JP3090294B2 - Sand core manufacturing method - Google Patents
Sand core manufacturing methodInfo
- Publication number
- JP3090294B2 JP3090294B2 JP04239427A JP23942792A JP3090294B2 JP 3090294 B2 JP3090294 B2 JP 3090294B2 JP 04239427 A JP04239427 A JP 04239427A JP 23942792 A JP23942792 A JP 23942792A JP 3090294 B2 JP3090294 B2 JP 3090294B2
- Authority
- JP
- Japan
- Prior art keywords
- sand core
- sand
- core prototype
- coating
- prototype
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011248 coating agent Substances 0.000 claims description 56
- 238000000576 coating method Methods 0.000 claims description 27
- 239000004576 sand Substances 0.000 claims description 26
- 229920001187 thermosetting polymer Polymers 0.000 claims description 26
- 229920003170 water-soluble synthetic polymer Polymers 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 124
- 238000000034 method Methods 0.000 description 21
- 238000005266 casting Methods 0.000 description 14
- 229920002125 Sokalan® Polymers 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000004584 polyacrylic acid Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004512 die casting Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920006186 water-soluble synthetic resin Polymers 0.000 description 1
- 239000012866 water-soluble synthetic resin Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F1/00—Cylinders; Cylinder heads
- F02F1/02—Cylinders; Cylinder heads having cooling means
- F02F1/10—Cylinders; Cylinder heads having cooling means for liquid cooling
- F02F2001/106—Cylinders; Cylinder heads having cooling means for liquid cooling using a closed deck, i.e. the water jacket is not open at the block top face
Landscapes
- Mold Materials And Core Materials (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Casting Devices For Molds (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は,例えば,クローズドデ
ッキタイプの自動車用エンジン等,アンダーカット部分
を有する鋳造品の高圧ダイカスト鋳造時に用いる耐圧性
および優れたコーティング性を有する砂中子の製造方法
に関するものである。さらに詳しくは,シェルモールド
法で造型した砂中子原型を非熱硬化性水溶性合成高分子
で処理することにより,同一コーティング剤を1回だけ
で厚くコーティングでき,しかも,高圧鋳造用にも適し
た砂中子の製造方法に関するものである。ここで,優れ
たコーティング性とは,砂中子原型にコーティング剤を
コーティングする際に,コーティング剤が,薄い液状で
砂中子原型の内部に広がった状態で深く浸み込まずに,
または,砂中子原型の表面からはじかれずに,砂中子原
型の表面層のみにかつ全面に,所定の厚さで均一に,か
つ,確実容易に強固に形成され,それが剥がれないよう
にコーティングされることであり,鋳造時の高圧の鋳込
圧力に充分に耐え得ることである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a sand core having excellent pressure resistance and excellent coating properties for use in high pressure die casting of a casting having an undercut portion, such as a closed deck type automobile engine. It is about. More specifically, by treating a sand core prototype molded by the shell mold method with a non-thermosetting water-soluble synthetic polymer, the same coating agent can be coated thickly only once, and it is also suitable for high-pressure casting. The present invention relates to a method for producing a sand core. Here, excellent coating properties mean that when coating the coating on the sand core prototype, the coating agent does not penetrate deeply in a thin liquid state while spreading inside the sand core prototype.
Alternatively, it is formed firmly and easily with a predetermined thickness uniformly and securely on the surface layer of the sand core prototype without being repelled from the surface of the sand core prototype. That is, it must be able to withstand the high casting pressure during casting.
【0002】[0002]
【従来の技術】従来より,例えば,クローズドデッキタ
イプの自動車用エンジンブロックやその他のアンダーカ
ット部分を有するアルミニウム合金やマグネシウム合金
等の鋳造品をダイカストで鋳造して製造する場合,崩壊
性砂中子を用いてダイカスト鋳造することが行われてい
る。そして,崩壊性砂中子を得る場合,まず,砂を所望
の形に固め,次に,その固めた砂中子原型の表面にコー
ティング剤を塗布し,高圧下での溶湯鋳込時には砂中子
が破損したり,溶湯が砂中子内に侵入しないようにし,
鋳造後には,ほとんど力を加えずに砂中子を崩壊させて
容易に取出せるようにし,かつ,砂が隅々まで充分に取
出せるようにすることが試みられている。勿論,その場
合,砂中子原型の成分,砂の固め方,コーティング剤の
成分,コーティングの仕方等,従来よりいろいろ試みら
れているが,充分に満足し得るものは得られていないの
が現状である。2. Description of the Related Art Conventionally, for example, when a closed deck type automobile engine block or other castings such as aluminum alloys and magnesium alloys having an undercut portion are manufactured by die casting, a collapsible sand core is used. Die-casting is performed using the same. In order to obtain a collapsible sand core, first, the sand is hardened to a desired shape, and then a coating agent is applied to the surface of the hardened sand core prototype. To prevent the breakage of the core or the molten metal from entering the sand core.
