JPS63188442A - Resin coating sand grain for shell mold - Google Patents
Resin coating sand grain for shell moldInfo
- Publication number
- JPS63188442A JPS63188442A JP2067987A JP2067987A JPS63188442A JP S63188442 A JPS63188442 A JP S63188442A JP 2067987 A JP2067987 A JP 2067987A JP 2067987 A JP2067987 A JP 2067987A JP S63188442 A JPS63188442 A JP S63188442A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- sand grains
- coated sand
- phenol resin
- aminophenol
- 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
- 239000004576 sand Substances 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title abstract 3
- 238000000576 coating method Methods 0.000 title abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000005011 phenolic resin Substances 0.000 claims abstract description 37
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 15
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 7
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 27
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 229920003987 resole Polymers 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 28
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004898 kneading Methods 0.000 abstract description 13
- 238000005452 bending Methods 0.000 abstract description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- WFNVGXBEWXBZPL-UHFFFAOYSA-N 3,5-diaminophenol Chemical compound NC1=CC(N)=CC(O)=C1 WFNVGXBEWXBZPL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000004312 hexamethylene tetramine Substances 0.000 abstract description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 65
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 methylol groups Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000011134 resol-type phenolic resin Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000010112 shell-mould casting Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000003110 molding sand Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Mold Materials And Core Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、シェルモールド用樹脂被覆砂粒に関するもの
で、特に混練時、鋳型造型時または注湯時の悪臭ガスの
発生の少ない低臭気なシェルモールド用樹脂被覆砂粒に
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to resin-coated sand grains for shell molds, and particularly to low-odor shells that generate less malodorous gas during kneading, mold making, or pouring. This invention relates to resin-coated sand grains for molds.
［従来の技術］
従来、混練時、鋳型造型時または、注湯時の悪臭ガス発
生の少ない低臭気なシェルモールド用樹脂被覆砂粒とし
て、アンモニアを主体とした固形アンモニアレゾール型
フェノール樹脂を用いたもの（特公昭５２−１２６５８
号公報）、アンモニアレゾール型フェノール樹脂にレゾ
ルシン、カテコールなと、または１価および２価金属の
塩化物、硝酸塩などの塩類および有機酸から選ばれた硬
化促進剤を添加したもの（特公昭５１−２７４０６号公
報）、アミン触媒とアルカリ金属触媒を併用した固形ア
ンモニアレゾール型フェノール樹脂、 を用いたもの
（特公昭５７−３４４７号公報）または固形アンモニア
レゾール型フェノール樹脂に尿素を添加したもの（特開
昭６１−１７２６４８号公報）などがある。[Prior Art] Conventionally, a solid ammonia resol type phenolic resin containing ammonia as a main component has been used as resin-coated sand grains for low-odor shell molds that generate little foul-smelling gas during kneading, mold making, or pouring. (Tokuko Sho 52-12658
Publication No. 1), an ammonia resol type phenolic resin with a curing accelerator selected from resorcinol, catechol, salts such as chlorides and nitrates of monovalent and divalent metals, and organic acids (Japanese Patent Publication No. 1973- 27406), a solid ammonia resol type phenol resin using a combination of an amine catalyst and an alkali metal catalyst (Japanese Patent Publication No. 57-3447), or a solid ammonia resol type phenol resin with urea added (Japanese Patent Publication No. 3447/1983). Publication No. 172648/1982).
［発明が解決しようとする問題点］
しかし上記のシェルモールド用樹脂被覆砂粒は、悪臭ガ
スの発生は少なく、低臭気であるが、鋳型の常温強度な
どや、鋳型造型時に必要な温間強度（硬化速度）が不十
分であり、一層の改善が望まれていた。[Problems to be Solved by the Invention] However, although the resin-coated sand grains for shell molding described above generate less malodorous gas and have a low odor, they do not have sufficient room-temperature strength of the mold or warm strength required during mold making. Curing speed) was insufficient, and further improvement was desired.
