JPH0390245A - Coated sand for manufacturing mold - Google Patents

Coated sand for manufacturing mold

Info

Publication number
JPH0390245A
JPH0390245A JP22907589A JP22907589A JPH0390245A JP H0390245 A JPH0390245 A JP H0390245A JP 22907589 A JP22907589 A JP 22907589A JP 22907589 A JP22907589 A JP 22907589A JP H0390245 A JPH0390245 A JP H0390245A
Authority
JP
Japan
Prior art keywords
resin
resin component
mold
sand
coated sand
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
Application number
JP22907589A
Other languages
Japanese (ja)
Other versions
JP2747053B2 (en
Inventor
Kazuhiko Kiuchi
一彦 木内
Shigeaki Takashina
重昭 高階
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP1229075A priority Critical patent/JP2747053B2/en
Publication of JPH0390245A publication Critical patent/JPH0390245A/en
Application granted granted Critical
Publication of JP2747053B2 publication Critical patent/JP2747053B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To shorten hardening time and to lower hardening temp. by applying resin component (a) 2.5-furan dialdehyde and compound which can generate the specific combination by coming into reaction with the resin component (a) and having solid-state at the room temp. and active hydrogen on sand. CONSTITUTION:The coated sand is formed with the resin component (a) 2.5-furan dialdehyde and the resin component (b) having solid-state ar room temp. and active hydrogen and being the compound which can generate the combination shown with the formula by coming into reaction with the resin component (a), e.g. phenol series monomer, phenol series resin, amino compound, etc. In the formula, X shows the aldehyde remain group. The resin components (a), (b) and curing agent are applied on surface of refractory aggregate and by using this to the coated sand for manufacturing the mold, as the hardening time is shortened and the hardening temp. can be lowered, strain to the metallic mold and strain to the mold come to a little.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は加熱硬化して鋳型を成型する被覆砂に関するも
のである。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to coated sand that is heated and hardened to form a mold.

〔従来の技術及びその課題〕[Conventional technology and its problems]

従来、加熱硬化鋳型の製造法としては、耐火性粒状骨材
にフェノールノボラック樹脂を被覆し、ヘキサメチレン
テトラ1ンを触媒として約300℃近辺で加熱硬化せし
める、所謂シェルモールド法がある。この加熱硬化法は
設備的に簡便であり、作業的に使用しやすい等の利点に
より現在加熱硬化鋳型製造法としては最も多く使用され
ている。しかしながら、硬化時間が長く、硬化温度が高
いため、金型の歪、鋳型の歪が多く、鋳型のパリ取り作
業が欠かせず、又、寸法精度も不充分であった。更に硬
化温度が高い事による作業環境の劣悪さ及びフェノール
樹脂、ヘキサメチレンテトラミンの熱分解臭気による作
業環境の汚染も著しく、これらの大幅な改善が望まれて
いた。
Conventionally, as a method for manufacturing heat-curing molds, there is a so-called shell molding method in which a refractory granular aggregate is coated with a phenol novolak resin and heated and cured at around 300° C. using hexamethylenetetraton as a catalyst. This heat-curing method is currently the most commonly used heat-curing mold manufacturing method due to its simple equipment and ease of use. However, since the curing time was long and the curing temperature was high, there were many mold distortions and mold distortions, mold deburring work was indispensable, and dimensional accuracy was insufficient. Furthermore, the working environment is extremely poor due to the high curing temperature, and the working environment is extremely polluted due to the odor of thermal decomposition of the phenol resin and hexamethylenetetramine, and it has been desired to significantly improve these conditions.

また、150℃から250″C近辺で耐火性粒状骨材に
フラン樹脂、フェノールレゾール樹脂やフ↓ノール又は
尿素/ホルマリン変性フラン樹脂等の酸硬化性樹脂と、
塩化アンモニウム、シュ・つ酸等の硬化触媒を混じた混
合物を加熱硬化し、鋳型を生産する方法がある。これは
硬化時間がシェルモールド法よりは短く、温度による歪
、寸法精度や熱的作業環境の面でも改善される。
In addition, acid-curing resins such as furan resin, phenol resol resin, phenol or urea/formalin-modified furan resin are added to the refractory granular aggregate from 150°C to around 250″C.
There is a method of producing a mold by heating and curing a mixture containing a curing catalyst such as ammonium chloride and oxalic acid. This method has a shorter curing time than the shell mold method, and is also improved in terms of temperature-induced distortion, dimensional accuracy, and thermal working environment.