After casting, attempts have been made to disintegrate the sand core with little force so that it can be easily taken out and that the sand can be taken out to every corner. Of course, in this case, various attempts have been made on the components of the sand core prototype, the method of hardening the sand, the components of the coating agent, the coating method, etc., but no satisfactory one has been obtained. It is.
【0003】その中で,砂を固めて砂中子原型を得る方
法として,ハードックス法,ウォームボックス法,
シェルモールド法,コールドボックス法等がある。
ハードックス法としては,例えば,特公昭64−989
8号公報に記載されている技術が知られている。そし
て,この方法においては,砂中子原型は砂,酸硬化性樹
脂および酸化剤を主成分とする結合剤からなっており,
二酸化硫黄によって硬化される。[0003] Among them, the hardening method, warm box method,
There are a shell mold method, a cold box method and the like.
As the Hardox method, for example, Japanese Patent Publication No. 64-989
The technique described in Japanese Patent Publication No. 8 is known. In this method, the sand core prototype is composed of a binder mainly composed of sand, an acid-curable resin and an oxidizing agent.
Cured by sulfur dioxide.
【0004】[0004]
【発明が解決しようとする課題】前記ハードックス法に
おいては,所望の形状に造型した砂を硬化して砂中子原
型を得る場合,二酸化硫黄すなわち亜硫酸ガスを使用し
て硬化する。したがって,亜硫酸ガスを使用するため,
作業環境が悪く,日本の工場では,人体に悪影響を与え
るようなガスの使用は好まれない。また,仮に亜硫酸ガ
スを使用するとしても,人体に悪影響を与えず,作業環
境も悪化させないようにするためには,その為の付属設
備の設置が大変であり,また,その設置,運転のために
法規制も受ける。In the above-mentioned Hardox method, when sand formed into a desired shape is hardened to obtain a sand core prototype, it is hardened using sulfur dioxide, that is, sulfurous acid gas. Therefore, because sulfur dioxide is used,
The working environment is poor, and Japanese factories do not like the use of gases that can harm the human body. Also, even if sulfurous acid gas is used, it is very difficult to install ancillary equipment to prevent adverse effects on the human body and the working environment from deteriorating. Are also subject to laws and regulations.
【0005】そのため,本発明者は,酸化剤と亜硫酸ガ
スの代りに結合剤を使用するシェルモールド法の良さを
見直すこととした。シェルモールド法では,砂と結合剤
の混合物を固めて砂中子原型を得るのに亜硫酸ガスを使
用するのではなく,予めフェノールレジン等の石炭酸系
合成樹脂をコーティングしたレジンコーテッドサンド
(RCS)を,砂中子原型造型用の金型内に圧縮空気で
吹込んで加熱硬化させて造型する。しかし,この場合,
前記ハードックス法ではかなり良好に行われていたコー
ティング剤と同一のコーティング剤を砂中子原型に塗布
しても,コーティング剤が濡れずにはじかれてうまくい
かなかった。[0005] Therefore, the present inventor has reviewed the merits of the shell mold method using a binder instead of the oxidizing agent and the sulfurous acid gas. In the shell mold method, instead of using a sulfur dioxide gas to solidify a mixture of sand and a binder to obtain a sand core prototype, a resin coated sand (RCS) previously coated with a phenolic synthetic resin such as phenolic resin is used. Then, it is blown with compressed air into a mold for sand core prototype molding, and is heated and cured to form a mold. However, in this case,
Even if the same coating agent that had been performed fairly well in the above-mentioned Hardox method was applied to the sand core prototype, the coating agent was repelled without getting wet, which did not work.