特に上記レゾルシン、１価および２価の金属塩、または
有機酸の添加は硬化速度が改善されるが、常温強度が低
くなるという問題点があり、またカテコールは硬化速度
、常温強度は満足がいくものの樹脂被覆砂粒の融着点が
低くなる欠点があり、樹脂被覆砂粒がブロッキングを起
しやすくなる問題点がある。アミン触媒とアルカリ金属
触媒を併用することにより、メチロール基を増加させ硬
化速度は改善できるが、常温強度の低下および樹脂のブ
ロッキング性の悪化などの問題点がある。一方尿素の添
加は、常温強度は改善できるが、樹脂被覆砂粒の融着点
が低下し、また吸湿による樹脂被覆砂粒のブロッキング
を起しやすくなる問題点がある。In particular, the addition of the above-mentioned resorcinol, monovalent and divalent metal salts, or organic acids improves the curing speed, but there is a problem in that the strength at room temperature decreases, while the curing speed and strength at room temperature of catechol are satisfactory. However, there is a drawback that the melting point of the resin-coated sand grains is low, and there is a problem that the resin-coated sand grains tend to cause blocking. By using an amine catalyst and an alkali metal catalyst in combination, the curing speed can be improved by increasing the number of methylol groups, but there are problems such as a decrease in room temperature strength and a deterioration in the blocking property of the resin. On the other hand, the addition of urea can improve the strength at room temperature, but has the problem of lowering the fusion point of the resin-coated sand grains and making the resin-coated sand grains more likely to block due to moisture absorption.
本発明は、上記問題点を克服するものであり、低臭気で
、硬化速度が速く、かつ常温強度に優れたシェルモール
ド用樹脂被覆砂粒を提供することを目的とする。The present invention has been made to overcome the above-mentioned problems, and aims to provide resin-coated sand grains for shell molds that have low odor, a fast curing speed, and excellent room-temperature strength.
［問題点を解決するための手段］
本発明のシェルモールド用樹脂被覆砂粒は、鋳物砂と該
鋳物砂の表面に被覆された熱硬化性フェノール樹脂結合
剤とからなり、該熱硬化性フェノール樹脂結合剤にモノ
アミノフェノール、およびジアミノフェノール（以下ア
ミノフェノール類という）の少なくとも１種を含むこと
を特徴とす ′る。[Means for Solving the Problems] The resin-coated sand grains for shell molds of the present invention consist of foundry sand and a thermosetting phenolic resin binder coated on the surface of the foundry sand, and the thermosetting phenolic resin It is characterized in that the binder contains at least one of monoaminophenol and diaminophenol (hereinafter referred to as aminophenols).
本発明のシェルモールド用樹脂被覆砂粒に使用する鋳物
砂は、造型前は流動性に富み、注湯時に鋳込、みに耐え
得る耐熱性を持つ、通常用いられているものを用いるこ
とができる。鋳物砂の種類としては、珪砂、オリビンサ
ンド、ジルコンサンド、溶融石英粒などが適しており、
その粒径は７０μ〜１０００μ程度がよい。The molding sand used for the resin-coated sand grains for the shell mold of the present invention can be any commonly used molding sand that is highly fluid before molding and has heat resistance that can withstand pouring and molding during pouring. . Suitable types of foundry sand include silica sand, olivine sand, zircon sand, and fused quartz grains.
The particle size is preferably about 70μ to 1000μ.
本発明のシェルモールド用樹脂被覆砂粒に使用する、鋳
物砂の表面に被覆する熱硬化性フェノール樹脂結合剤は
フェノール１モルに対してホルムアルデヒドを１モル以
上使用し、アルカリ触媒の存在下で反応させた熱硬化性
フェノール樹脂結合剤であり、アンモニア、またはアミ
ン化合物などのアミン系触媒からなる固形アンモニアレ
ゾール型フェノール樹脂、およびアミン触媒とアルカリ
金属触媒との併用触媒からなる固形アンモニアレゾール
型フェノール樹脂、およびアルカリ金属触媒からなる固
形レゾール型フェノール樹脂、および上記レゾール型フ
ェノール樹脂に、フェノール１モルに対してホルムアル
デヒドを１モル未満使用し、酸性触媒の存在下で反応さ
せたノボラック型フェノール樹脂を含有する固形レゾー
ル型フェノール樹脂である。The thermosetting phenolic resin binder used for the resin-coated sand grains for shell molds of the present invention and coated on the surface of the foundry sand contains at least 1 mol of formaldehyde per 1 mol of phenol, and is reacted in the presence of an alkali catalyst. A solid ammonia aresol type phenol resin which is a thermosetting phenolic resin binder and is made of ammonia or an amine catalyst such as an amine compound; and a solid resol-type phenolic resin consisting of an alkali metal catalyst, and a novolac-type phenolic resin in which less than 1 mol of formaldehyde is used per 1 mol of phenol and reacted in the presence of an acidic catalyst. It is a solid resol type phenolic resin.
