JP2007231218A - Curing agent composition for alkali phenolic resin - Google Patents
Curing agent composition for alkali phenolic resin Download PDFInfo
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- JP2007231218A JP2007231218A JP2006057443A JP2006057443A JP2007231218A JP 2007231218 A JP2007231218 A JP 2007231218A JP 2006057443 A JP2006057443 A JP 2006057443A JP 2006057443 A JP2006057443 A JP 2006057443A JP 2007231218 A JP2007231218 A JP 2007231218A
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- phenol resin
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- phenolic resin
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 29
- 239000003513 alkali Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract 4
- 229920001568 phenolic resin Polymers 0.000 title abstract 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002596 lactones Chemical class 0.000 claims abstract description 13
- -1 γ-butyrolactone Chemical class 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical group CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 235000019645 odor Nutrition 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000000197 pyrolysis Methods 0.000 description 11
- 239000004576 sand Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 4
- PPXUHEORWJQRHJ-UHFFFAOYSA-N ethyl isovalerate Chemical compound CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 150000002895 organic esters Chemical class 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
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- TVQGDYNRXLTQAP-UHFFFAOYSA-N ethyl heptanoate Chemical compound CCCCCCC(=O)OCC TVQGDYNRXLTQAP-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- XHIUFYZDQBSEMF-UHFFFAOYSA-N 2-methylbutyl acetate Chemical compound CCC(C)COC(C)=O XHIUFYZDQBSEMF-UHFFFAOYSA-N 0.000 description 1
- ZARFDQHJMNVNLE-UITAMQMPSA-N 3-methylbutyl (z)-2-methylbut-2-enoate Chemical compound C\C=C(\C)C(=O)OCCC(C)C ZARFDQHJMNVNLE-UITAMQMPSA-N 0.000 description 1
- LJSJTXAZFHYHMM-UHFFFAOYSA-N 7-methyloctyl acetate Chemical compound CC(C)CCCCCCOC(C)=O LJSJTXAZFHYHMM-UHFFFAOYSA-N 0.000 description 1
- ZARFDQHJMNVNLE-UHFFFAOYSA-N Angelinsaeure-isoamylester Natural products CC=C(C)C(=O)OCCC(C)C ZARFDQHJMNVNLE-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ZCZSIDMEHXZRLG-UHFFFAOYSA-N acetic acid heptyl ester Natural products CCCCCCCOC(C)=O ZCZSIDMEHXZRLG-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- XAPCMTMQBXLDBB-UHFFFAOYSA-N butanoic acid hexyl ester Natural products CCCCCCOC(=O)CCC XAPCMTMQBXLDBB-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- JPXGPRBLTIYFQG-UHFFFAOYSA-N heptan-4-yl acetate Chemical compound CCCC(CCC)OC(C)=O JPXGPRBLTIYFQG-UHFFFAOYSA-N 0.000 description 1
- 150000002485 inorganic esters Chemical class 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DILOFCBIBDMHAY-UHFFFAOYSA-N methyl 2-(3,4-dimethoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(OC)C(OC)=C1 DILOFCBIBDMHAY-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- CFNJLPHOBMVMNS-UHFFFAOYSA-N pentyl butyrate Chemical compound CCCCCOC(=O)CCC CFNJLPHOBMVMNS-UHFFFAOYSA-N 0.000 description 1
- FGPPDYNPZTUNIU-UHFFFAOYSA-N pentyl pentanoate Chemical compound CCCCCOC(=O)CCCC FGPPDYNPZTUNIU-UHFFFAOYSA-N 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- Mold Materials And Core Materials (AREA)
Abstract
Description
本発明は、アルカリフェノール樹脂用硬化剤組成物に関する。 The present invention relates to a curing agent composition for an alkali phenol resin.
従来より、鋳型を製造する際に使用される粘結剤として、各種の有機系粘結剤が使用されている。その中でもアルカリフェノール樹脂は鋳物品質及び作業環境を改善しうる有機系粘結剤として、特に鋳鋼分野に多用されてきている。しかしながら、有機系であるが故に、注湯時、注湯後、及び型ばらし時に熱分解ガスによる異臭が発生し、これが環境悪化の原因となっている。これまで混練工程から造型、抜型工程、注湯、及び型ばらしにおけるホルムアルデヒドによる臭気に対しては、さまざまな提案がされてきた（例えば、特許文献１、２）。 Conventionally, various organic binders have been used as binders used in the production of molds. Among them, alkali phenol resins have been frequently used especially in the field of cast steel as an organic binder that can improve casting quality and working environment. However, because it is organic, a bad odor due to the pyrolysis gas is generated during pouring, after pouring, and when the mold is released, which causes environmental degradation. So far, various proposals have been made for the odor caused by formaldehyde in the kneading process, the molding process, the molding process, the pouring process, and the mold release (for example, Patent Documents 1 and 2).