【0006】[0006]
【課題を解決するための手段】本発明においては、RC
Sを用いて砂中子原型を造型する工程と、この砂中子原
型を非熱硬化性水溶性合成高分子で処理する工程と、こ
の非熱硬化性水溶性合成高分子で処理した砂中子原型を
乾燥する工程と、この乾燥した砂中子原型の表面に粉末
状の耐火物を主成分とする中性水分散体からなるスラリ
状のコ−ティング剤をコ−ティングする工程と、このコ
−ティングして得た砂中子を乾燥させる工程によって優
れたコ−ティングを有する砂中子を得る。なお、砂中子
を処理する非熱硬化性水溶性合成高分子は、その分子構
造がアクリル基、メタアクリル基、ビニル基、エ−テル
基、無水マレイン酸の1つまたは2つ以上の主鎖から構
成され、側鎖に水溶性置換基を持ったものが大多数を占
める。水溶性置換基としては、スルホン酸塩基、カルボ
キシル基とその無水物、水酸基、アミド基、アミノ基、
エ−テル基、ピロリドン基、エチレンイミン基、水溶性
グリシジルエ−テル基等がある。非熱硬化性水溶性合成
高分子の具体例としては、ポリアクリル酸、ポリビニル
アルコ−ル、ポリエチレングリコ−ル、ポリプロピレン
グリコ−ル、ポリアクリルアミド、ポリビニルピロリド
ン、水溶性アルキッド、ポリビニルエ−テル、マレイン
酸共重合体等が挙げられる。また、砂中子原型を非熱硬
化性水溶性合成高分子で処理する場合は、例えば、ポリ
アクリル酸水溶液のような非熱硬化性水溶性合成高分子
溶液中に浸漬したり、非熱硬化性水溶性合成高分子溶液
を砂中子原型の表面に刷毛塗りしたり、吹付けたりす
る。According to the present invention, RC
A step of molding a sand core prototype using S, a step of treating the sand core prototype with a non-thermosetting water-soluble synthetic polymer, and a step of treating the sand core prototype with the non-thermosetting water-soluble synthetic polymer. A step of drying the child prototype; and a step of coating a slurry-like coating agent comprising a neutral aqueous dispersion containing a powdered refractory as a main component on the surface of the dried sand core prototype, By drying the sand core obtained by this coating, a sand core having an excellent coating is obtained. The non-thermosetting water-soluble synthetic polymer for treating the sand core has a molecular structure of one or more of an acrylic group, a methacrylic group, a vinyl group, an ether group, and maleic anhydride. Most of them have a water-soluble substituent on the side chain. Examples of the water-soluble substituent include a sulfonic acid group, a carboxyl group and its anhydride, a hydroxyl group, an amide group, an amino group,
Examples include ether groups, pyrrolidone groups, ethyleneimine groups, and water-soluble glycidyl ether groups. Specific examples of the non-thermosetting water-soluble synthetic polymer include polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyacrylamide, polyvinylpyrrolidone, water-soluble alkyd, polyvinyl ether, and maleic. Acid copolymers and the like can be mentioned. When the sand core prototype is treated with a non-thermosetting water-soluble synthetic polymer, for example, it may be immersed in a non-thermosetting water-soluble synthetic polymer solution such as a polyacrylic acid aqueous solution, or may be non-thermosetting. A water-soluble synthetic polymer solution is brushed or sprayed on the surface of the sand core prototype.
【0007】[0007]
【作用】本発明においては,まず,例えば,前記したよ
うにRCSを用いて砂中子原型を造型した後,その砂中
子原型をポリアクリル酸水溶液等の非熱硬化性水溶性合
成高分子水溶液中に浸漬するなどして砂中子原型の内部
に非熱硬化性水溶性合成高分子を浸み込ませ,次いで,
この砂中子原型を乾燥する。次に,非熱硬化性水溶性合
成高分子で処理した後乾燥して得たこの砂中子原型の表
面に,粉末状の耐火物を主成分とする中性水分散体から
なるスラリ状のコーティング剤をコーティングする。こ
の場合,造型した砂中子原型を,コーティングする前
に,例えばポリアクリル酸水溶液等の非熱硬化性水溶性
合成高分子水溶液の中に浸漬すれば,砂中子原型の表層
部や中に非熱硬化性水溶性合成高分子が付着したり浸み
込んだりする。この砂中子原型を浸漬槽から引き上げた
後,80〜200℃で数分〜2時間乾燥させると砂中子
原型の表層部に非熱硬化性水溶性合成高分子の皮膜が均
一に形成し,砂中子原型表面の空隙(毛管)が目詰めさ
れ,かつ砂中子原型表面が親水化される。According to the present invention, first, a sand core prototype is formed by using RCS as described above, and then the sand core prototype is subjected to a non-thermosetting water-soluble synthetic polymer such as an aqueous solution of polyacrylic acid. Infiltrate the non-thermosetting water-soluble synthetic polymer into the sand core prototype by immersing it in an aqueous solution, and then
The sand core prototype is dried. Next, after treating with a non-thermosetting water-soluble synthetic polymer and drying, the surface of this sand core prototype is coated with a slurry-like neutral water dispersion mainly composed of powdered refractory. Coating a coating agent. In this case, if the molded sand core prototype is immersed in a non-thermosetting water-soluble synthetic polymer aqueous solution such as a polyacrylic acid aqueous solution before coating, the sand core prototype becomes in the surface layer or inside of the sand core prototype. Non-thermosetting water-soluble synthetic polymer adheres or penetrates. When the sand core prototype is pulled out of the dipping tank and dried at 80 to 200 ° C. for several minutes to 2 hours, a non-thermosetting water-soluble synthetic polymer film is uniformly formed on the surface of the sand core prototype. The voids (capillaries) on the surface of the sand core prototype are clogged, and the surface of the sand core prototype is hydrophilized.