しかしながら、これらのフラン樹脂、フェノールレゾー
ル樹脂やフェノール又は尿素/ホルマリン変性フラン樹
脂等の酸硬化性樹脂は常温で液体であり、従ってこれを
鋳物用耐火性骨材と混合した場合、混練砂は湿った状態
であり、シェルモールド法のような乾態砂に比較し、充
填性が劣るためブロ一方案等の対応が必要である。
However, acid-curing resins such as furan resins, phenol resol resins, and phenol- or urea/formalin-modified furan resins are liquid at room temperature, so when mixed with refractory aggregate for foundries, the kneading sand becomes wet. Compared to dry sand such as the shell mold method, the filling properties are inferior, so measures such as blow blowing are required.

このように従来の加熱硬化鋳型造型法に用いられる鋳物
砂には各々一長一短があり、これらの長所を兼ね備える
ような更に優れた鋳物砂が望まれている。
As described above, each of the molding sands used in the conventional heat-hardening mold making method has its advantages and disadvantages, and there is a desire for an even better molding sand that combines these advantages.

〔課題を解決するための手段〕[Means to solve the problem]

本発明者らは上記課題を解決すべく鋭意研究の結果、特
定の樹脂成分と硬化剤成分を耐火性粒状骨材表面に予め
コーティングし、骨材表面に固形のレジンコーティング
層を形成した鋳型製造用被覆砂が他の性能を低下させる
ことなく大幅に鋳型の硬化速度及び充填性を向上できる
ことを見出し本発明を完成するに至った。
As a result of intensive research to solve the above problems, the present inventors manufactured a mold by pre-coating the surface of fire-resistant granular aggregate with a specific resin component and curing agent component to form a solid resin coating layer on the surface of the aggregate. The present inventors have discovered that the coating sand can significantly improve the curing speed and filling properties of molds without deteriorating other properties, and have completed the present invention.

すなわち本発明は、次の樹脂成分(イ)、(ロ)と硬化
剤とを耐火性骨材表面に被覆した鋳型製造用被覆砂を提
供するものである。
That is, the present invention provides coated sand for mold production in which the surface of a fire-resistant aggregate is coated with the following resin components (a) and (b) and a curing agent.

樹脂成分(イ)・・・2.5−フランジアルデヒド。Resin component (a)...2,5-furandialdehyde.

樹脂成分(ロ)・・・常温で固体であり、活性水素を持
ち樹脂成分(イ)と反 応して−CH−結合(X  、ア ルデヒド残基)を生威し得 る化合物。
Resin component (b): A compound that is solid at room temperature, has active hydrogen, and can react with resin component (a) to form a -CH- bond (X, aldehyde residue).

本発明に用いられる樹脂成分(ロ)としては、例えばフ
ェノール系モノマー、フェノール系樹脂、アミノ化合物
、アミノ系樹脂、芳香族炭化水素系樹脂等が挙げられる
。好ましくはビスフェノールA、ビスフェノールF、レ
ゾルシノール、キシレノール等のフェノール系モノマー
フェノール系樹脂、尿素、尿素樹脂、キシレン樹脂等が
挙げられる。
Examples of the resin component (b) used in the present invention include phenolic monomers, phenolic resins, amino compounds, amino resins, aromatic hydrocarbon resins, and the like. Preferred examples include phenolic monomers such as bisphenol A, bisphenol F, resorcinol, and xylenol, phenolic resins, urea, urea resins, and xylene resins.

また、本発明に用いられる樹脂成分には従来公知の変性
剤の少なくとも一種を混合もしくは共縮合させることも
できる。
Furthermore, at least one of conventionally known modifiers may be mixed or co-condensed with the resin component used in the present invention.