一方、注湯時、注湯後、及び型ばらし時の熱分解ガスによる異臭を低減させることに対しては、鋳型燃焼工程に発生する特有の異臭をマスキングする方法として、例えば特許文献３、４が提案されている。
しかしながら、有機エステル硬化剤の中でもラクトン類、特にγ−ブチロラクトンは、速硬化用の硬化剤として好適であるが、エステル硬化型アルカリフェノール樹脂の硬化剤として使用した場合は、注湯時、注湯後、及び型ばらし時の熱分解ガスによる異臭が顕著であり、ラクトン類の硬化速度を維持しつつ、このような異臭を低減するという点では、特許文献１〜４の技術も十分な効果を奏さない。 However, among organic ester curing agents, lactones, particularly γ-butyrolactone, are suitable as a curing agent for fast curing. However, when used as a curing agent for ester curable alkali phenol resin, The odors due to the pyrolysis gas at the time of separation and mold release are remarkable, and the techniques of Patent Documents 1 to 4 have sufficient effects in terms of reducing such odors while maintaining the curing rate of lactones. I don't play.
本発明は、鋳型用粘結剤であるアルカリフェノール樹脂の硬化剤として、ラクトン類を用いる場合において、ラクトン類の注湯時、注湯後、及び型ばらし時の熱分解ガスによる異臭を効果的に低減できるエステル硬化型アルカリフェノール樹脂硬化剤組成物を提供することを目的とする。 The present invention is effective when a lactone is used as a curing agent for an alkali phenol resin, which is a binder for a mold, and when a lactone is poured, after the pouring, and when a mold is released, an odor due to a pyrolysis gas is effectively removed. It aims at providing the ester hardening type alkali phenol resin hardening | curing agent composition which can be reduced to this.
本発明は、ラクトン類（ａ）〔以下、（ａ）成分という〕と、１０１３２５Ｐａでの沸点が２１０℃以下の脂肪族エステル類（ｂ）〔以下、（ｂ）成分という〕と、を含有するアルカリフェノール樹脂用硬化剤組成物、及び該アルカリフェノール樹脂用硬化剤組成物を用いる鋳型の製造法に関する。なお、１０１３２５Ｐａとは、標準大気圧のことである。 The present invention contains a lactone (a) [hereinafter referred to as component (a)] and an aliphatic ester (b) having a boiling point of 210 ° C. or lower at 101325 Pa (hereinafter referred to as component (b)). The present invention relates to a curing agent composition for an alkali phenol resin and a method for producing a mold using the curing agent composition for an alkali phenol resin. Note that 101325 Pa is the standard atmospheric pressure.
本発明によれば、鋳型用粘結剤であるアルカリフェノール樹脂の硬化剤として、ラクトン類を用いる場合において、ラクトン類の注湯時、注湯後、及び型ばらし時の熱分解ガスによる異臭を効果的に低減できるエステル硬化型アルカリフェノール樹脂硬化剤組成物が提供される。 According to the present invention, when a lactone is used as a curing agent for an alkali phenol resin that is a binder for a mold, an odor caused by a pyrolysis gas at the time of pouring the lactone, after pouring, and at the time of mold release. An ester curable alkali phenol resin curing agent composition that can be effectively reduced is provided.
本発明は、アルカリフェノール樹脂を鋳型用粘結剤として用いる場合において、そのアルカリフェノール樹脂を硬化させるために使用する硬化組成物に関する。 The present invention relates to a curing composition used for curing an alkali phenol resin when the alkali phenol resin is used as a binder for a mold.
＜（ａ）成分＞
（ａ）成分としては、γ−ブチロラクトン、プロピオラクトン、ε−カプロラクトン等が挙げられる。中でも、硬化速度を低下させることなく注湯後の臭気を低減する点において、より効果的であることから、γ−ブチロラクトンが好ましい。
<(A) component>
Examples of the component (a) include γ-butyrolactone, propiolactone, ε-caprolactone, and the like. Among these, γ-butyrolactone is preferable because it is more effective in reducing the odor after pouring without reducing the curing rate.