【0008】一方,このような非熱硬化性水溶性合成高
分子処理および乾燥を経て得た砂中子原型に,粉末状の
耐火物を主成分とする中性水分散体からなるスラリ状の
コーティング剤を塗布すれば,該砂中子原型の表面およ
び表面近くに形成した非熱硬化性水溶性合成高分子の皮
膜により砂中子原型表面の空隙が目詰めされ,かつ砂中
子原型表面が均一に親水化されることにより,コーティ
ング剤が該砂中子原型の表面ではじかれることなく,該
砂中子原型の表面に厚くコーティングできる。その後こ
れを乾燥すれば,所望の厚さの均質なコーティング層が
形成される。On the other hand, a sand core prototype obtained through such a non-thermosetting water-soluble synthetic polymer treatment and drying is added to a slurry-like neutral water dispersion mainly composed of a powdery refractory. When a coating agent is applied, the voids on the surface of the sand core prototype are clogged by the non-thermosetting water-soluble synthetic polymer film formed on and near the surface of the sand core prototype, and the surface of the sand core prototype is Is uniformly hydrophilized, so that the coating agent can be thickly coated on the surface of the sand core prototype without being repelled by the surface of the sand core prototype. Thereafter, when this is dried, a homogeneous coating layer having a desired thickness is formed.
【0009】このようにすれば,シェルモールド法で
も,砂中子原型を固めることができ,かつ,砂中子原型
の表面にコーティング剤を所望の状態で確実容易にコー
ティングすることができる。そして,この発明によって
得られたコーティング砂中子を用いれば,高圧ダイカス
トのように高圧下での溶湯鋳込時に砂中子が破損したり
クラックが入ったりすることもなく,溶湯が砂中子内に
侵入することもない。In this way, even with the shell mold method, the sand core prototype can be hardened, and the surface of the sand core prototype can be coated easily and reliably with a coating agent in a desired state. When the coated sand core obtained by the present invention is used, the sand core is not broken or cracked at the time of casting the molten metal under high pressure as in the case of high-pressure die casting, and the molten metal is used as the sand core. No intrusion.
【0010】[0010]
【実施例】砂中子原型を製造するときは,まず,フェノ
ールレジン等の石炭酸系合成樹脂を砂にコーティングし
たレジンコーテッドサンド(RCS)を用意する。RC
Sは混練温度,フェノール樹脂等の石炭酸系合成樹脂の
性状からコールド法,セミホット法,ドライホット法で
製造されるが,生産性,安定性,コストの面からドライ
ホット法が好ましい。すなわち,130〜160℃に加
熱された砂に固形樹脂をミキサーで溶融コーティングし
たのち,ノボラック樹脂の場合は硬化剤のヘキサミン水
溶液,レゾール樹脂の場合は水のみを投入して,水の蒸
発潜熱およびエアレーションによって急冷しながら砂粒
同志の固着が少なくなった時点でステアリン酸カルシウ
ム等のワックスを分散させて乾態易流動性のRCSを得
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS To manufacture a sand core prototype, first, a resin-coated sand (RCS) in which phenolic resin such as phenolic resin is coated on sand is prepared. RC
S is produced by a cold method, a semi-hot method, or a dry hot method based on the kneading temperature and properties of a phenolic resin such as a phenol resin, but the dry hot method is preferred in terms of productivity, stability, and cost. That is, after a solid resin is melt-coated on sand heated to 130 to 160 ° C. by a mixer, a hexamine aqueous solution as a curing agent for novolak resin, and only water for resol resin, are charged to evaporate latent heat of water and A wax such as calcium stearate is dispersed when the adhesion of the sand particles is reduced while rapidly cooling by aeration, thereby obtaining a dry, free-flowing RCS.
【0011】なお,砂は,硅砂,ジルコンサンド,クロ
マイトサンド,セラビーズ等あるいはそれらの再生砂を
用いる。このRCSを,所定の砂中子形状のキャビティ
を有する金型内に加圧空気とともに吹込み,いわゆる,
シェルモールド法と呼ばれている方法で砂中子原型を成
型した。この場合,中子成型用の金型の加熱温度は例え
ば200〜300℃,好ましくは,230〜270℃程
度とし,30秒〜2分程度加熱して,砂中子原型を所定
の強度に硬化させた。例えば,抗折力20〜50kgの
砂中子原型を得た。As the sand, silica sand, zircon sand, chromite sand, cerabeads or the like or their regenerated sand is used. The RCS is blown together with pressurized air into a mold having a predetermined sand core-shaped cavity.
