加・混練し成型した砂型にガス状又はエ
ロゾル状の二酸化硫黄を添加して鋳型を成型する
際に用いられる組成物であつて、特定の希釈安定
化剤を含有する過酸化物組成物を有する硬化性鋳
型組成物に関するものである。 従来、高速で鋳型を製造するには耐火性粒状骨
材にフエノールノボラツク樹脂を被覆した、所謂
レジンコーテツドサンドを成型して熱硬化させる
シエルモールド法が使用されて来た。 しかし、鋳型製造時の省エネルギー、鋳型生産
速度、更に鋳型、鋳物の生産品質を改善するため
ガスを添加する事により常温で化学反応をし、硬
化せしめて鋳型を製造する所謂コールドボツクス
法が代替する鋳型の製造法として鋳物業界で真剣
に導入の検討がされている。 現在コールドボツクス法にはフラン樹脂を代表
とする酸硬化性樹脂を過酸化物を酸化剤として二
酸化硫黄により硬化する所謂フランコールドボツ
クス法とポリオールとポリイソシアネートをエロ
ゾル状の第3級アミンを触媒として硬化するウレ
タンコールドボツクス法があり、フラン自硬性で
多品種少量鋳物製造分野で好結果が証明されてい
るフランコールドボツクス法が最近急速に注目を
集めている。 シエルモールド法の一つの難点として鋳物製造
工程の内注湯後のバラシ工程での鋳型の崩壊性が
悪く、特にアルミ鋳物等では中子の砂型を取り出
すには熱処理を施す必要があり、砂型取出時の省
エネルギー、合理化のためにも代替する鋳型プロ
セスが要求されている。 本発明者らは高速鋳型造型法の中でも崩壊性の
良いフランコールドボツクス法の更に崩壊性を改
良せしめるべく鋭意研究の結果、本発明に到達し
た。 即ち、本発明は耐火性粒状材料に酸硬化性樹脂
と過酸化物組成物を添加混練し成型した砂型に、
ガス状又はエロゾル状の二酸化硫黄を吹き込んで
鋳型を製造する際に用いられる組成物であつて、
過酸化物組成物がハイドロパーオキサイド又はケ
トンパーオキサイド40〜60重量%と希釈安定化剤
60〜40重量%からなり、該希釈安定化剤が一般式
HOOC(−CH2−)oCOOH(但しn=1〜10)で表わ
される脂肪族二塩基酸のメチルエステルの少なく
とも一種を30〜100重量%含有するものである事
を特徴とする硬化性鋳型組成物に係るものであ
る。 希釈安定化剤は上記一般式で表わされる脂肪族
二塩基酸のメチルエステルのみでもよいが、公知
の過酸化物の希釈安定化剤を70重量%まで含有さ
せ得る。 かかる希釈安定化剤としては次の〔I〕〜
〔V〕で示される化合物の1種又は2種以上を使
用し得るが、70重量%よりも多いと鋳型の崩壊性
改良効果が不充分である。 〔I〕
The present invention is a composition that is used when forming a mold by adding gaseous or aerosol sulfur dioxide to a sand mold made by adding and kneading acid-curable resin and peroxide to fire-resistant granular aggregate. The present invention relates to curable mold compositions having peroxide compositions containing certain dilution stabilizers. Conventionally, in order to manufacture molds at high speed, a shell molding method has been used in which so-called resin coated sand, in which refractory granular aggregate is coated with phenolic novolac resin, is molded and heat cured. However, in order to save energy during mold manufacturing, mold production speed, and improve the production quality of molds and castings, the so-called cold box method, in which molds are manufactured by chemical reaction at room temperature by adding gas and hardening, has been replaced. The foundry industry is seriously considering its introduction as a mold manufacturing method. Currently, cold box methods include the so-called furan cold box method, in which acid-curing resins such as furan resin are cured with sulfur dioxide using peroxide as an oxidizing agent, and polyols and polyisocyanates are cured using an aerosol of tertiary amine as a catalyst. There is a urethane cold box method that hardens, and the Franco cold box method, which has been proven to have good results in the field of manufacturing high-mix, low-volume castings due to its self-hardening properties, has recently been rapidly attracting attention. One of the drawbacks of the shell mold method is that the mold does not easily disintegrate during the disassembly process after internal pouring in the casting manufacturing process, and especially for aluminum castings, it is necessary to perform heat treatment to remove the sand mold of the core. An alternative molding process is required in order to save energy and streamline the process. The present inventors have arrived at the present invention as a result of intensive research to further improve the disintegration of the Francold Box method, which has good disintegration among high-speed mold making methods. That is, the present invention involves adding and kneading an acid-curing resin and a peroxide composition to a fire-resistant granular material, and molding the resulting sand mold.
A composition used when producing a mold by blowing gaseous or aerosol sulfur dioxide, the composition comprising:
The peroxide composition contains 40-60% by weight of hydroperoxide or ketone peroxide and a dilution stabilizer.
60 to 40% by weight, and the dilution stabilizer has the general formula
A curable mold containing 30 to 100% by weight of at least one methyl ester of an aliphatic dibasic acid represented by HOOC(-CH 2 -) o COOH (n = 1 to 10). This relates to a composition. The dilution stabilizer may be only the methyl ester of the aliphatic dibasic acid represented by the above general formula, but it may contain up to 70% by weight of a known peroxide dilution stabilizer. Such dilution stabilizers include the following [I]~
One or more of the compounds represented by [V] may be used, but if the amount exceeds 70% by weight, the effect of improving mold disintegration will be insufficient. [I]