＜（ｂ）成分＞
１０１３２５Ｐａでの沸点が２１０℃以下の脂肪族エステル類である（ｂ）成分としては、エチルアセトアセテート、ジエチルマロネート、２−メチルブチルアセテート、アミルバレレート、エチルアセテート、エチルヘプタノエート、エチルヘキサノエート、エチルオクタノエート、エチルプロピオネート、エチルイソバレレート、エチル−ｎ−ブチレート、エチルイソブチレート、ヘプチルアセテート、ヘキシルアセテート、ヘキシルブチレート、オクチルアセテート、イソアミルアセテート、イソアミルイソバレレート、イソアミル−ｎ−ブチレート、イソノニルアセテート、ｎ−アミルアセテート、ｎ−アミル−ｎ−ブチレート、ｎ−ブチルアセテート、アリルヘキサノエート、シス−３−ヘキシルアセテート、シス−３−ヘキシルブチレート、シス−３−ヘキシルヘプタノエート、シス−３−ヘキシルヘキサノエート、シス−３−ヘキシルオクタノエート、シス−３−ヘキシルプロピオネート、シス−３−ヘキシルイソバレレート、シス−３−ヘキシル−ｎ−バレレート、シス−３−ヘキシルティグレート、シス−３−ヘキシルフォーメート、シス−３−ヘキシルイソブチレート、イソアミルアンジェレート、イソアミルクロトネート、トランス−２−ヘキシルアセテート等を好ましく例示することができる。これらは２種以上を併用してもよい。中でも、異臭低減効果の観点から、エチルアセトアセテート、エチルアセテート、エチルプロピオネート、エチル−ｎ−ブチレート、エチルイソブチレート、エチルイソバレレートが好ましく、エチルアセトアセテートがより好ましい。
<(B) component>
The component (b) which is an aliphatic ester having a boiling point of not more than 210 ° C. at 101325 Pa includes ethyl acetoacetate, diethyl malonate, 2-methylbutyl acetate, amyl valerate, ethyl acetate, ethyl heptanoate, ethyl hexa Noate, ethyl octanoate, ethyl propionate, ethyl isovalerate, ethyl-n-butyrate, ethyl isobutyrate, heptyl acetate, hexyl acetate, hexyl butyrate, octyl acetate, isoamyl acetate, isoamyl isovalerate, Isoamyl-n-butyrate, isononyl acetate, n-amyl acetate, n-amyl-n-butyrate, n-butyl acetate, allyl hexanoate, cis-3-hexyl acetate, cis-3-hexyl Tyrate, cis-3-hexylheptanoate, cis-3-hexylhexanoate, cis-3-hexyloctanoate, cis-3-hexylpropionate, cis-3-hexylisovalerate, cis-3 Preferred examples include -hexyl-n-valerate, cis-3-hexyl tigrate, cis-3-hexyl formate, cis-3-hexyl isobutyrate, isoamyl angelate, isoamyl milk rotonate, trans-2-hexyl acetate can do. Two or more of these may be used in combination. Of these, ethyl acetoacetate, ethyl acetate, ethyl propionate, ethyl-n-butyrate, ethyl isobutyrate, and ethyl isovalerate are preferred, and ethyl acetoacetate is more preferred from the viewpoint of off-flavor reduction effects.
＜アルカリフェノール樹脂用硬化剤組成物＞
本発明のアルカリフェノール樹脂用硬化剤組成物は、（ａ）成分１００重量部に対して、（ｂ）成分を０．１〜５重量部、更に０．５〜４重量部、特に１〜３重量部含有することが、（ａ）成分の硬化特性を維持しつつ、すなわち速硬化用の硬化剤としての好適な効果特性を損なうことなく優れた異臭低減効果が得られる点から好ましい。なお、本発明のアルカリフェノール樹脂用硬化剤組成物中の（ａ）成分の含有量は、硬化剤としての効果を発現する観点から、８０重量％以上が好ましく、９０重量％以上がより好ましい。
<Curing agent composition for alkali phenol resin>
The curing agent composition for an alkali phenol resin of the present invention comprises 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, particularly 1 to 3 parts by weight of component (b) with respect to 100 parts by weight of component (a). It is preferable to contain by weight because the excellent odor reduction effect can be obtained while maintaining the curing characteristics of the component (a), that is, without impairing the advantageous effect characteristics as a curing agent for fast curing. In addition, 80 weight% or more is preferable and 90 weight% or more is more preferable from a viewpoint of expressing the effect as a hardening | curing agent in content of the (a) component in the hardening | curing agent composition for alkali phenol resins of this invention.
