JPH0791352B2 - Method for producing novolac type phenolic resin for shell mold - Google Patents
Method for producing novolac type phenolic resin for shell moldInfo
- Publication number
- JPH0791352B2 JPH0791352B2 JP62291894A JP29189487A JPH0791352B2 JP H0791352 B2 JPH0791352 B2 JP H0791352B2 JP 62291894 A JP62291894 A JP 62291894A JP 29189487 A JP29189487 A JP 29189487A JP H0791352 B2 JPH0791352 B2 JP H0791352B2
- Authority
- JP
- Japan
- Prior art keywords
- novolac type
- phenol resin
- parts
- shell mold
- phenolic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000010680 novolac-type phenolic resin Substances 0.000 title description 6
- 239000005011 phenolic resin Substances 0.000 claims description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010112 shell-mould casting Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 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 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ethylenebisstearoyl amide Chemical class 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical class OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical class OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Landscapes
- Mold Materials And Core Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は鋳造に用いるシェル鋳型造型時に発生する悪臭
の少ないシェルモールド用ノボラック型フェノール樹脂
に関するものである。TECHNICAL FIELD The present invention relates to a novolac-type phenol resin for shell molds, which has less offensive odor generated during molding of shell molds used for casting.
シェルモールド用の結合剤としは、一般にノボラック型
フェノール樹脂が使用されている。しかし、ノボラック
型フェノール樹脂を用いて製造されたレジンコーテッド
サンドを250〜350℃に加熱された金型を用いて鋳型を生
産する際に、悪臭が発生し、鋳型造型工場内の作業環境
及び工場外への拡散により自然環境を悪化させ社会問題
となっている。As a binder for the shell mold, a novolac type phenol resin is generally used. However, when producing mold using resin coated sand manufactured using novolac type phenol resin with a mold heated to 250 to 350 ° C, a bad odor is generated, and the working environment and factory in the mold making factory It has become a social problem by deteriorating the natural environment by spreading it outside.
また、硬化剤としてヘキサミンを併用しないレゾール型
フェノール樹脂を結合剤として使用する試みもなされて
いるが悪臭を低減するには不充分であった。Attempts have also been made to use a resol-type phenolic resin, which does not use hexamine as a curing agent, as a binder, but it was insufficient to reduce a bad odor.
ノボラック型フェノール樹脂を用いたレジンコーテッド
サンドのシェル鋳型造型時に発生する悪臭は、ノボラッ
ク型フェノール樹脂に含有する低分子成分の加熱による
揮散と、硬化剤として併用するヘキサミンの熱分解によ
る分解生成物の揮散などによる。ノボラック型フェノー
ル樹脂に含有する低分子成分の中の１核体成分が悪臭の
原因になることは従来より認められていることである
が、本発明者らは臭気物質について詳細に検討した結
果、さらに２核体成分も悪臭の大きな原因となることを
見い出した。この結果に基いて鋳型造型時に発生する悪
臭を低下し、且つシェル鋳型の造型作業性及び強度の良
好なノボラック型フェノール樹脂を得んとして研究を重
ねた結果、ノボラック型フェノール樹脂中の１核体の含
有量が１重量部未満、且つ２核体成分の含有量が２重量
％未満であるノボラック型フェノール樹脂が特に有効で
あることを見い出し、本発明を完成するに至った。The malodor generated during shell molding of resin coated sand using novolac type phenolic resin is caused by the volatilization of low molecular components contained in the novolac type phenolic resin due to heating and the decomposition products of the thermal decomposition of hexamine used as a curing agent. Due to volatilization, etc. It has been conventionally recognized that the mononuclear component in the low-molecular component contained in the novolac type phenol resin causes the malodor, but as a result of a detailed study on the odorous substance, the present inventors found that Furthermore, it has been found that the binuclear component also contributes significantly to the malodor. Based on these results, we conducted research to obtain a novolak-type phenol resin that reduces the malodor generated during mold making and has good shell mold molding workability and strength. It was found that a novolac type phenol resin having a content of less than 1 part by weight and a content of a binuclear component of less than 2% by weight is particularly effective, and completed the present invention.