【式】 (式中nは1〜3でありn=1の場合Xは炭素数
1〜20のアルキル基、アルケニル基、アルキニル
基、シクロアルキル基、アリール基又はアルアル
キル基である。 n=2の場合 Xは炭素数2〜26のアルキレン基、アルケニレ
ン基、アルキニレン基、シクロアルキレン基、フ
エニレン基、アルアルキレン基又はこれらのアル
キル置換体である。 n=3の場合
[Formula] (In the formula, n is 1 to 3, and when n = 1, X is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms. n = In the case of 2, X is an alkylene group having 2 to 26 carbon atoms, an alkenylene group, an alkynylene group, a cycloalkylene group, a phenylene group, an aralkylene group, or an alkyl substituent thereof. In the case of n=3

【式】【formula】

【式】又 は【Formula】Also teeth

【式】 である。 n=1〜3について、R1は、すべて同じでも
異なつても良く、R1の炭素数のすべての和がn
〜60のアルキル基、アルケニル基、アリキニル
基、シクロアルキル基、アリール基、アルアルキ
ル基又は、これらのハロゲン、アルコキシ、アシ
ルオキシ、アルコキシカルボニル置換体である。) 〔〕
[Formula] is. For n=1 to 3, R 1 may be the same or different, and the sum of all the carbon numbers of R 1 is n
~60 alkyl groups, alkenyl groups, alikynyl groups, cycloalkyl groups, aryl groups, aralkyl groups, or halogen, alkoxy, acyloxy, or alkoxycarbonyl substituted products thereof. ) []

〔〕[]

(式中R4,R5,R6は水素原子又は、炭素数のす
べての和が1〜60のアルキル基、アルケニル基、
アルキニル基、シクロアルキル基アリール基又は
アルアルキル基である。ただしR4,R5,R6はの
うち少なくとも1つは炭素原子ではない。) 〔〕リン系エステル類
(In the formula, R 4 , R 5 , R 6 are hydrogen atoms, or alkyl groups or alkenyl groups having a total number of carbon atoms of 1 to 60,
They are an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group. However, at least one of R 4 , R 5 , and R 6 is not a carbon atom. ) [] Phosphorus esters