注湯時、注湯後、及び型ばらし時の熱分解ガスの中には一般にホルムアルデヒドを含んでいる。そのため作業環境を改善する目的で、従来から知られているホルムアルデヒド捕捉剤として有効なレゾルシノールを、本発明の硬化剤組成物中に１〜１０重量％、好ましくは２〜５重量％含有させることが好ましい。この範囲は、硬化速度に影響が少なく、ホルムアルデヒド低減効果に優れる点から、好ましい。 The pyrolysis gas at the time of pouring, after pouring, and at the time of mold release generally contains formaldehyde. Therefore, for the purpose of improving the working environment, 1 to 10% by weight, preferably 2 to 5% by weight, of resorcinol effective as a formaldehyde scavenger, which has been conventionally known, is contained in the curing agent composition of the present invention. preferable. This range is preferable because it has little influence on the curing rate and is excellent in the effect of reducing formaldehyde.
また、（ａ）成分、（ｂ）成分以外のエステル化合物を組成物中に配合することもできる。他のエステル化合物としては、従来より使用されてきたものを利用することが可能である。すなわち、プロピレンカーボネートのような無機エステル、炭素数１〜１０の一価もしくは多価アルコールと炭素数１〜１０の有機カルボン酸より導かれる有機エステル等が挙げられ、これらは、単独で或いは混合して用いられる。具体的にはギ酸エチル、エチレングリコールジアセテート、エチレングリコールモノアセテート、トリアセチン等の有機エステルが用いられる。 Moreover, ester compounds other than (a) component and (b) component can also be mix | blended in a composition. As other ester compounds, those conventionally used can be used. That is, inorganic esters such as propylene carbonate, organic esters derived from monohydric or polyhydric alcohols having 1 to 10 carbon atoms and organic carboxylic acids having 1 to 10 carbon atoms, and the like can be used alone or in combination. Used. Specifically, organic esters such as ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, and triacetin are used.
本発明の硬化剤組成物により硬化させるアルカリフェノール樹脂としては、例えばフェノール、クレゾール、レゾルシノール、ビスフェノールＡ、その他置換フェノールを含めたフェノール類を原料として、アルカリ性触媒のもとアルデヒド化合物等と反応させることによって得られるフェノール樹脂が挙げられる。 As an alkali phenol resin to be cured by the curing agent composition of the present invention, for example, phenols including cresol, cresol, resorcinol, bisphenol A, and other substituted phenols as raw materials are reacted with an aldehyde compound or the like under an alkaline catalyst. The phenol resin obtained by is mentioned.
公知になっている樹脂の中でも、特開平５−１９２７３７号公報等に示されている、樹脂に有機窒素化合物を含んだアルカリフェノール樹脂がホルムアルデヒドを低減するのに効果的であるため好ましい。 Among known resins, an alkali phenol resin containing an organic nitrogen compound in the resin as shown in JP-A-5-192737 is preferable because it is effective for reducing formaldehyde.
本発明の硬化剤組成物を用いて鋳型を製造する方法としては、いわゆる自硬性鋳型造型法を採用することが好ましい。具体的には、本発明の硬化剤組成物と鋳物砂とアルカリフェノール樹脂とを均一に混練し、抜型することにより鋳型を製造することができる。この場合、上記の通り、特開平５−１９２７３７号公報に開示されているように、有機含窒素化合物を混練時に存在させることが好ましい。 As a method for producing a mold using the curing agent composition of the present invention, it is preferable to employ a so-called self-hardening mold making method. Specifically, the mold can be produced by uniformly kneading and removing the curing agent composition of the present invention, foundry sand and alkali phenol resin. In this case, as described above, as disclosed in JP-A-5-192737, it is preferable that an organic nitrogen-containing compound is present during kneading.