（発明の構成） 本発明は、フェノール類とホルムアルデヒド類とを酸性
触媒の存在下で加熱反応させ、その後水、フェノール類
及び２核体フェノール樹脂を除去することにより、フェ
ノール樹脂中の１核体の含有量が１重量％未満であり、
２核体の含有量が２重量％未満とすることを特徴とする
シェルモールド用ノボラック型フェノール樹脂の製造方
法である。(Structure of the Invention) In the present invention, a phenol and a formaldehyde are heated and reacted in the presence of an acidic catalyst, and then water, the phenols and the binuclear phenol resin are removed to obtain a mononuclear compound in the phenol resin. Content of less than 1% by weight,
A method for producing a novolac-type phenol resin for shell molding, characterized in that the content of the binuclear body is less than 2% by weight.
フェノール樹脂中の１核体成分は未反応の遊離モノマー
及び２−メチロールフェノール類、４−メチロールフェ
ノール類などであるが遊離モノマーが大部分である。The mononuclear component in the phenol resin is unreacted free monomer and 2-methylolphenols, 4-methylolphenols, etc., but most of the free monomers are free monomers.
フェノール樹脂中の２核体成分は2,2′−ジヒドロキシ
ジフェニルメタン類、2,4′−ジヒドロキシジフェニル
メタン類及び4,4′−ジヒドロキシジフェニルメタン類
などである。The binuclear component in the phenol resin is 2,2'-dihydroxydiphenylmethanes, 2,4'-dihydroxydiphenylmethanes and 4,4'-dihydroxydiphenylmethanes.
これらの１核体成分及び２核体成分の含有量は高速液体
クロマトグラフィーにより分析可能である。The contents of these mononuclear body component and dinuclear body component can be analyzed by high performance liquid chromatography.
ノボラック型フェノール樹脂の数平均分子量は300〜750
である。数平均分子量が300未満ではフェノール樹脂の
融点が低下し、固結が生じやすくなる。また750を上回
ると樹脂の流動性が低下して得られたシェル鋳型の強度
が低下する。Novolak type phenolic resin has a number average molecular weight of 300-750
Is. If the number average molecular weight is less than 300, the melting point of the phenol resin is lowered, and caking is likely to occur. On the other hand, when it exceeds 750, the fluidity of the resin is lowered and the strength of the obtained shell mold is lowered.
ここでフェノール類としては、フェノール、クレゾー
ル、キシレノール、レゾルシン、ビスフェノールＡ、カ
テコールなどが単独又は併用して使用される。Here, as the phenols, phenol, cresol, xylenol, resorcin, bisphenol A, catechol and the like are used alone or in combination.
ホルムアルデヒド類としては、ホルマリン、パラホルム
アルデヒド、トリオキサンなどが単独又は併用して使用
される。As formaldehyde, formalin, paraformaldehyde, trioxane, etc. are used alone or in combination.
触媒として用いられる酸性物質としては蓚酸、塩酸、硫
酸、パラトルエンスルホン酸、酢酸亜鉛、炭酸亜鉛、酢
酸など一般にノボラック型フェノール樹脂を製造する際
に用いられる有機酸、無機酸又はそれ等の金属塩が使用
される。Examples of the acidic substance used as a catalyst include oxalic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, zinc acetate, zinc carbonate, acetic acid, and other organic acids generally used in the production of novolac phenolic resins, inorganic acids, or metal salts thereof. Is used.