ここにおいて使用するフェノールとは、フェノール、メ
タクレゾール、パラクレゾール、ビスフェノールＡ１キ
シレノールなどである。ホルムアルデヒドとしてはホル
マリン、バラホルムアルデヒドなどが使用できる。アミ
ン系触媒のアミン化合物とは、モノメチルアミン、モノ
エチルアミン、ジメチルアミン、エタノールアミンなど
の第１級、第２級アミンである。アルカリ金属触媒は、
ナトリウム、カリウムなどのアルカリ金属の水酸化物ま
たは酸化物、バリウム、カルシウムなどのアルカリ土類
金属の水酸化物または酸化物である。ノボラック型フェ
ノール樹脂に使用する酸性触媒は、塩酸、硫酸、シュウ
酸などの酸であり、また酢酸亜鉛のような２価金属の酢
酸塩などが使用できる。The phenol used here includes phenol, meta-cresol, para-cresol, bisphenol A1 xylenol, and the like. As the formaldehyde, formalin, rose formaldehyde, etc. can be used. The amine compounds of the amine catalyst are primary and secondary amines such as monomethylamine, monoethylamine, dimethylamine, and ethanolamine. Alkali metal catalysts are
These are hydroxides or oxides of alkali metals such as sodium and potassium, and hydroxides or oxides of alkaline earth metals such as barium and calcium. The acidic catalyst used in the novolac type phenolic resin is an acid such as hydrochloric acid, sulfuric acid, or oxalic acid, and an acetate of a divalent metal such as zinc acetate can be used.
本発明のシェルモールド用樹脂被覆砂粒に使用するアミ
ンフェノール類としては、オルソアミノフェノール、メ
タアミノフェノール、バラアミノフェノール、２．３−
ジアミノフェノール、２．４−ジアミノフェノール、３
．５−ジアミノフェノールが使用でき、特にメタアミノ
フェノール、３．５−ジアミノフェノールが望ましい。The amine phenols used in the resin-coated sand grains for shell molds of the present invention include ortho-aminophenol, meta-aminophenol, para-aminophenol, 2.3-
Diaminophenol, 2,4-diaminophenol, 3
．． 5-diaminophenol can be used, and meta-aminophenol and 3,5-diaminophenol are particularly preferred.
このアミノフェノール類は、熱硬化性フェノール樹脂の
反応終了後、減圧脱水終了後、または、混練時のいずれ
の時期に添加してもよい。このアミノフェノール類の添
加割合は、熱硬化性フェノール樹脂ｉｏｏ重量部に対し
て、１．０〜５．０重量部であり、好ましくは２．０〜
４，０重量部である。１．０重量部未満では、アミノフ
ェノール類添加の効果がなく、また５、０重量部を超え
るとコストアップになるので好ましくない。The aminophenols may be added at any time after the reaction of the thermosetting phenol resin is completed, after the vacuum dehydration is completed, or during kneading. The addition ratio of the aminophenols is 1.0 to 5.0 parts by weight, preferably 2.0 to 5.0 parts by weight, based on ioo parts by weight of the thermosetting phenol resin.
It is 4.0 parts by weight. If it is less than 1.0 parts by weight, the addition of aminophenols will not be effective, and if it exceeds 5.0 parts by weight, it will increase the cost, which is not preferable.
次に、本発明のシェルモールド用樹脂被覆砂粒の製造方
法の概要を説明する。Next, the outline of the method for producing resin-coated sand grains for shell molds of the present invention will be explained.
■反応容器中にフェノール１モルとホルムアルデヒド１
〜３モルを仕込み、アルカリ触媒を添加する。そして５
０〜１００℃に加熱して約１〜３時開綿合反応を行う。■1 mole of phenol and 1 mole of formaldehyde in the reaction vessel
Charge ~3 mol and add alkaline catalyst. and 5
The mixture is heated to 0 to 100° C. for about 1 to 3 hours to carry out the cotton-opening reaction.
（ここで必要によってアミノフェノール類を添加する。(At this point, add aminophenols if necessary.
）次に減圧下、温度１００℃以下で締金物中の水及び未
反応物を除去し、黄色ないし黄褐色の高粘性の透明樹脂
が得られる。（この時点でアミノフェノール類を添加す
る場合もある。）反応容器からこの樹脂を取出し急冷す
ると固形の熱硬化性フェノール樹脂が得られる。) Next, water and unreacted substances in the clamped material are removed under reduced pressure at a temperature of 100° C. or lower to obtain a yellow to yellow-brown, highly viscous transparent resin. (Aminophenols may be added at this point.) The resin is removed from the reaction vessel and rapidly cooled to obtain a solid thermosetting phenol resin.
上記の縮合反応終了時又は、減圧脱水終了時に周知の方
法で合成したノボラック型フェノール樹脂を添加するこ
とが出来る。A novolac type phenol resin synthesized by a known method can be added at the end of the above condensation reaction or at the end of vacuum dehydration.