従来公知の変性剤を具体的に例示すれば、クマロン・イ
ンデン樹脂、石油樹脂、ポリエステル、アルキッド樹脂
、ポリビニルアルコール、エポキシ樹脂、エチレン・ビ
ニルアセテート、ポリビニルアセテート、ポリブタジェ
ン、ポリエーテル、ポリエチレンイミン、ポリ塩化ビニ
ル、ポリアクリル酸エステル、ポリビニルブチラール、
フェノキシ樹脂、酢酸セルロース、キシレン樹脂、トル
エン樹脂、ポリアミド、スチレン樹脂、ポリビニルホル
マール、アクリル樹脂、ウレタン樹脂、ナイロン等のポ
リマー及びオリゴマーや、リグニン、リグニンスルホン
酸、ロジン、エステルガム、植物油、ビチューメン、重
油、カシューナツト殻液、バニリン、タンニン類等の天
然物や、澱粉、コーンスターチ、グルコース、デキスト
リン等のII類及びその誘導体や、レゾルシン残渣、ク
レゾール残渣、2.2.4−トリメチル−4−(ヒドロ
キシフェニル)クマロンとイソプロペニルフェノールの
反応副生物、テレフタル酸とエチレングリコールの反応
副生物等の反応残渣及び副生物や、ポリエチレングリコ
ール等の多価アルコールや、アセトン、シクロヘキサノ
ン、アセトフェノン等のケトン類及びアルデヒドとの縮
合物や、ジシアンジアミド、アクリルア果ド、チオ尿素
等のアミノもしくはイミノ化合物及びそれらのアルデヒ
ド縮金物や、フルフラール、グリオキザール等のアルデ
ヒド化合物や、イソシアヌル酸エステル、不飽和脂肪酸
エステル等のエステル化合物などである。
Specific examples of conventionally known modifiers include coumaron/indene resin, petroleum resin, polyester, alkyd resin, polyvinyl alcohol, epoxy resin, ethylene/vinyl acetate, polyvinyl acetate, polybutadiene, polyether, polyethyleneimine, and polychloride. Vinyl, polyacrylic ester, polyvinyl butyral,
Polymers and oligomers such as phenoxy resin, cellulose acetate, xylene resin, toluene resin, polyamide, styrene resin, polyvinyl formal, acrylic resin, urethane resin, nylon, lignin, lignin sulfonic acid, rosin, ester gum, vegetable oil, bitumen, heavy oil , cashew nut shell liquid, vanillin, natural products such as tannins, class II and its derivatives such as starch, corn starch, glucose, dextrin, resorcin residue, cresol residue, 2.2.4-trimethyl-4-(hydroxy Reaction residues and by-products such as reaction by-products of phenyl)coumarone and isopropenylphenol, reaction by-products of terephthalic acid and ethylene glycol, polyhydric alcohols such as polyethylene glycol, ketones and aldehydes such as acetone, cyclohexanone, and acetophenone. amino or imino compounds such as dicyandiamide, acrylamide, thiourea, and their aldehyde condensates, aldehyde compounds such as furfural and glyoxal, and ester compounds such as isocyanuric acid esters and unsaturated fatty acid esters. It is.

本発明に用いられる樹脂成分は(イ)、(ロ)ともに常
温で固体であるが、これを微粉砕するか、あるいは塊状
のまま加熱した鋳物砂中に投入するか、あるいは溶剤に
溶解した後、鋳物砂中に投入することにより耐火性骨材
表面に均一に付着させる。
The resin components (a) and (b) used in the present invention are both solid at room temperature, but they can be finely pulverized, put into heated molding sand as a lump, or dissolved in a solvent and then By pouring it into foundry sand, it is made to adhere uniformly to the surface of the refractory aggregate.

本発明において、樹脂成分(イ)、(口〉は耐火性骨材
100重量部に対しくイ)+(ロ)総量で0.5〜8重
量部、好ましくは1〜5重量部を配合する。
In the present invention, resin components (a) and (b) are blended in a total amount of 0.5 to 8 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the fire-resistant aggregate. .

そのうち、樹脂成分(イ)の2.5−フランジアルデヒ
ドは耐火性骨材100重量部に対し0.1〜5重量部、
好ましくは0.3〜3重量部を配合する。
Among them, the resin component (a) 2,5-furandialdehyde is 0.1 to 5 parts by weight per 100 parts by weight of the fire-resistant aggregate;
Preferably, 0.3 to 3 parts by weight is blended.

本発明の樹脂成分〈イ〉9(ロ)は予め一部反応させた
状態で砂に被覆してもよいが、一般には反応させない状
態で砂に被覆する。被覆中に砂は加熱されているので、
その熱により一部反応が進行することがある。
The resin component (A) 9 (B) of the present invention may be coated on the sand after being partially reacted in advance, but generally it is coated on the sand without being reacted. Since the sand is heated during coating,
Part of the reaction may proceed due to the heat.