本発明のノボラック型フェノール樹脂はこれらのフェノ
ール類、ホルムアルデヒド類及び触媒を反応釜に仕込み
後、加熱し付加縮合させた後脱水反応することにより得
られる。特に脱水反応において減圧下で反応生成物の温
度を230〜270℃まで昇温させて得る方法、あるいは 反応生成物の温度が180〜250℃まで不活性ガス及び又は
水蒸気を吹込みながら加熱する方法などにより１核体成
分を１重量％未満、且つ２核体成分を２重量％未満とす
る。The novolac type phenol resin of the present invention can be obtained by charging these phenols, formaldehydes and catalysts into a reaction vessel, heating them for addition condensation, and then dehydrating the mixture. In particular, in the dehydration reaction, a method of raising the temperature of the reaction product to 230 to 270 ° C under reduced pressure, or a method of heating the reaction product to a temperature of 180 to 250 ° C while blowing an inert gas and / or steam. For example, the content of mononuclear components is less than 1% by weight and the content of dinuclear components is less than 2% by weight.
本発明のノボラック型フェノール樹脂にシェル鋳型の向
上剤として一般に用いられるシランカップリング剤、エ
チレンビスステアロイルアマイドなどの滑剤及びステア
リン酸カルシウムなどの固結防止剤の添加も可能であ
る。It is also possible to add a silane coupling agent, a lubricant such as ethylenebisstearoyl amide and the like, and an anti-caking agent such as calcium stearate, which are generally used as a shell mold improving agent, to the novolac type phenolic resin of the present invention.
本発明によるノボラック型フェノール樹脂を使用するこ
とによりシェル鋳型の造型作業性及び特性を損うことな
く、シェル鋳型造型時に発生する悪臭を大幅に減少でき
るので、シェル鋳型造型工場の作業環境の改善ができ、
更に工場外への悪臭の拡散がなくなり良好な自然環境の
維持向上に効果的である。By using the novolac type phenolic resin according to the present invention, it is possible to significantly reduce the malodor generated at the time of molding the shell mold without impairing the molding workability and characteristics of the shell mold, thus improving the working environment of the shell molding factory. You can
Furthermore, it is effective in maintaining and improving a good natural environment because the offensive odor is not diffused outside the factory.
以下、本発明を実施例により説明する。しかし本発明は
これらの実施例によって限定されるものではない。ま
た、実施例及び比較例に記載されている「部」及び
「％」はすべて「重量部」及び「重量％」を示す。Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples. Moreover, all "parts" and "%" described in the examples and comparative examples represent "parts by weight" and "% by weight".
実施例１ 冷却器と撹拌器付きの反応容器に、フェノール1500部、
37％ホルマリン711部、次いで蓚酸15部を仕込んだ。徐
々に昇温して温度95℃に達してから180分間還流反応を
行なった。次いで60Torrの減圧下で脱水反応を行ない、
温度が150℃に到達した時より窒素ガスを吸込みながら
脱水を続け、加熱を継続して内温を210℃にし、この温
度で更に４時間継続した。Example 1 1500 parts of phenol in a reaction vessel equipped with a condenser and a stirrer,
711 parts of 37% formalin and then 15 parts of oxalic acid were charged. The temperature was gradually raised, and after reaching 95 ° C., a reflux reaction was performed for 180 minutes. Then dehydration reaction under reduced pressure of 60 Torr,
When the temperature reached 150 ° C, dehydration was continued while sucking nitrogen gas, heating was continued to bring the internal temperature to 210 ° C, and this temperature was continued for another 4 hours.
次いで20Torrの減圧下で真空脱水を１時間行なった後、
反応容器より排出して常温で固形のノボラック型フェノ
ール樹脂1150部を得た。Then, after vacuum dehydration for 1 hour under a reduced pressure of 20 Torr,
The product was discharged from the reaction vessel to obtain 1150 parts of a novolac type phenol resin which was solid at room temperature.
実施例２ 冷却器と撹拌器付きの反応容器にフェノール1200部、ク
レゾール300部、37％ホルマリン693部、次いで25％塩酸
水５部を仕込んだ。次いで実施例１と同じ反応脱水方法
を行ない、常温で固形のクレゾール変性ノボラック型フ
ェノール樹脂1180部を得た。Example 2 A reaction vessel equipped with a condenser and a stirrer was charged with 1200 parts of phenol, 300 parts of cresol, 693 parts of 37% formalin, and then 5 parts of 25% hydrochloric acid water. Then, the same reaction dehydration method as in Example 1 was carried out to obtain 1180 parts of a solid cresol-modified novolac type phenol resin at room temperature.