■次に、鋳物砂を１２０〜１６０℃に加熱し、混練器に
投入する。その後上記の熱硬化性フェノール樹脂結合剤
を、鋳物砂１００重量部に対して２〜３Ｍ量部添加する
。（ここでアミンフェノール類、およびノボラック型フ
ェノール樹脂を添加する場合もある。）３０秒混練のの
ち、鋳物砂１００重量部に対して、１．０〜１．５重量
部の冷却をするための水を添加し、鋳物砂が崩壊するま
で混練を続ける。次いで鋳物砂１００重量部に対し、０
．０３〜０．１重量部のステアリン酸カルシウムを加え
ることにより、本発明のシェルモールド用樹脂被覆砂粒
が得られる。(2) Next, the foundry sand is heated to 120 to 160°C and put into a kneader. Thereafter, the above-mentioned thermosetting phenolic resin binder is added in an amount of 2 to 3 M parts per 100 parts by weight of foundry sand. (Amine phenols and novolac type phenolic resin may be added here.) After kneading for 30 seconds, 1.0 to 1.5 parts by weight of the foundry sand for cooling is added to 100 parts by weight of foundry sand. Add water and continue mixing until the foundry sand disintegrates. Next, to 100 parts by weight of foundry sand, 0
．． By adding 0.3 to 0.1 parts by weight of calcium stearate, the resin-coated sand grains for shell molds of the present invention can be obtained.
［作用］
鋳型の常温強度は、混線時の樹脂結合剤の流動性はもち
ろん、鋳型造型時の樹脂結合剤の流動性に大きく影響さ
れる。[Function] The room-temperature strength of a mold is greatly influenced by the fluidity of the resin binder at the time of cross-contact, as well as the fluidity of the resin binder at the time of mold making.
アミンフェノール類を添加することにより鋳物砂に被覆
された樹脂結合剤の流動性が良好になり、鋳型の常温強
度の向上が得られる。また樹脂結合剤の硬化段階におい
て、アミノフェノール類が架橋触媒作用及び自ら架橋剤
として鋳型の硬化を促進し、優れた鋳型の温間強度をも
たらす。Addition of amine phenols improves the fluidity of the resin binder coated on the foundry sand, and improves the room temperature strength of the mold. In addition, in the curing step of the resin binder, aminophenols act as a crosslinking catalyst and themselves act as crosslinking agents to promote the curing of the mold, resulting in excellent warm strength of the mold.
［実施例］ 以下実施例により本発明を説明する。[Example] The present invention will be explained below with reference to Examples.
（樹脂結合剤の製造方法）
（１）攪拌機、コンデンサ、温度計を備えた三ツロフラ
スコにフェノール１０００ｇ、８５％バラホルムアルデ
ヒド６２０ｇ、２０％水酸化ナトリウム水溶液８ｇを秤
量し、攪拌しながらウォータバスで加熱し、９０℃で４
５分間反応させた後５０℃まで冷却、２５％アンモニア
水１８０ｇを攪拌しながら加える。７０℃で白濁するま
で反応を行ったのち、−６５〜−７０ｃｍＨｇの減圧下
で濃縮を行い内温が９８℃になった時フラスコから排出
し、冷却固化したのち、破砕して６〜２０メツシユの固
形アンモニアレゾール型フェノール樹脂（Ａ）を得た。(Production method of resin binder) (1) Weigh out 1000 g of phenol, 620 g of 85% paroxysmaldehyde, and 8 g of 20% aqueous sodium hydroxide solution into a Mitsuro flask equipped with a stirrer, condenser, and thermometer, and heat in a water bath while stirring. 4 at 90℃
After reacting for 5 minutes, the mixture was cooled to 50° C., and 180 g of 25% ammonia water was added with stirring. After the reaction was carried out at 70°C until it became cloudy, it was concentrated under reduced pressure of -65 to -70 cmHg, and when the internal temperature reached 98°C, it was discharged from the flask, cooled and solidified, and then crushed into 6 to 20 mesh pieces. A solid ammonia aresol type phenol resin (A) was obtained.
（２） （１） と同様−６５〜−７０ｃｍ１（Ｈ
の減圧下で濃縮を行い、内湯が９８℃になった時、常圧
にもどし、すばやくメタアミノフェノールを４２ｇｆｉ
加溶解させた後、フラスコから排出し、冷却固化後破砕
して６〜２０メツシユのメタアミノフェノ−ル含有固形
アンモニアレゾール型フェノール樹脂（Ｂ）を得た。(2) Same as (1) -65 to -70 cm1 (H
Concentration was carried out under reduced pressure, and when the indoor bath temperature reached 98℃, the pressure was returned to normal and 42gfi of meta-aminophenol was quickly extracted.