A sand core prototype was molded by a method called a shell mold method. In this case, the heating temperature of the mold for core molding is, for example, about 200 to 300 ° C., preferably about 230 to 270 ° C., and heating is performed for about 30 seconds to 2 minutes to harden the sand core prototype to a predetermined strength. I let it. For example, a sand core prototype having a bending strength of 20 to 50 kg was obtained.
【0012】次に,このようにして成型した砂中子原型
を,非熱硬化性水溶性合成高分子の水溶液で処理する。
この非熱硬化性水溶性合成高分子としては,ポリアクリ
ル酸,ポリビニルアルコール,ポリアクリルアミド等が
挙げられる。これらの非熱硬化性水溶性合成高分子の水
溶液中に砂中子原型を浸漬し,砂中子原型に吸収させた
後,加熱乾燥させる。水溶液の濃度は稀釈倍率200倍
以内である。稀釈倍率が200倍を越えるとコーティン
グ厚みが薄く,処理効果がなくなる。浸漬時間は,処理
液の濃度および砂中子原型と処理液との親和性によって
も異なるが,0.5秒の短時間から5分程度である。Next, the sand core prototype thus formed is treated with an aqueous solution of a non-thermosetting water-soluble synthetic polymer.
Examples of the non-thermosetting water-soluble synthetic polymer include polyacrylic acid, polyvinyl alcohol, and polyacrylamide. The sand core prototype is immersed in an aqueous solution of these non-thermosetting water-soluble synthetic polymers, absorbed by the sand core prototype, and then dried by heating. The concentration of the aqueous solution is within 200 times the dilution ratio. If the dilution ratio exceeds 200 times, the coating thickness is too thin and the treatment effect is lost. The immersion time varies depending on the concentration of the treatment liquid and the affinity between the sand core prototype and the treatment liquid, but is as short as 0.5 seconds to about 5 minutes.
【0013】もし,砂中子原型が処理液に濡れにくい場
合は,予め砂中子原型をメタノール等の親水性有機溶媒
に短時間浸漬した後に処理液に浸漬するか,処理液に上
記親水性有機溶媒を砂中子原型が処理液に濡れるように
なるまで混合してから処理する。浸漬処理した砂中子原
型の加熱乾燥は,温度が高いほど時間が短くてすみ,目
安として120℃で30分程度である。If the sand core prototype is difficult to get wet with the processing solution, the sand core prototype is immersed in a hydrophilic organic solvent such as methanol for a short time before being immersed in the processing solution, or The organic solvent is mixed until the sand core prototype becomes wet with the processing solution before processing. Heat drying of the immersion-treated sand core prototype requires a shorter time as the temperature is higher, and is approximately 30 minutes at 120 ° C. as a guide.
【0014】つぎに,上記のように処理された砂中子原
型の表面にコーティング剤をコーティングする。この場
合,この砂中子原型をコーティング剤中に浸漬してもよ
いし,この砂中子原型の表面にコーティング剤を刷毛塗
りしたり吹付けたりしてもよい。コーティング剤は,微
粉末シリカと微粉末アルミナを主成分とし,少量のコロ
イドシリカを加えた固形分50〜90重量%のスラリと
した。固形分が50重量%以下ではコーティング層の厚
みが薄くなり,90重量%以上になるとスラリを撹拌す
るのが極めて困難となる。なお,このコーティング剤の
pHを7.0±1.0に維持していなければ,撹拌下で
も沈殿,凝固することがある。Next, the surface of the sand core prototype treated as described above is coated with a coating agent. In this case, the sand core prototype may be dipped in the coating agent, or the surface of the sand core prototype may be brushed or sprayed with the coating agent. The coating agent was a slurry having a solid content of 50 to 90% by weight containing fine powder silica and fine powder alumina as main components and a small amount of colloidal silica. If the solid content is less than 50% by weight, the thickness of the coating layer becomes thin, and if it exceeds 90% by weight, it becomes extremely difficult to stir the slurry. If the pH of the coating agent is not maintained at 7.0 ± 1.0, precipitation and solidification may occur even under stirring.
【0015】なお,コーティング剤としては,他のコー
ティング剤を用いることもできる。例えば,グラファイ
ト,マイカ,ヒューズドシリカ,アルミナ,マグネシ
ア,カーボンブラックおよびジルコン粉末等の無機耐火
性材料約30〜80重量%と,コロイドシリカ,アルミ
ナゾル,粘土およびアミン処理ベントナイト等の無機結
合剤約1〜25重量%と,水からなるものを用いてもよ
い。この場合,より好ましいものは,ヒューズドシリカ
とコロイドシリカである。なお,これに約10容量%の
メタノールとカオリンを加えても良い。As the coating agent, other coating agents can be used. For example, about 30 to 80% by weight of an inorganic refractory material such as graphite, mica, fused silica, alumina, magnesia, carbon black and zircon powder, and about 1 inorganic binder such as colloidal silica, alumina sol, clay and amine-treated bentonite. It is also possible to use water consisting of up to 25% by weight and water. In this case, more preferred are fused silica and colloidal silica. In addition, about 10% by volume of methanol and kaolin may be added.