比較例１ 冷却器と撹拌器付きの反応容器にフェノール1500部、37
％ホルマリン840部、次いで蓚酸15部を仕込んだ。徐々
に昇温して温度95℃に達してから180分間還流反応を行
なった。次いで60Torrの減圧下で脱水反応を行ない、温
度が150℃に到達した後反応容器より排出して常温で固
形のノボラック型フェノール樹脂1450部を得た。Comparative Example 1 Phenol 1500 parts, 37 in a reaction vessel equipped with a condenser and a stirrer
% Formalin 840 parts and then 15 parts of oxalic acid were charged. The temperature was gradually raised, and after reaching 95 ° C., a reflux reaction was performed for 180 minutes. Then, dehydration reaction was carried out under a reduced pressure of 60 Torr, and after the temperature reached 150 ° C., the product was discharged from the reaction container to obtain 1450 parts of a novolac type phenol resin which was solid at room temperature.
比較例２ 冷却器と撹拌器付きの反応容器にフェノール1500部、37
％ホルマリン776部、次いで蓚酸15部を仕込んだ。徐々
に昇温して温度95℃に達してから180分間還流反応を行
なった。次いで60Torrの減圧下で脱水反応を行ない、温
度200℃まで加熱した。更に温度200〜210℃、真空度20T
orrで１時間真空脱水を行なった後、反応容器より排出
して常温で固形のノボラック型フェノール樹脂1420部を
得た。Comparative Example 2 Phenol 1500 parts, 37 in a reaction vessel equipped with a condenser and a stirrer
% Formalin 776 parts and then 15 parts oxalic acid were charged. The temperature was gradually raised, and after reaching 95 ° C., a reflux reaction was performed for 180 minutes. Then, dehydration reaction was performed under reduced pressure of 60 Torr, and the temperature was raised to 200 ° C. Furthermore, temperature is 200-210 ℃, vacuum degree is 20T
After vacuum dehydration with orr for 1 hour, the product was discharged from the reaction vessel to obtain 1420 parts of a solid novolac type phenol resin at room temperature.
実施例１、２及び比較例１、２で得られた４種類のノボ
ラック型フェノール樹脂の高速液体クロマトグラフィー
による１核体成分含有量、２核体成分含有量及び数平均
分子量を表−１に示す。Table 1 shows the mononuclear component content, the dinuclear component content and the number average molecular weight by high performance liquid chromatography of the four kinds of novolac phenolic resins obtained in Examples 1 and 2 and Comparative Examples 1 and 2. Show.
次に、コーテッドサンドを製造するために、温度145℃
に加熱された8000部のフラタリー珪砂をワールミキサー
に仕込み、実施例１、２及び比較例１、２のノボラック
型フェノール樹脂各192部を各々別々に添加した後、45
秒間混合した。次いでヘキサミン24部を水88部に溶解し
たヘキサミン水溶液を添加し10秒後より空冷を始め、こ
の状態で混練を30秒間行なった後、ステアリン酸カルシ
ウム８部を添加し、更に15秒間混合した。次いでワール
ミキサーより排出してレジンコーテッドサンドを得た。
得られた４種のレジンコーテッドサンドを使用して各々
の臭気濃度及び鋳型特性を下記の方法で測定し、その結
果を表−２に示す。Then, in order to produce the coated sand, the temperature is 145 ° C.
8000 parts of the flattered silica sand heated to 1 are charged into a whirl mixer, and 192 parts of each of the novolac type phenolic resins of Examples 1 and 2 and Comparative Examples 1 and 2 are added separately, and then 45
Mix for seconds. Next, an aqueous solution of hexamine in which 24 parts of hexamine was dissolved in 88 parts of water was added, and after 10 seconds, air cooling was started. After kneading for 30 seconds in this state, 8 parts of calcium stearate was added and further mixed for 15 seconds. Then, it was discharged from the whirl mixer to obtain a resin coated sand.