After dissolving, the mixture was discharged from the flask, cooled and solidified, and then crushed to obtain 6 to 20 meshes of meta-aminophenol-containing solid ammonia resol type phenol resin (B).
（３）攪拌機、コンデンサ、温度計を備えた三ツロフラ
スコにフェノール１０００ｇ、８５％バラホルムアルデ
ヒド５２６ｇを秤量し、５０℃を超えない様に冷却しな
がら２５％アンモニア水を１５０ｇ添加する。次に５０
℃で白濁するまで反応させ、さらに２時間反応を行った
のち、−６５〜−７０ｃｍＨｇの減圧下で濃縮を行い内
温が９８℃になった時フラスコから排出し、冷却固化し
たのち、破砕して６〜２０メツシユの固形アンモニアレ
ゾール型フェノール樹脂（Ｃ）を得た。(3) Weigh out 1000 g of phenol and 526 g of 85% formaldehyde into a Mitsuro flask equipped with a stirrer, condenser, and thermometer, and add 150 g of 25% ammonia water while cooling to a temperature not exceeding 50°C. then 50
The reaction was carried out at ℃ until it became cloudy, and after further reaction for 2 hours, it was concentrated under reduced pressure of -65 to -70 cmHg, and when the internal temperature reached 98 ℃, it was discharged from the flask, and after cooling and solidifying, it was crushed. 6 to 20 meshes of solid ammonia aresol type phenol resin (C) were obtained.
（４） （３）と同様に反応させ−６５〜−７０ｃｍ
Ｈｇの減圧下で濃縮を行い内温が９８℃になった時、常
圧にもどし、すばやくメタアミノフェノールを３８ｇ添
加溶解させたのち、フラスコから排出し、冷却固化後破
砕して６〜２０メツシユのメタアミノフェノール含有固
形アンモニアレゾール型フェノール樹脂（Ｄ）を得た。(4) React in the same manner as in (3) -65 to -70 cm
Concentration was carried out under reduced pressure of Hg, and when the internal temperature reached 98°C, the pressure was returned to normal, and 38 g of meta-aminophenol was quickly added and dissolved, then discharged from the flask, cooled and solidified, and then crushed into 6 to 20 mesh pieces. A meta-aminophenol-containing solid ammonia aresol type phenol resin (D) was obtained.
（５）攪拌機、コンデンサ、温度計を備えた三ツロフラ
スコに、フェノール１０００ｇ、パラホルムアルデヒド
１２５ｇ、３７％ホルマリン２５０ｇを秤量し、攪拌し
ながら７０℃まで昇温してパラホルムアルデヒドを溶解
し、５０％酢酸亜鉛水溶液１０ｇを添加したのち徐々に
昇温して４時間還流反応を行った。(5) Weigh out 1,000 g of phenol, 125 g of paraformaldehyde, and 250 g of 37% formalin into a Mitsuro flask equipped with a stirrer, condenser, and thermometer, raise the temperature to 70°C while stirring, dissolve the paraformaldehyde, and dissolve 50% acetic acid. After adding 10 g of a zinc aqueous solution, the temperature was gradually raised to perform a reflux reaction for 4 hours.
その後−６５〜−７０ｃｍＨｇの減圧下、濃縮を行い内
温が１７０℃に達した時、常圧にもどし、エチレンビス
ステアロアミド２０ｇを添加溶解させ、フラスコから排
出し、冷却固化後破砕し６〜２０メツシユのノボラック
型フェノール樹脂（Ｅ）を得た。Thereafter, it was concentrated under a reduced pressure of -65 to -70 cmHg, and when the internal temperature reached 170°C, it was returned to normal pressure, and 20 g of ethylene bisstearamide was added and dissolved, discharged from the flask, cooled and solidified, and then crushed. ~20 meshes of novolac type phenolic resin (E) were obtained.
〈実施例１〉
スピードミキサーＮ５Ｃ−２型（遠州鉄工■製）に１６
０℃に加熱したフーカ砂１０ｋｇを投入し、砂温か１５
０℃になった時固形アンモニアレゾール型フェノール樹
脂（Ａ）を１９４ｇとメタアミノフェノール６ｇを添加
し、３０秒間混練したのち、冷却水を１５０ｇ仕込み、
被覆砂粒が崩壊するまで混練したのち、１０ｇのステア
リン酸カルシウムを添加し、さらに２０秒間混練し、排
砂してエアレーションを行いシェルモールド用樹脂被覆
砂粒を得た。該砂粒の特性を表に示す。<Example 1> Speed mixer N5C-2 type (manufactured by Enshu Tekko) 16
Pour 10kg of fuka sand heated to 0℃, and let the sand temperature rise to 15℃.