本発明における樹脂成分(イ)、(ロ)には本発明の効
果を更に一層大きくするためにシランカップリング剤(
例えばT−ウレイドプロピルトリエトキシシラン)、滑
材(例えばステアリン酸カルシウム)等を配合してもよ
い。
In order to further enhance the effects of the present invention, the resin components (a) and (b) in the present invention include a silane coupling agent (
For example, T-ureidopropyltriethoxysilane), a lubricant (for example, calcium stearate), etc. may be added.

また、本発明における硬化剤としてはシュウ酸、サリチ
ル酸、マレイン酸、ホウ酸、ベンゼンスルホン酸、トル
エンスルホン酸、キシレンスルホン酸等の有機スルホン
酸等の酸の少なくとも1種、あるいはシュウ酸、サリチ
ル酸、マレイン酸、ホウ酸、トルエンスルホン酸、キシ
レンスルホン酸、ベンゼンスルホン酸等の有機スルホン
酸等と銅、鉄、アルミニウム、亜鉛、尿素、メラミン、
アミンなどとの塩、塩化銅、塩化鉄等のルイス酸等の常
温で固体の酸あるいは塩が使用され、その配合量は、樹
脂成分(イ)+(ロ)総量に対して0.5〜50重量%
、好ましくは10〜40重量%である。この硬化剤を樹
脂成分と共に砂に被覆することにより鋳型造型時の被覆
砂の硬化時間を短くすることができる。
Further, as the curing agent in the present invention, at least one acid such as oxalic acid, salicylic acid, maleic acid, boric acid, benzenesulfonic acid, toluenesulfonic acid, organic sulfonic acid such as xylene sulfonic acid, or oxalic acid, salicylic acid, Organic sulfonic acids such as maleic acid, boric acid, toluenesulfonic acid, xylene sulfonic acid, benzenesulfonic acid, etc. and copper, iron, aluminum, zinc, urea, melamine,
Acids or salts that are solid at room temperature are used, such as salts with amines, Lewis acids such as copper chloride, iron chloride, etc., and the blending amount is 0.5 to 0.5 to the total amount of resin components (a) + (b). 50% by weight
, preferably 10 to 40% by weight. By coating the sand with this curing agent together with the resin component, the curing time of the coated sand during mold making can be shortened.

本発明において用いられる耐火性粒状骨材としては、石
英質を主成分とする珪砂の他、ジルコン砂、クロマイト
砂、オリピン砂等が使用されるが、特にこれらに限定さ
れものではない。
The refractory granular aggregate used in the present invention includes, but is not particularly limited to, silica sand containing quartz as a main component, zircon sand, chromite sand, oripin sand, and the like.

〔実 施 例〕〔Example〕

以下実施例にて本発明を説明するが、本発明はこれらの
実施例に限定されるものではない。
The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

実施例1〜8 オーストラリア産フラタリー珪砂100重量部に、表−
1に示す如き硬化剤の20%メタノール溶液を2重量部
、表−1に示す如き樹脂成分(口:の20%メタノール
溶液5重量部を加えて亀キサ−にて混練し、溶剤を蒸発
させた後、2,5−フランジアルデヒド(100mes
h pass)を1重量部及びステアリン酸カルシウム
0゜1重量部を加えて混練し、種々の流動性のある被覆
砂を得た。
Examples 1 to 8 100 parts by weight of Australian flattery silica sand was added with the table below.
2 parts by weight of a 20% methanol solution of the curing agent shown in Table 1 and 5 parts by weight of a 20% methanol solution of the resin components shown in Table 1 were kneaded in a kettle mixer, and the solvent was evaporated. After that, 2,5-furandialdehyde (100 mes
0.1 part by weight of calcium stearate was added and kneaded to obtain coated sand with various fluidities.

これらの被覆砂を、予め180°Cに加熱した25X 
25 X 250m/mの型枠に加圧空気と共に吹き込
んで充填し、10秒間焼威して鋳型を成型した。
These coated sands were heated to 180°C in advance at 25X.
A mold of 25 x 250 m/m was filled by blowing with pressurized air and baked for 10 seconds to form a mold.

抜型後10秒後の曲げ強度及び鋳型かさ比重を測定した
。結果を表−1に示す。
The bending strength and bulk specific gravity of the mold were measured 10 seconds after the mold was removed. The results are shown in Table-1.