The odor concentration and the mold characteristics of each of the obtained four kinds of resin coated sands were measured by the following methods, and the results are shown in Table 2.
（１）臭気濃度 ４種のレジンコーテッドサンド各1gを各々別々にセラミ
ックボードに乗せ、ついで300℃に保持されたセラミッ
クの燃焼管に各々別々に挿入し、同時に清浄空気をキャ
リアーガスとして１／分の流量で10分間送り、10lの
清浄なサンプル袋に分解ガスをキャリアーガスと共に捕
集した。(1) Odor concentration 4 kinds of resin coated sand 1g each is placed on a ceramic board separately and then inserted into a ceramic combustion tube held at 300 ° C separately, and at the same time, clean air is used as a carrier gas for 1 / min. At a flow rate of 10 minutes, and the decomposition gas was collected together with the carrier gas in a clean sample bag of 10 liters.
このガスを東京都三点比較臭袋法に準じ、30倍、100
倍、300倍、1000倍、3000倍に希釈した後、６人の測定
者がこの希釈ガスを嗅ぎ臭気を感じる最高希釈倍率から
臭気濃度を統計的に計算して求めた。According to the Tokyo three-point comparison odor bag method, this gas is 30 times, 100
After doubling, diluting 300 times, diluting 1000 times, and diluting 3000 times, the odor concentration was statistically calculated from the highest dilution ratio at which 6 measurers sense the smell and smell.
（２）シェル鋳型特性 冷間曲げ強さ:JACT試験法SM−１による。造型条件2
50℃、60秒 熱間引張り強さ:JACT試験法SM−10による。造型条
件250℃、40秒 (2) Shell mold characteristics Cold bending strength: According to JACT test method SM-1. Molding condition 2
50 ° C, 60 seconds Hot tensile strength: According to JACT test method SM-10. Molding conditions 250 ℃, 40 seconds
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−103215（ＪＰ，Ａ) 特開 昭60−133017（ＪＰ，Ａ) 特開 昭62−212410（ＪＰ，Ａ) 特開 昭63−77915（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-56-103215 (JP, A) JP-A-60-133017 (JP, A) JP-A-62-212410 (JP, A) JP-A-63- 77915 (JP, A)
Claims (2)
性触媒の存在下で加熱反応させ、その後水、フェノール
類及び２核体フェノール樹脂を除去することにより、フ
ェノール樹脂中の１核体の含有量が１重量％未満であ
り、２核体の含有量が２重量％未満とすることを特徴と
するシェルモールド用ノボラック型フェノール樹脂の製
造方法。1. A phenol and a formaldehyde are heated and reacted in the presence of an acidic catalyst, and then water, the phenol and the binuclear phenol resin are removed, whereby the content of the mononuclide in the phenol resin is reduced. A method for producing a novolac-type phenol resin for shell mold, which is less than 1% by weight and the content of the binuclear body is less than 2% by weight.
であることを特徴とする特許請求範囲第１項記載のシェ
ルモールド用ノボラック型フェノール樹脂の製造方法。2. A phenol resin having a number average molecular weight of 300 to 750.