When the temperature reached 0°C, 194 g of solid ammonia aresol type phenol resin (A) and 6 g of meta-aminophenol were added, and after kneading for 30 seconds, 150 g of cooling water was added.
After kneading the coated sand grains until they disintegrated, 10 g of calcium stearate was added, kneading was further continued for 20 seconds, and the sand was removed for aeration to obtain resin-coated sand grains for shell molding. The properties of the sand grains are shown in the table.
〈実施例２〉
メタアミノフェノールをオルソアミノフェノールに変え
たこと以外は実施例１と同様の方法で樹脂被覆砂粒を得
た。該砂粒の特性を表に示す。<Example 2> Resin-coated sand grains were obtained in the same manner as in Example 1 except that meta-aminophenol was changed to ortho-aminophenol. The properties of the sand grains are shown in the table.
〈実施例３〉
固形アンモニアレゾール型フェノール樹脂（Ａ）を１９
４ｇとメタアミノフェノール６ｇをメタアミノフェノー
ル含有固形アンモニアレゾール型フェノール樹脂（Ｂ）
を２００ｇにかえた以外は実施例１と同様の方法で樹脂
被覆砂粒を得た。<Example 3> Solid ammonia aresol type phenol resin (A)
4g and 6g of meta-aminophenol to solid ammonia aresol type phenol resin (B) containing meta-aminophenol.
Resin-coated sand grains were obtained in the same manner as in Example 1, except that the amount was changed to 200 g.
該砂粒の特性を表に示す。The properties of the sand grains are shown in the table.
〈実施例４〉
固形アンモニアレゾール型フェノール樹脂（Ａ）を固形
アンモニアレゾール型フェノール樹脂（Ｃ）にかえた以
外は実施例１と同様の方法で樹脂被覆砂粒を得た。該砂
粒の特性を表に示す。<Example 4> Resin-coated sand grains were obtained in the same manner as in Example 1, except that the solid ammonia resol type phenol resin (A) was replaced with the solid ammonia resol type phenol resin (C). The properties of the sand grains are shown in the table.
〈実施例５〉
メタアミノフェノール含有固形アンモニアレゾール樹脂
（Ｂ）を、メタアミノフェノール含有固形アンモニアレ
ゾール樹脂（Ｄ）にかえた以外は実施例３と同様の方法
で樹脂被覆砂粒を得た。<Example 5> Resin-coated sand grains were obtained in the same manner as in Example 3, except that the meta-aminophenol-containing solid ammonia resol resin (B) was replaced with the meta-aminophenol-containing solid ammonia resol resin (D).
該砂粒の特性を表に示す。The properties of the sand grains are shown in the table.
〈実施例６〉
スピードミキサーＮ５Ｃ−２型（遠州鉄工■製）に１６
０℃に加熱したフーカ砂１０ｋｇを投入し、砂温が１５
０℃になった時固形アンモニアレゾール型フェノール樹
脂（Ａ）１５５ｇとノボラック型フェノール樹脂（Ｅ）
３９ｇおよびメタアミノフェノール６ｇの混合物を添加
し、３０秒間混練したのち、冷却水１５０ｇを仕込み、
被覆砂粒が崩壊するまで混練したのち１０ｇのステアリ
ン酸カルシウムを添加し、さらに２０秒間混練し、エア
レーションを行い樹脂被覆砂粒を得た。<Example 6> Speed mixer N5C-2 type (manufactured by Enshu Tekko) 16
Add 10kg of fuka sand heated to 0℃, and the sand temperature becomes 15℃.
155g of ammonia aresol type phenolic resin (A) and novolac type phenolic resin (E) which are solid when the temperature reaches 0℃
After adding a mixture of 39 g and 6 g of meta-aminophenol and kneading for 30 seconds, 150 g of cooling water was added.
After kneading the coated sand grains until they disintegrated, 10 g of calcium stearate was added, kneading was further continued for 20 seconds, and aeration was performed to obtain resin-coated sand grains.
該砂粒の特性を表に示す。The properties of the sand grains are shown in the table.
〈実施例７〉
メタアミノフェノールをオルソアミノフェノールにかえ
た以外は実施例６と同様の方法で樹脂被覆砂粒を得た。<Example 7> Resin-coated sand grains were obtained in the same manner as in Example 6 except that meta-aminophenol was replaced with ortho-aminophenol.
該砂粒の特性を表に示す。The properties of the sand grains are shown in the table.