実施例１
＜鋳型の製造＞
γ−ブチロラクトンを９４重量％、エチルアセトアセテート（１０１３２５Ｐａでの沸点１８１℃）を２重量％、及びレゾルシノールを４重量％含有する硬化剤組成物を得た。次に、骨材として珪砂（カケツフセン５号新砂）１００重量部に対して、アルカリフェノール樹脂（花王クエーカー株式会社製 カオーステップＳ−６６２）１．５重量部、及び前述の硬化剤組成物０．３重量部を添加し、混練機にて各々６０秒間混練し、混練砂を得た。混練砂を木型に充填し、硬化後、階段状試験片（図１）鋳型を得た。
Example 1
<Manufacture of mold>
A curing agent composition containing 94% by weight of γ-butyrolactone, 2% by weight of ethyl acetoacetate (boiling point 181 ° C. at 101325 Pa) and 4% by weight of resorcinol was obtained. Next, 1.5 parts by weight of an alkali phenol resin (Kao Step S-662 manufactured by Kao Quaker Co., Ltd.) and 100 parts by weight of the above-mentioned curing agent composition with respect to 100 parts by weight of silica sand (Kakatsufusen No. 5 new sand). 3 parts by weight was added and kneaded for 60 seconds in a kneader to obtain kneaded sand. The kneaded sand was filled into a wooden mold, and after curing, a stepped test piece (FIG. 1) mold was obtained.
＜臭気指数の測定及び臭気の評価＞
鋳型内に材質ＦＣ−２５０の熔湯を注湯温度１４２０℃、注湯所要時間約７秒間で注湯した。尚、Ｓ／Ｍ（サンドメタル）比は３であった。注湯１分後、上部面中央に１５０ｍｍ（Ｗ）×１５０ｍｍ（Ｄ）の穴のあいた、１０００ｍｍ（Ｗ）×１０００ｍｍ（Ｄ）×１０００（Ｈ）ｍｍの木枠箱をかぶせ、その２分後に該穴部より、サンプリング用ポンプにて３Ｌテドラーバッグに熱分解ガスをサンプリングした。パネラー５人による３点比較式におい袋法による官能試験により、各鋳型から発生した熱分解ガスの臭気指数を求めた。また、この鋳造の際、注湯後の鋳型から発生する臭気をパネラーが木枠箱上部の穴から嗅いだ時の印象を定性的に評価した。結果を表１に示す。
<Measurement of odor index and evaluation of odor>
A molten metal of material FC-250 was poured into the mold at a pouring temperature of 1420 ° C. and a pouring time of about 7 seconds. The S / M (sand metal) ratio was 3. After 1 minute of pouring, a 1000 mm (W) x 1000 mm (D) x 1000 (H) mm wooden frame box with a hole of 150 mm (W) x 150 mm (D) in the center of the upper surface was placed, and 2 minutes later From this hole, the pyrolysis gas was sampled into a 3 L Tedlar bag with a sampling pump. The odor index of the pyrolysis gas generated from each mold was obtained by a sensory test by a three-point comparison type smell bag method by five panelists. In addition, during this casting, the impression when the panel sniffs the odor generated from the mold after pouring from the hole in the upper part of the crate box was qualitatively evaluated. The results are shown in Table 1.
比較例１
骨材として珪砂（カケツフセン５号新砂）１００重量部に対して、アルカリフェノール樹脂（花王クエーカー株式会社製 カオーステップ Ｓ−６６２）１．５重量部、及びγ−ブチロラクトン０．３重量部添加し、混練機にて各々６０秒間混練し、混練砂を得た。実施例１と同様にして臭気指数と臭気を評価した。結果を表１に示す。
Comparative Example 1
As an aggregate, 100 parts by weight of silica sand (Kakatsufusen No. 5 new sand), 1.5 parts by weight of an alkali phenol resin (Kao Step S-662 manufactured by Kao Quaker Co., Ltd.) and 0.3 parts by weight of γ-butyrolactone are added, Each kneading machine kneaded for 60 seconds to obtain kneaded sand. The odor index and odor were evaluated in the same manner as in Example 1. The results are shown in Table 1.
（＊）臭気指数は以下の意味を持つ。
３０：熱分解ガスが１，０００倍希釈まで臭気を感じる
４０：熱分解ガスが１０，０００倍希釈まで臭気を感じる
５０：熱分解ガスが１００，０００倍希釈まで臭気を感じる
(*) Odor index has the following meaning.
30: Pyrolysis gas feels odor up to 1,000 times dilution 40: Pyrolysis gas feels odor up to 10,000 times dilution 50: Pyrolysis gas feels odor up to 100,000 times dilution
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| US10427212B2 (en) | 2015-12-18 | 2019-10-01 | Ha-International, Llc | Compositions and methods for modified ester-curatives and reduction of formaldehyde emission and odor in ester-cured phenolic binder systems |
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