【式】【formula】

【式】 又は【formula】 or

【式】 (式中R7,R8,R9は水素原子又は、炭素数1〜
20のアルキル基、アルケニル基、アルキニル基、
アリール基、アルアルキル基又はこれらのハロゲ
ン、アルコキシ、アシルオキシ置換体である。た
だし、R7,R8,R9のうち少なくとも1つは水素
原子ではない。) 本発明において、希釈安定化剤として特に一般
式HOOC(−CH2−)nCOOH(但しm=2〜8)で
表わされる脂肪族二塩基酸のメチルエステルの少
なくとも1種を50〜100重量%含有するものを使
用するのが好ましい。又、過酸化物としてはハイ
ドロパーオキサイド、ケトンパーオキサイドが使
用され、好ましくはケトンパーオキサイドを使用
する。 通常耐火性粒状材料100重量部に対し、酸硬化
性樹脂を0.5〜3重量部、該過酸化物組成物を0.1
〜1重量部添加・混練し成型した砂型にガス状も
しくはエロゾル状の二酸化硫黄を吹き込み鋳型を
製造する。 耐火性粒状骨材としては石英質を主成分とする
硅砂他、ジルコンサンド、クロマイトサンド等が
使用されているが、これらにより本発明を限定す
るものではない。 酸硬化性樹脂としては、フラン樹脂、フエノー
ル樹脂、尿素樹脂、あるいはそれらの共重縮合物
乃至は混合物を使用するが、これらの酸硬化性樹
脂により本発明を限定するものではない。 更に詳細に実施例により本発明の利点を説明す
るが、以下の実施例により本発明の範囲を制限す
るものではない。 実施例1〜5及び比較例1〜3 硅砂1000重量部にフラン樹脂12重量部、メチル
エチルケトンパーオキサイドと表−1記載の希釈
安定化剤とを同量含有し、活性酸素量が10%であ
るメチルエチルケトンパーオキサイド組成物5重
量部を添加混練した混合物を50m/mφ×50m/
mHの型枠に充填した後、二酸化硫黄を1秒、圧
縮空気を5秒通気して鋳型を成型した。 成型した鋳型を750℃の炉内に5分間加熱し圧
縮強度を測定して加熱前後の強度により鋳型の崩
れやすさを測定した。結果を表−1に示す。
[Formula] (In the formula, R 7 , R 8 , R 9 are hydrogen atoms or have 1 to 1 carbon atoms.
20 alkyl groups, alkenyl groups, alkynyl groups,
An aryl group, an aralkyl group, or a halogen-, alkoxy-, or acyloxy-substituted product thereof. However, at least one of R 7 , R 8 , and R 9 is not a hydrogen atom. ) In the present invention, at least one methyl ester of an aliphatic dibasic acid represented by the general formula HOOC (-CH 2 -) n COOH (where m = 2 to 8) is used as a dilution stabilizer in an amount of 50 to 100% by weight. It is preferable to use one containing %. Further, as the peroxide, hydroperoxide and ketone peroxide are used, and ketone peroxide is preferably used. Normally, 0.5 to 3 parts by weight of the acid-curing resin and 0.1 part by weight of the peroxide composition per 100 parts by weight of the fire-resistant granular material.
Gaseous or aerosol sulfur dioxide is blown into the molded sand mold by adding ~1 part by weight and kneading to produce a mold. As the refractory granular aggregate, silica sand containing quartz as a main component, zircon sand, chromite sand, etc. are used, but the present invention is not limited to these. As the acid-curable resin, furan resin, phenol resin, urea resin, or a copolycondensate or mixture thereof is used, but the present invention is not limited to these acid-curable resins. The advantages of the present invention will be explained in more detail with reference to examples, but the scope of the present invention is not limited by the following examples. Examples 1 to 5 and Comparative Examples 1 to 3 1000 parts by weight of silica sand contains 12 parts by weight of furan resin, the same amount of methyl ethyl ketone peroxide and the dilution stabilizer listed in Table 1, and the amount of active oxygen is 10%. A mixture obtained by adding and kneading 5 parts by weight of the methyl ethyl ketone peroxide composition was heated to 50 m/mφ
After filling the mH mold, a mold was formed by passing sulfur dioxide for 1 second and compressed air for 5 seconds. The formed mold was heated in a furnace at 750°C for 5 minutes and its compressive strength was measured, and the ease with which the mold would collapse was determined by the strength before and after heating. The results are shown in Table-1.