く比較例１〉
固形アンモニアレゾール型フェノール樹脂（Ａ）１９４
ｇとメタアミノフェノール６ｇを、固形アンモニアレゾ
ール型フェノール樹脂（Ａ）２００ｇにかえた以外は実
施例１と同様の方法で樹脂被覆砂粒を得た。該砂粒の特
性を表に示す。Comparative Example 1> Solid ammonia aresol type phenolic resin (A) 194
Resin-coated sand grains were obtained in the same manner as in Example 1, except that 200 g of solid ammonia resol type phenol resin (A) was used instead of 6 g of meta-aminophenol. The properties of the sand grains are shown in the table.
〈比較例２〉
メタアミノフェノールをカテコールにかえた以外は実施
例１と同様の方法で樹脂被覆砂粒を得た６該砂粒の特性
を表に示す。<Comparative Example 2> Resin-coated sand grains were obtained in the same manner as in Example 1 except that meta-aminophenol was replaced with catechol.The properties of the six sand grains are shown in the table.
く比較例３〉
固形アンモニアレゾール型フェノール樹脂（Ａ）を固形
アンモニアレゾール型フェノール樹脂（Ｃ）にかえた以
外は比較例１と同様の方法で樹脂被覆砂粒を得た。該砂
粒の特性を表に示す。Comparative Example 3 Resin-coated sand grains were obtained in the same manner as in Comparative Example 1, except that the solid ammonia resol type phenolic resin (A) was replaced with the solid ammonia resol type phenol resin (C). The properties of the sand grains are shown in the table.
く比較例４〉
固形アンモニアレゾール型フェノール樹脂（Ａ）１５５
ｇとノボラック型フェノール樹脂３９ｇおよびメタアミ
ノフェノール６ｇの混合物を固形アンモニアレゾール型
フェノール樹脂ｔ６ｏｇとノボラック型フェノール樹脂
４０ｇの混合物にかえた以外は実施例６と同様の方法で
樹脂被覆砂粒を得た。該砂粒の特性を表に示す。Comparative Example 4> Solid ammonia aresol type phenolic resin (A) 155
Resin-coated sand grains were obtained in the same manner as in Example 6, except that the mixture of g, 39 g of novolac type phenol resin, and 6 g of meta-aminophenol was replaced with a mixture of solid ammonia resol type phenol resin t6og and 40 g of novolac type phenol resin. The properties of the sand grains are shown in the table.
表より明らかに、各実施例の樹脂被覆砂粒は、融着点の
低下をもたらすことなく、常温曲げ強度、および温間曲
げ強度が比較例のそれに比べ、それぞれの樹脂結合剤共
に向上している。It is clear from the table that the resin-coated sand grains of each example have improved room-temperature bending strength and warm bending strength with each resin binder compared to those of the comparative example, without causing a decrease in the fusion point. .
なお、常温曲げ強度はＪＡＣＴ試験法５Ｍ−１、温間曲
げ強度はＪＡＣＴ試験法５Ｍ−５、融着点はＪＡＣＴ試
験法Ｃ−１に準拠して行った。Note that the room temperature bending strength was measured in accordance with JACT test method 5M-1, the warm bending strength was measured in accordance with JACT test method 5M-5, and the fusion point was measured in accordance with JACT test method C-1.
［発明の効果コ
以上説明したように本発明に従えば、硬化剤としてヘキ
サメチレンテトラミンや、ホルムアルデヒド源を用いる
必要性がないので、混練時、鋳型造型時および注湯時に
アンモニアやホルムアルデヒドの発生が少なく、低臭気
のシェルモールド用樹脂被覆砂粒が得られる。ざらにア
ミノフェノール類の作用により、混練時はもちろん鋳型
造型時の樹脂結合剤の流動性が良く、常温曲げ強度が高
く、樹脂結合剤の使用量を低減でき、経済性の面でも有
効である。[Effects of the Invention] As explained above, according to the present invention, there is no need to use hexamethylenetetramine as a hardening agent or a formaldehyde source, so ammonia and formaldehyde are not generated during kneading, mold making, and pouring. Resin-coated sand grains for shell molding with low odor can be obtained. Due to the action of the aminophenols, the resin binder has good fluidity not only during kneading but also during mold making, has high bending strength at room temperature, reduces the amount of resin binder used, and is also effective in terms of economic efficiency. .
