JPS6252656B2 - - Google Patents
Info
- Publication number
- JPS6252656B2 JPS6252656B2 JP17249381A JP17249381A JPS6252656B2 JP S6252656 B2 JPS6252656 B2 JP S6252656B2 JP 17249381 A JP17249381 A JP 17249381A JP 17249381 A JP17249381 A JP 17249381A JP S6252656 B2 JPS6252656 B2 JP S6252656B2
- Authority
- JP
- Japan
- Prior art keywords
- mold
- organic binder
- parts
- strength
- resin
- 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
Links
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000004576 sand Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 241000960399 Benkara Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical class C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- -1 metaxylene sulfonic acid Chemical compound 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions 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
- B22C1/20—Compositions 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
- B22C1/22—Compositions 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
- B22C1/2233—Compositions 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
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
Description
この発明は、ホツトボツクス法に使用する鋳型
の造型に好適な鋳型用有機バインダー（以下単に
有機バインダーという）に関するものである。
従来、この種の有機バインダーとしてフエノー
ル樹脂、フラン樹脂及び尿素樹脂等を主体とする
ものが知られている。そして鋳型造型時には湿態
砂にこれら有機バインダーと酸性物質からなる硬
化剤とを併用して所定の温度に予め加温した金型
内にこれら混合物を吹き込むことによつて鋳型の
造型がなされる。
しかし、この酸硬化型有機バインダー、特にフ
エノール樹脂を主体とする有機バインダーを使用
して得られた鋳型は剛性が大きく急熱膨張率が大
きいという不具合を有する。この不具合により、
鋳型は造型時に割れやクラツクが発生しやすく、
また鋳バリやベーニングが生起しやすいという欠
点を有する。
上記熱膨張は、SiO2分の多い砂粒を使用した
時にさらに顕著に現われる。その理由は、砂粒が
溶湯の熱を受けて加熱された時に575℃附近で
SiO2がα−β変態を起して急激に膨張するため
と考えられている。
この熱膨張を仰制する手段として、ベンガラ
（酸化鉄）等のクツシヨン材を鋳物砂に添加する
方法等が知られているが、いずれも鋳型強度が低
下し、且つその効果も充分満足されず鋳物砂がコ
スト高となる欠点を有する。
そこでこの発明の目的は熱膨張率、とくに急熱
膨張率がきわめて小さい鋳型を得ることができる
安価なホツトボツクス用有機バインダーを提供す
ることである。
この発明の目的は特許請求の範囲に記載した事
項を実施することによつて達成される。
まず、この発明に使用するビスフエノールＡ精
製残査（SR酸）とは、硫酸または濃塩酸のよう
な触媒の存在下でフエノールとアセトンとを反応
させ、この反応生成物からビスフエノールＡを精
製する過程で副生した副生物で、種々の形態のビ
スフエノール類、クロマン化合物、未反応フエノ
ール等を含有している。
この発明の有機バインダーは、フエノール類
と、上記SR酸とを重量で、予め７：３〜２：８
好ましくは５：５〜３：７の割合に混合（フエノ
ール類混合物）し、これにアルカリ性触媒の存在
下でホルムアルヒデヒドを上記フエノール類混合
物100重量部（以下部は重量部を意味する）に対
して16〜78部を反応させることによつて得られ
る。得られた有機バインダーは、種々の物質で変
性された変性フエノール液状樹脂であり、複雑な
組成の混合物の形態をなしているレゾール樹脂で
ある。
このようにして得られた樹脂を使用して常法に
したがつて得られた鋳型は、従来の有機バインダ
ーのそれに比べて、温間の鋳型強度は若干劣る
が、放置強度に優れ、且つ著るしく小さい急熱膨
張率を有することが実験により確認された。又、
上記温間強度もベンカラ等を添加し、急熱膨張を
仰制して得られた鋳型に比べると優れている。
（実施例１、２及び比較例）
The present invention relates to an organic binder for molds (hereinafter simply referred to as organic binder) suitable for molding molds used in the hot box method. Conventionally, as this type of organic binder, those mainly composed of phenol resin, furan resin, urea resin, etc. are known. When making a mold, the organic binder and a curing agent made of an acidic substance are combined with the wet sand, and the mixture is blown into a mold that has been preheated to a predetermined temperature. However, molds obtained using this acid-curable organic binder, particularly an organic binder mainly composed of phenolic resin, have a problem of high rigidity and a high coefficient of rapid thermal expansion. Due to this defect,
Molds are prone to cracks and cracks during molding,
It also has the disadvantage of being prone to burrs and veining. The above thermal expansion becomes even more noticeable when sand grains with a large SiO2 content are used. The reason is that when the sand grains are heated by the heat of the molten metal, the temperature reaches around 575℃.