【表】 実施例6〜7及び比較例4〜5 希釈安定化剤としてアジピン酸ジメチルとアジ
ピン酸ジイソプロピルの比率をかえたメチルエチ
ルケトンパーオキサイド組成物を使用して実施例
1と同様に試験した。結果を表−2に示す。
[Table] Examples 6 to 7 and Comparative Examples 4 to 5 Tests were conducted in the same manner as in Example 1 using methyl ethyl ketone peroxide compositions with different ratios of dimethyl adipate and diisopropyl adipate as dilution stabilizers. The results are shown in Table-2.

【表】【table】

Claims (1)

【特許請求の範囲】 1 耐火性粒状材料に酸硬化性樹脂と過酸化物組
成物を添加混練し成型した砂型に、ガス状又はエ
ロゾル状の二酸化硫黄を吹き込んで鋳型を製造す
る際に用いられる組成物であつて、過酸化物組成
物がハイドロパーオキサイド又はケトンパーオキ
サイド40〜60重量%と希釈安定化剤60〜40重量%
からなり、該希釈安定化剤が一般式HOOC(−
CH2−)oCOOH(但しn=1〜10)で表わされる脂
肪族二塩基酸のメチルエステルの少なくとも一種
を30〜100重量%含有するものである事を特徴と
する硬化性鋳型組成物。 2 過酸化物組成物の希釈安定化剤が一般式
HOOC(−CH2−)nCOOH(但しm=2〜8)で表
わされる脂肪族二塩基酸のメチルエステルの少な
くとも一種を50〜100重量%含有するものである
特許請求の範囲第1項記載の硬化性鋳型組成物。
[Scope of Claims] 1 Used when manufacturing a mold by blowing gaseous or aerosol sulfur dioxide into a sand mold made by adding and kneading an acid-curing resin and a peroxide composition to a fire-resistant granular material. a composition, wherein the peroxide composition comprises 40-60% by weight of a hydroperoxide or ketone peroxide and 60-40% by weight of a dilution stabilizer;
The dilution stabilizer has the general formula HOOC (-
A curable mold composition containing 30 to 100% by weight of at least one methyl ester of an aliphatic dibasic acid represented by CH2- ) oCOOH (where n=1 to 10 ). 2 The dilution stabilizer of the peroxide composition has the general formula
Claim 1, which contains 50 to 100% by weight of at least one methyl ester of an aliphatic dibasic acid represented by HOOC(-CH 2 -) n COOH (where m = 2 to 8) curable mold composition.
JP22935683A 1983-12-05 1983-12-05 Composition for curable casting mold Granted JPS60121036A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22935683A JPS60121036A (en) 1983-12-05 1983-12-05 Composition for curable casting mold

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22935683A JPS60121036A (en) 1983-12-05 1983-12-05 Composition for curable casting mold

Publications (2)

Publication Number Publication Date
JPS60121036A JPS60121036A (en) 1985-06-28
JPH0325255B2 true JPH0325255B2 (en) 1991-04-05

Family

ID=16890878

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22935683A Granted JPS60121036A (en) 1983-12-05 1983-12-05 Composition for curable casting mold

Country Status (1)

Country Link
JP (1) JPS60121036A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4629131B2 (en) * 2008-09-03 2011-02-09 大日本印刷株式会社 Image converter
JP4661829B2 (en) * 2007-06-14 2011-03-30 株式会社富士通ゼネラル Image data conversion device and camera device provided with the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58112627A (en) * 1981-12-21 1983-07-05 アクゾ・ナ−ムロ−ゼ・フエンノ−トシヤツプ Manufacture of mold or core

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58112627A (en) * 1981-12-21 1983-07-05 アクゾ・ナ−ムロ−ゼ・フエンノ−トシヤツプ Manufacture of mold or core

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4661829B2 (en) * 2007-06-14 2011-03-30 株式会社富士通ゼネラル Image data conversion device and camera device provided with the same
JP4629131B2 (en) * 2008-09-03 2011-02-09 大日本印刷株式会社 Image converter

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Publication number Publication date
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