また、アミノフェノール類が架橋触媒作用及び自ら架橋
剤として硬化を促進するため、温間曲げ強度が高く鋳型
造型時間の短縮が可能となる。さらにカテコールのよう
に融着点を低下させることがないので、樹脂被覆砂粒の
ブロッキングを起すことがなく、流動性に富んだ樹脂被
覆砂粒が得られるという効果がある。In addition, since aminophenols have a crosslinking catalytic effect and act as crosslinking agents themselves to promote curing, warm bending strength is high and mold making time can be shortened. Furthermore, unlike catechol, it does not lower the melting point, so there is no blocking of the resin-coated sand grains, and resin-coated sand grains with high fluidity can be obtained.
特許出願人 アイシン化工株式会社 代表者栗木清二Patent applicant: Aisin Kako Co., Ltd. Representative Seiji Kuriki
Claims (5)
フェノール樹脂結合剤とからなり、該熱硬化性フェノー
ル樹脂結合剤にモノアミノフェノールおよびジアミノフ
ェノールの少なくとも１種を含むことを特徴とするシェ
ルモールド用樹脂被覆砂粒。(1) Consisting of foundry sand and a thermosetting phenol resin binder coated on the surface of the foundry sand, the thermosetting phenol resin binder containing at least one of monoaminophenol and diaminophenol. Features resin-coated sand grains for shell molds.
１級アミンおよび第２級アミンから選ばれた少なくとも
１種を主たる触媒とした固形アンモニアレゾール型フェ
ノール樹脂である特許請求の範囲第１項記載のシェルモ
ールド用樹脂被覆砂粒。(2) Claim 1, wherein the thermosetting phenolic resin binder is a solid ammonia resol type phenol resin containing at least one selected from ammonia, primary amines, and secondary amines as a main catalyst. resin-coated sand grains for shell molds.
ール樹脂を含有するアンモニア、第１級アミンおよび第
２級アミンから選ばれた少なくとも１種を主たる触媒と
した固形アンモニアレゾール型樹脂である特許請求の範
囲第１項または第２項記載のシェルモールド用樹脂被覆
砂粒。(3) The thermosetting phenolic resin is a solid ammonia resol type resin containing a novolac type phenolic resin and using at least one selected from ammonia, a primary amine, and a secondary amine as a main catalyst. Resin-coated sand grains for shell molds according to item 1 or 2.
ェノールの添加割合が熱硬化性フェノール樹脂結合剤１
００重量部に対して、１．０〜５．０重量部である特許
請求の範囲第１、２または３項記載のシェルモールド用
樹脂被覆砂粒。(4) The addition ratio of monoaminophenol or/and diaminophenol is 1 to 1 in the thermosetting phenol resin binder.
The resin-coated sand grains for shell molds according to claim 1, 2 or 3, wherein the amount is 1.0 to 5.0 parts by weight based on 00 parts by weight.
である特許請求の範囲第１、２、３または４項記載のシ
ェルモールド用樹脂被覆砂 粒。(5) The resin-coated sand grains for shell mold according to claim 1, 2, 3 or 4, wherein the monoaminophenol is meta-aminophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020679A JPH0824992B2 (en) | 1987-01-30 | 1987-01-30 | Resin-coated sand grains for shell mold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020679A JPH0824992B2 (en) | 1987-01-30 | 1987-01-30 | Resin-coated sand grains for shell mold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63188442A true JPS63188442A (en) | 1988-08-04 |
| JPH0824992B2 JPH0824992B2 (en) | 1996-03-13 |
Family
ID=12033865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62020679A Expired - Lifetime JPH0824992B2 (en) | 1987-01-30 | 1987-01-30 | Resin-coated sand grains for shell mold |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824992B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1864728A4 (en) * | 2005-02-16 | 2008-10-15 | Asahi Organic Chem Ind | Resin-coated sand for multilayered casting mold |
| CN104226888A (en) * | 2014-08-29 | 2014-12-24 | 吴江市液铸液压件铸造有限公司 | Easily-scattered precoated sand and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684143A (en) * | 1979-12-12 | 1981-07-09 | Kao Corp | Manufacture of casting mold |
-
1987
- 1987-01-30 JP JP62020679A patent/JPH0824992B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684143A (en) * | 1979-12-12 | 1981-07-09 | Kao Corp | Manufacture of casting mold |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1864728A4 (en) * | 2005-02-16 | 2008-10-15 | Asahi Organic Chem Ind | Resin-coated sand for multilayered casting mold |
| CN104226888A (en) * | 2014-08-29 | 2014-12-24 | 吴江市液铸液压件铸造有限公司 | Easily-scattered precoated sand and preparation method thereof |
| CN104226888B (en) * | 2014-08-29 | 2016-07-06 | 吴江市液铸液压件铸造有限公司 | A kind of easy defeated and dispersed precoated sand and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0824992B2 (en) | 1996-03-13 |
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