比較例1.2 オーストラリア産フラタリー珪砂100重量部に対し、
軟化点85°C1平均分子量1150のノボラック型フ
ェノール樹脂2重量部、20%へキサメチレンテトラミ
ン水溶液1.5重量部、ステアリン酸カルシウム0.1
重量部を被覆した樹脂被覆砂を、予め表−1に示す温度
に加熱した25 X 25X 250m/+++の金型
に加圧空気と共に吹き込んで充填し、表−1に示す時間
焼成して鋳型を成型し、実施例1と同様の評価を行った
。結果を表−1に示す。
Comparative Example 1.2 For 100 parts by weight of Australian flattery silica sand,
2 parts by weight of novolac type phenolic resin with a softening point of 85°C and an average molecular weight of 1150, 1.5 parts by weight of a 20% hexamethylenetetramine aqueous solution, and 0.1 parts by weight of calcium stearate.
The resin-coated sand coated with the weight part was blown and filled with pressurized air into a 25 x 25 x 250 m/+++ mold that had been preheated to the temperature shown in Table 1, and was fired for the time shown in Table 1 to form the mold. It was molded and evaluated in the same manner as in Example 1. The results are shown in Table-1.

比較例3.4 オーストラリア産フラタリー珪砂100重量部に表−1
に示す如き硬化剤の20%水溶液を0.45重量部、尿
素変性フラン樹脂を1.5重量部使用して作った被覆砂
を、予め表−1に示す温度に加熱した25 X 25 
X 250+++/mの金型に加圧空気と共に吹き込ん
で充填し、表−1に示す時間焼成して鋳型を成型し、実
施例1と同様の評価を行った。結果を表−1に示す。
Comparative Example 3.4 Add Table 1 to 100 parts by weight of Australian flattery silica sand
A coated sand prepared by using 0.45 parts by weight of a 20% aqueous solution of a curing agent as shown in Table 1 and 1.5 parts by weight of a urea-modified furan resin was heated in advance to the temperature shown in Table 1.
The mixture was blown into a mold of X 250+++/m and filled with pressurized air, and fired for the time shown in Table 1 to form a mold, and the same evaluation as in Example 1 was performed. The results are shown in Table-1.

Claims (1)

【特許請求の範囲】 1 次の樹脂成分(イ)、(ロ)と硬化剤とを耐火性骨
材表面に被覆した鋳型製造用被覆砂。 樹脂成分(イ)・・・2,5−フランジアルデヒド。 樹脂成分(ロ)・・・常温で固体であり、活性水素を持
ち樹脂成分(イ)と反 応して▲数式、化学式、表等があります▼結合(X;ア ルデヒド残基)を生成し得 る化合物。
[Scope of Claims] 1. A coated sand for mold manufacturing, in which the surface of a refractory aggregate is coated with the following resin components (a) and (b) and a curing agent. Resin component (a)...2,5-furandialdehyde. Resin component (b): A compound that is solid at room temperature, has active hydrogen, and can react with resin component (a) to form a bond (X; aldehyde residue) that has mathematical formulas, chemical formulas, tables, etc. .
JP1229075A 1989-09-04 1989-09-04 Coated sand for mold production Expired - Fee Related JP2747053B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1229075A JP2747053B2 (en) 1989-09-04 1989-09-04 Coated sand for mold production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1229075A JP2747053B2 (en) 1989-09-04 1989-09-04 Coated sand for mold production

Publications (2)

Publication Number Publication Date
JPH0390245A true JPH0390245A (en) 1991-04-16
JP2747053B2 JP2747053B2 (en) 1998-05-06

Family

ID=16886350

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1229075A Expired - Fee Related JP2747053B2 (en) 1989-09-04 1989-09-04 Coated sand for mold production

Country Status (1)

Country Link
JP (1) JP2747053B2 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5823177A (en) * 1981-08-03 1983-02-10 オ−トメ−シヨン・インダストリ−ズ・インコ−ポレ−テツド Shielding cover for rapid return type electric connector

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5823177A (en) * 1981-08-03 1983-02-10 オ−トメ−シヨン・インダストリ−ズ・インコ−ポレ−テツド Shielding cover for rapid return type electric connector

Also Published As

Publication number Publication date
JP2747053B2 (en) 1998-05-06

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