【0016】前記コーティング剤中に,非熱硬化性水溶
性合成高分子処理次いで加熱乾燥された砂中子原型を数
秒間浸漬し,その後,加熱乾燥を行う。乾燥条件は,1
20℃,10分程度である。コーティングの厚みは,非
熱硬化性水溶性合成高分子処理を行わない場合には砂中
子原型からはじかれてほとんど塗れないのに対して,充
分に厚く,砂中子原型への浸透も少なく,しかも,塗膜
は堅固である。コーティング層は1層でもよいが,製品
とコーティング層との離型性を良くするため,2層の方
がより好ましい。2層目のコーティング層を形成するた
めのコーティング剤としては,例えば,3%水溶性フェ
ノール樹脂溶液1リットルに対し,雲母粉500グラ
ム,湿潤剤としてドデシルベンゼンスルホン酸ナトリウ
ム10グラム,消泡剤としてオクチルアルコール1グラ
ムをよく撹拌混合したもの等を用いることができる。こ
のコーティングは前記第1層コーティングを終えた砂中
子原型を第2層コーティング剤中に浸漬したり,該砂中
子原型の表面に第2層コーティング剤を刷毛塗りしたり
吹付けたりした後,乾燥して形成する。A non-thermosetting water-soluble synthetic polymer treatment and a heat-dried sand core prototype are immersed in the coating agent for several seconds, and then heat-dried. Drying condition is 1
20 ° C., about 10 minutes. If the coating is not treated with a non-thermosetting water-soluble synthetic polymer, the coating is repelled from the sand core prototype and hardly painted, but is sufficiently thick and has little penetration into the sand core prototype. Moreover, the coating film is firm. One coating layer may be used, but two layers are more preferable in order to improve the releasability between the product and the coating layer. As a coating agent for forming the second coating layer, for example, 1 g of a 3% aqueous phenol resin solution, 500 g of mica powder, 10 g of sodium dodecylbenzenesulfonate as a wetting agent, and a defoaming agent One obtained by well stirring and mixing 1 gram of octyl alcohol can be used. This coating is performed by immersing the sand core prototype after the first layer coating in the second layer coating agent, or brushing or spraying the second layer coating agent on the surface of the sand core prototype. , Formed by drying.
【0017】さらに詳しい実施例として,実験例をつぎ
に示す。 (実験例1〜4,および比較例) フラタリ砂100部に対して2部のフェノール樹脂(硬
化剤ヘキサミンを含む)をコーティングしたRCSを用
いて,重量約2Kgのエンジンブロック用砂中子原型を
シェルモールド法で複数個造型した。造型条件は金型温
度250℃,吹込み圧0.8Kg/cm2 ,加熱時間9
0秒であった。1日放置した後の砂中子原型の抗折力は
38Kgであった。このうちの1個は,後記する非熱硬
化性水溶性合成高分子処理を何ら行わずに,本実験例と
同一のコーティングを行ったので,比較例として後記す
る表1に示す。An experimental example will be described below as a more detailed example. (Experimental Examples 1-4, and Comparative Example) Using a RCS obtained by coating 2 parts of a phenolic resin (including a hardener hexamine) with 100 parts of flat sand, a sand core prototype for an engine block weighing about 2 kg was used. A plurality of pieces were formed by a shell mold method. Molding conditions were: mold temperature 250 ° C., blowing pressure 0.8 kg / cm 2, heating time 9
It was 0 seconds. The bending strength of the sand core prototype after standing for one day was 38 kg. One of them was coated with the same coating as that of the present experimental example without any treatment of a non-thermosetting water-soluble synthetic polymer described later, and is shown in Table 1 below as a comparative example.