The method for producing a novolac-type phenol resin for shell mold according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291894A JPH0791352B2 (en) | 1987-11-20 | 1987-11-20 | Method for producing novolac type phenolic resin for shell mold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291894A JPH0791352B2 (en) | 1987-11-20 | 1987-11-20 | Method for producing novolac type phenolic resin for shell mold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01135814A JPH01135814A (en) | 1989-05-29 |
| JPH0791352B2 true JPH0791352B2 (en) | 1995-10-04 |
Family
ID=17774830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62291894A Expired - Lifetime JPH0791352B2 (en) | 1987-11-20 | 1987-11-20 | Method for producing novolac type phenolic resin for shell mold |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791352B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2610363B2 (en) * | 1990-10-31 | 1997-05-14 | アイシン化工株式会社 | Novolak type phenolic resin composition for shell mold |
| US6790886B2 (en) * | 1999-12-27 | 2004-09-14 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
| JP2006152075A (en) * | 2004-11-26 | 2006-06-15 | Asahi Organic Chem Ind Co Ltd | Phenol resin composite |
| JP2008169285A (en) * | 2007-01-11 | 2008-07-24 | Sumitomo Bakelite Co Ltd | Alkylbenzene-modified novolak type phenol resin, novolak type phenol resin for shell mold and resin-coated sand |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56103215A (en) * | 1980-01-21 | 1981-08-18 | Sumitomo Bakelite Co Ltd | Crystalline phenolic novolak resin |
| JPS60133017A (en) * | 1983-12-20 | 1985-07-16 | Dainippon Ink & Chem Inc | Phenolic resin for shell molding and its production |
| JPS61117413A (en) * | 1984-11-13 | 1986-06-04 | Toyota Motor Corp | Arithmetic unit for vehicle location |
| FR2572394B1 (en) * | 1984-10-30 | 1986-12-19 | Snecma | METHOD FOR MANUFACTURING A CERAMIC TURBINE RING INTEGRATED WITH AN ANNULAR METAL SUPPORT |
| US4893673A (en) * | 1984-10-31 | 1990-01-16 | Rockwell International Corporation | Entry port inserts for internally manifolded stacked, finned-plate heat exchanger |
| JPH0662731B2 (en) * | 1986-03-14 | 1994-08-17 | 旭チバ株式会社 | Production method of novolac resin |
| JPH0730151B2 (en) * | 1986-09-22 | 1995-04-05 | 日本化薬株式会社 | Method for producing phenolic novolac composition |
-
1987
- 1987-11-20 JP JP62291894A patent/JPH0791352B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01135814A (en) | 1989-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPWO2003042267A1 (en) | NOVOLAC TYPE PHENOL RESIN AND PROCESS FOR PRODUCING THE SAME | |
| JPH0798893B2 (en) | Phenolic resin composition | |
| JPH0791352B2 (en) | Method for producing novolac type phenolic resin for shell mold | |
| JPH0818102B2 (en) | Method for producing phenol-formaldehyde resin binder | |
| JP4435791B2 (en) | Method for producing novolac-type phenolic resin and resin-coated sand | |
| JPH11244991A (en) | Resin coated sand manufacturing method | |
| JPS5978745A (en) | Resin coated sand for casting | |
| JP2002102999A (en) | Resin coated sand for shell mold | |
| JP4439774B2 (en) | Novolac type phenolic resin and resin coated sand for shell mold | |
| JP4221632B2 (en) | Binder for shell mold | |
| JPH0270717A (en) | Novolac phenol resin for shell mold | |
| JP4013111B2 (en) | Method for producing resole resin | |
| JP4221633B2 (en) | Resin binder for shell mold | |
| JP2647254B2 (en) | Method for producing novolak type phenol resin for shell mold | |
| JPH11267789A (en) | Mold-forming composition and method for molding a mold using the composition | |
| JPS63132917A (en) | Production of quick-curing phenolic resin | |
| JP3249010B2 (en) | Manufacturing method of casting mold | |
| JPH01154843A (en) | Manufacture of resin coated sand for gas hardening mold | |
| JP2006095574A (en) | Phenol resin composition for shell molding and resin-coated sand for shell molding | |
| JPS61108445A (en) | Production of resin coated sand grain for shell mold | |
| JPH0764905B2 (en) | Method for producing novolac type phenolic resin for shell mold | |
| JPH03128143A (en) | Manufacture of resin coated sand granule for shell mold and itself | |
| JPS58196137A (en) | Resin coated sand for shell mold method | |
| JP2003191044A (en) | Denatured phenolic resin binder for shell mold and resin coated sand for casting using the same | |
| JPH0890151A (en) | Resin coated sand composition for shell mold |