It is thought that this is because SiO 2 undergoes α-β transformation and expands rapidly. As a means to suppress this thermal expansion, methods of adding cushioning materials such as red iron oxide (iron oxide) to foundry sand are known, but in either case the strength of the mold decreases and the effect is not fully satisfactory. The disadvantage of using foundry sand is that it is expensive. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an inexpensive organic binder for hot boxes which can produce a mold having an extremely small coefficient of thermal expansion, particularly a coefficient of rapid thermal expansion. The objects of the invention are achieved by carrying out the matters described in the claims. First, the bisphenol A purified residue (SR acid) used in this invention is produced by reacting phenol with acetone in the presence of a catalyst such as sulfuric acid or concentrated hydrochloric acid, and purifying bisphenol A from this reaction product. It is a by-product produced during the process, and contains various forms of bisphenols, chroman compounds, unreacted phenols, etc. The organic binder of this invention is prepared by mixing phenols and the above-mentioned SR acid in a ratio of 7:3 to 2:8 by weight.
Preferably, the ratio is 5:5 to 3:7 (phenol mixture), and formalhydehyde is added to the above phenol mixture in the presence of an alkaline catalyst to 100 parts by weight (the following parts mean parts by weight). It is obtained by reacting 16 to 78 parts. The obtained organic binder is a modified phenol liquid resin modified with various substances, and is a resol resin in the form of a mixture with a complex composition. A mold obtained using the resin thus obtained according to a conventional method has slightly lower warm mold strength than that of a conventional organic binder, but has excellent standing strength and remarkable strength. It has been experimentally confirmed that this material has a significantly lower coefficient of rapid thermal expansion. or,
The above-mentioned warm strength is also superior to that of a mold obtained by adding Benkara or the like to suppress rapid thermal expansion. (Examples 1, 2 and comparative example)
【表】
撹拌機、コンデンサーおよび温度計を備えた容
量２のフラスコに、上表１の各配合物を、それ
ぞれの配合割合にて仕込み、1Nの苛性ソーダで
PHを8.0に調整したのち、徐々に加温して昇温
し、フラスコ内液の温度が90℃に達した時、この
温度を保持しつつ、１時間反応させた。その後減
圧下でフラスコ内の反応物を加温しつつ、更に反
応させ該反応物の温度が90℃に達した時、ただち
に水をフラスコ内に添加し、粘度を約200CPSに
調整して、各実施例１、２及び比較例に相当する
レゾール樹脂（有機バインダー）を得た。
更にこれら有機バインダーの性能をみる為に以
下の手法にてレジンサンドを調合した。
三栄銀砂６号（珪砂）５Kgと、60％メタキシレ
ンスルホン酸水溶液15gとをシンプソン式サンド
ミルで３分間混合し、ついで上記実施例１、２及
び３で得られた有機バインダーを個々に150g加
え、さらに３分間混合、混練して、３種のレジン
サンドを得た。
これらレジンサンドの物性に関する試験結果を
下表２に示す。[Table] Into a 2-capacity flask equipped with a stirrer, condenser, and thermometer, each compound in Table 1 above was charged at the respective mixing ratio, and mixed with 1N caustic soda.
After adjusting the pH to 8.0, the temperature was gradually increased, and when the temperature of the liquid in the flask reached 90°C, the reaction was continued for 1 hour while maintaining this temperature. Thereafter, the reactant in the flask was heated under reduced pressure and further reacted, and when the temperature of the reactant reached 90°C, water was immediately added to the flask to adjust the viscosity to about 200 CPS. Resol resins (organic binders) corresponding to Examples 1 and 2 and Comparative Examples were obtained. Furthermore, in order to examine the performance of these organic binders, resin sand was prepared using the following method. 5 kg of Sanei Silver Sand No. 6 (silica sand) and 15 g of a 60% metaxylene sulfonic acid aqueous solution were mixed for 3 minutes in a Simpson sand mill, and then 150 g of the organic binders obtained in Examples 1, 2, and 3 above were added individually. The mixture was further mixed and kneaded for 3 minutes to obtain three types of resin sand. Test results regarding the physical properties of these resin sands are shown in Table 2 below.
【表】
尚上表２で用いた試験方法を以下に記す。
温間強度：22.3×22.3×203.2mmのテストピースの
型温250℃金型脱型から30秒経過後の曲げ強さ
放置強度：金型脱型から１時間経過後の曲げ強さ
可使時間：型温250℃で30秒間焼成し、この鋳型
の強度が混練直後の鋳型に対して20％劣化する
のに要した時間
急熱膨張率：JACT試験法SM−７に準ずる。
以上、表２から明らかな如く、この発明は鋳型
強度を損うことなく、急熱膨張率の小さい有機バ
インダーを提供している。即ち本願の有機バイン
ダーを使用して得られた鋳型は従来の鋳型の割れ
や、クラツクの発生を防止し、鋳バリやベーニン
グの発生を防止しうる。
また本発明はホツトボツクス法に特に要求され
る可使時間をも従来品に比べて、損うことのない
有機バインダーを提供している。[Table] The test method used in Table 2 above is described below. Warm strength: Bending strength of a 22.3 x 22.3 x 203.2 mm test piece at a mold temperature of 250°C 30 seconds after demolding. Standing strength: Bending strength after 1 hour from mold demolding. Pot life. : Baking at a mold temperature of 250°C for 30 seconds, time required for the strength of this mold to deteriorate by 20% compared to the mold immediately after kneading Rapid thermal expansion coefficient: According to JACT test method SM-7. As is clear from Table 2, the present invention provides an organic binder with a low rapid thermal expansion coefficient without impairing mold strength. That is, the mold obtained using the organic binder of the present invention can prevent the cracking and cracking of conventional molds, and can also prevent the occurrence of burrs and vening. Furthermore, the present invention provides an organic binder that does not impair pot life, which is particularly required for the hot box method, compared to conventional products.