【0018】ポリアクリル酸(重合度:3000)1部
に水を各々9部,49部,99部,199部混合して,
稀釈倍率10,50,100,200倍の水溶液をそれ
ぞれ調製した。この水溶液に砂中子原型を1〜2秒間浸
漬した後,120℃の循環式熱風加熱炉で30分間乾燥
した。(実験例1〜4)9 parts, 49 parts, 99 parts and 199 parts of water were mixed with 1 part of polyacrylic acid (degree of polymerization: 3000),
Aqueous solutions having a dilution ratio of 10, 50, 100, and 200 times were prepared. The sand core prototype was immersed in this aqueous solution for 1 to 2 seconds, and then dried in a circulating hot air heating furnace at 120 ° C. for 30 minutes. (Experimental Examples 1-4)
【0019】これらポリアクリル酸処理を行わなかった
ものとそれぞれ濃度が異なった液によってポリアクリル
酸処理された砂中子原型を同一のコーティング剤に1〜
2秒間浸漬した後,120℃の循環式熱風加熱炉で10
分間乾燥した。コーティング剤の組成は,微粉末シリカ
50部と微粉末アルミナ30部にコロイドシリカ3部を
水20部に懸濁させたもので,pHは7.2に調製され
たものであった。比較例のものおよび実験例4のもの
は,コーティングが不良ないしやや良程度であった。こ
れにより,ポリアクリル酸稀釈倍率は150〜200倍
以下が良いことが推定された。The non-polyacrylic acid-treated sand core prototypes treated with polyacrylic acid by liquids having different concentrations from each other were applied to the same coating agent in the same coating agent.
After immersion for 2 seconds, 10 minutes in a circulating hot air heating furnace at 120 ° C.
Dried for minutes. The composition of the coating agent was prepared by suspending 3 parts of colloidal silica in 20 parts of water in 50 parts of fine powder silica and 30 parts of fine powder alumina, and the pH was adjusted to 7.2. In the case of the comparative example and the case of the experimental example 4, the coating was defective or slightly good. Thus, it was estimated that the dilution ratio of polyacrylic acid was preferably 150 to 200 times or less.
【0020】前記の第1層コーティングを終えた後,次
に第2層目のコーティングを行った。第2層のコーティ
ング剤としては,3%水溶性フェノール樹脂溶液1リッ
トルに対し,雲母粉500グラム,湿潤剤としてドデシ
ルベンゼンスルホン酸ナトリウム10グラム,消泡剤と
してオクチルアルコール1グラムをよく撹拌混合したも
のを用いた。すなわち,前記第1層コーティングを済ま
せた砂中子原型をこの第2層コーティング剤中に1〜2
秒間浸漬した後,120℃の循環式熱風加熱炉で10分
間乾燥した。After finishing the first layer coating, a second layer coating was next performed. As a coating agent for the second layer, 500 g of mica powder, 10 g of sodium dodecylbenzenesulfonate as a wetting agent, and 1 g of octyl alcohol as a defoaming agent were thoroughly mixed with 1 liter of a 3% aqueous phenol resin solution. Was used. That is, the sand core prototype having been coated with the first layer is added to the second layer coating agent by 1 to 2 times.
After immersion for 2 seconds, it was dried in a circulating hot air heating furnace at 120 ° C. for 10 minutes.
【0021】[0021]
【表1】 [Table 1]
【0022】以上のようにして得た砂中子を金型にセッ
トし,アルミニウム合金ADC10を鋳造圧力600k
g/cm2 ,湯口速度200mm/sec,注湯温度7
60℃の条件下で高圧鋳造した。鋳造後に350℃で3
0分加熱処理したのち通常のコアノックアウトマシンで
砂落しを行ったところ,実験例1〜3の場合には中子砂
は完全に除去され,優れた鋳造品が得られた。実験例4
の場合には中子砂の除去はやや良であったが,比較例の
場合には溶湯が砂中子原型に差込んでおり中子砂の除去
は不良であった。まとめて,結果を表1に示す。The sand core obtained as described above is set in a mold, and an aluminum alloy ADC10 is cast at a casting pressure of 600 k.
g / cm 2 , Gate speed 200 mm / sec, Pouring temperature 7
High pressure casting was performed at 60 ° C. 3 at 350 ° C after casting
After the heat treatment for 0 minutes, sand removal was performed with a normal core knockout machine. In the case of Experimental Examples 1 to 3, the core sand was completely removed, and an excellent cast product was obtained. Experimental example 4
In the case of (1), the removal of the core sand was slightly good, but in the case of the comparative example, the molten metal was inserted into the sand core prototype and the removal of the core sand was poor. The results are summarized in Table 1.
【0023】(実験例5〜8,および比較例)実験例1
〜4のポリアクリル酸の代りにポリビニルアルコール
(重合度:2000)を使用し,それ以外は全く同様に
処理,操作したところ,ポリアクリル酸の場合と同様に
優れた結果が得られた。その結果を表2に示す。(Experimental Examples 5 to 8 and Comparative Example) Experimental Example 1
Polyvinyl alcohol (degree of polymerization: 2000) was used in place of polyacrylic acid of Nos. 4 to 4, and the same treatment and operation were performed except for the above, and excellent results were obtained as in the case of polyacrylic acid. Table 2 shows the results.
【0024】[0024]
【表2】 [Table 2]
【0025】[0025]
【発明の効果】このように,本発明においては,石炭酸
系合成樹脂をコーティングしたレジンコーテッドサンド
を用いて砂中子原型を造型する工程と,この砂中子原型
を非熱硬化性水溶性合成高分子で処理する工程と,この
非熱硬化性水溶性合成高分子で処理した砂中子原型を乾
燥する工程と,この乾燥した砂中子原型の表面に粉末状
の耐火物を主成分とする中性水分散体からなるスラリ状
のコーティング剤をコーティングする工程と,このコー
ティングして得た砂中子を乾燥させる工程によってコー
ティングされた砂中子を製造するようにしたので,コー
ティング剤でコーティングするとき,コーティング剤は
砂中子原型の表面ではじかれたり,砂中子原型内に浸み
込んだりすることなく,均一で適当な厚さのコーティン
グ層を形成する。したがって,砂中子は,鋳造時には高
圧の鋳込圧力に充分耐えることができる。As described above, according to the present invention, a step of molding a sand core prototype using a resin-coated sand coated with a carboxylate-based synthetic resin, and a step of synthesizing the sand core prototype with a non-thermosetting water-soluble synthetic resin A step of treating with a polymer, a step of drying the sand core prototype treated with the non-thermosetting water-soluble synthetic polymer, and a step of coating the surface of the dried sand core prototype with a powdered refractory as a main component. The coated core is manufactured by the step of coating a slurry-like coating agent composed of a neutral aqueous dispersion and the step of drying the core obtained by coating. When coating, the coating agent forms a uniform and appropriate thickness coating layer without being repelled on the surface of the sand core prototype or penetrating into the sand core prototype. Therefore, the sand core can sufficiently withstand high casting pressure during casting.
【0026】すなわち,本発明で得られた砂中子を用い
てダイカストのような高圧鋳造を行った場合,砂中子中
に溶湯が差込むことがなく,砂を排出した後の製品の鋳
肌面には砂は全く残留せず,非常に平滑である。したが
って,このような砂中子を,例えば,クローズドデッキ
型のエンジンブロックの冷却ジャケット部分のように,
非常に複雑な形状を有する製品を鋳造する際に用いて
も,充分に満足のいく作業状態と製品を確実容易に得る
ことができる。That is, when high-pressure casting such as die casting is performed using the sand core obtained in the present invention, the molten metal is not inserted into the sand core, and the product after the sand is discharged is cast. There is no sand left on the skin and it is very smooth. Therefore, such a sand core is used, for example, in the cooling jacket portion of a closed deck type engine block.
Even when used for casting a product having a very complicated shape, a sufficiently satisfactory working state and the product can be obtained easily and reliably.
Claims (1)
ンコーテッドサンドを用いて砂中子原型を造型する工程
と,この砂中子原型を非熱硬化性水溶性合成高分子で処
理する工程と,この非熱硬化性水溶性合成高分子で処理
した砂中子原型を乾燥する工程と,この乾燥した砂中子
原型の表面に粉末状の耐火物を主成分とする中性水分散
体からなるスラリ状のコーティング剤をコーティングす
る工程と,このコーティングして得た砂中子を乾燥させ
る工程からなる砂中子の製造方法。1. A step of molding a sand core prototype using a resin-coated sand coated with a carboxylate synthetic resin, a step of treating the sand core prototype with a non-thermosetting water-soluble synthetic polymer, and A step of drying the sand core prototype treated with the non-thermosetting water-soluble synthetic polymer, and a slurry comprising a powdered refractory-based neutral water dispersion on the surface of the dried sand core prototype. A method for producing a sand core, comprising the steps of: coating a coating agent in a shape; and drying the sand core obtained by coating.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP04239427A JP3090294B2 (en) | 1992-09-08 | 1992-09-08 | Sand core manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP04239427A JP3090294B2 (en) | 1992-09-08 | 1992-09-08 | Sand core manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0679404A JPH0679404A (en) | 1994-03-22 |
JP3090294B2 true JP3090294B2 (en) | 2000-09-18 |
Family
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JP04239427A Expired - Fee Related JP3090294B2 (en) | 1992-09-08 | 1992-09-08 | Sand core manufacturing method |
Country Status (1)
Country | Link |
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JP (1) | JP3090294B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014126060A (en) * | 2012-12-25 | 2014-07-07 | Pdm Co Ltd | Adhesive insulation composition |
CN114951543B (en) * | 2022-05-26 | 2023-08-29 | 共享新材料(山东)有限公司 | Release agent and preparation method thereof |
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1992
- 1992-09-08 JP JP04239427A patent/JP3090294B2/en not_active Expired - Fee Related
Also Published As
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JPH0679404A (en) | 1994-03-22 |
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