Claims (1)
混合比を７：３〜２：８に予め混合して得られた
フエノール類混合物と、該フエノール類混合物
100重量部に対し、ホルムアルデヒド類を16〜78
重量部配合し、アルカリ性触媒の存在下で反応さ
せて得られることを特徴とするホツトボツクス用
変性フエノール液状樹脂バインダー。1 A phenol mixture obtained by pre-mixing phenols and bisphenol A purified residue at a mixing ratio of 7:3 to 2:8, and the phenol mixture
16 to 78 parts of formaldehyde per 100 parts by weight
A modified phenol liquid resin binder for hot boxes, characterized in that it is obtained by blending parts by weight and reacting in the presence of an alkaline catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17249381A JPS5874240A (en) | 1981-10-27 | 1981-10-27 | Organic binder for mold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17249381A JPS5874240A (en) | 1981-10-27 | 1981-10-27 | Organic binder for mold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5874240A JPS5874240A (en) | 1983-05-04 |
| JPS6252656B2 true JPS6252656B2 (en) | 1987-11-06 |
Family
ID=15942994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17249381A Granted JPS5874240A (en) | 1981-10-27 | 1981-10-27 | Organic binder for mold |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5874240A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6452970A (en) * | 1987-08-25 | 1989-03-01 | Honda Motor Co Ltd | Key device |
| JPS6433135U (en) * | 1987-08-25 | 1989-03-01 | ||
| JPH0350170U (en) * | 1989-09-21 | 1991-05-16 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6092037A (en) * | 1983-10-24 | 1985-05-23 | Sumitomo Deyurezu Kk | Binder composition for molding sand |
| JPS60261639A (en) * | 1984-06-07 | 1985-12-24 | Dainippon Ink & Chem Inc | Self-curing binder composition for casting mold |
| WO2001046101A1 (en) * | 1999-12-22 | 2001-06-28 | Borden Chemical, Inc. | Stable bisphenolic compositions |
-
1981
- 1981-10-27 JP JP17249381A patent/JPS5874240A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6452970A (en) * | 1987-08-25 | 1989-03-01 | Honda Motor Co Ltd | Key device |
| JPS6433135U (en) * | 1987-08-25 | 1989-03-01 | ||
| JPH0350170U (en) * | 1989-09-21 | 1991-05-16 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5874240A (en) | 1983-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5474606A (en) | Heat curable foundry binder systems | |
| EP0363385B1 (en) | Modifiers for aqueous basic solutions of phenolic resole resins | |
| JPS6252656B2 (en) | ||
| JP7079093B2 (en) | Binder composition for mold molding | |
| EP0398463B1 (en) | Ester hardeners for phenolic resin binder systems | |
| US4529751A (en) | Resin coated sand for casting | |
| US4113916A (en) | Shell sand with improved thermal shock resistance | |
| JPS6096345A (en) | Production of casting mold | |
| US5036116A (en) | Ester hardeners for phenolic resin binder systems | |
| JPS6195735A (en) | Bonding agent of phenol resin for shell mold | |
| CN1325192C (en) | Acid-curable, refractory particulate material composition for forming mold | |
| JPS5942582B2 (en) | Foundry sand grains coated with resin | |
| JPS6056729B2 (en) | Manufacturing method of modified phenolic resin for shell mold | |
| JP3043812B2 (en) | Binders for thermosetting molds and their uses | |
| JP2504660B2 (en) | Organic ester-curable molding sand curing agent composition and method for producing mold using the same | |
| JP2542144B2 (en) | Binder composition for organic ester-curable foundry sand and method for producing mold using the same | |
| JPS6015648B2 (en) | Manufacturing method of resin for shell mold | |
| US2876512A (en) | Shell molding | |
| JPH0146219B2 (en) | ||
| JPS598466B2 (en) | Manufacturing method of resin-coated sand for foundries | |
| JPH07116771A (en) | Production of casting mold for casting | |
| JP2006021232A (en) | Acid-curing composition of refractoriness granular material | |
| JPS6213097B2 (en) | ||
| JPH04135035A (en) | Binder composition for molding sand | |
| JPS598465B2 (en) | Manufacturing method of resin-coated sand for foundries |