JP5089935B2 - Furan resin composition for mold production - Google Patents
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Description
本発明は、鋳型等を製造する際、耐火性粒状材料に添加するために使用するフラン樹脂組成物に関するものである。 The present invention relates to a furan resin composition used for adding to a refractory granular material when a mold or the like is produced.
自硬性鋳型は、珪砂等の耐火性粒状材料に、フルフリルアルコール等の酸硬化性樹脂からなる結合剤とリン酸やベンゼンスルホン酸等の硬化剤を添加混練した後、この混練砂を型に充填し、結合剤を硬化させて製造される。しかし、フルフリルアルコールを主体とする結合剤は、硬化速度、鋳型強度が低くなるという傾向があり、これを改善するために、尿素を共縮合した尿素・ホルマリン変性フラン樹脂が一般的に用いられている（非特許文献１）。 The self-hardening mold is prepared by adding and kneading a binder made of an acid-curable resin such as furfuryl alcohol and a curing agent such as phosphoric acid or benzenesulfonic acid to a fire-resistant granular material such as silica sand, and then using this kneaded sand as a mold. Manufactured by filling and curing the binder. However, binders mainly composed of furfuryl alcohol tend to have low curing speed and low mold strength. To improve this, urea-formalin-modified furan resin co-condensed with urea is generally used. (Non-Patent Document 1).
更に、酸硬化性樹脂を含む粘結剤組成物の硬化特性を改善するために、種々の方策が提案されている。例えば、特許文献１には、尿素、グリオキサール、ホルムアルデヒドを特定の比率で反応させた組成物とフルフリルアルコールとを併用した鋳物砂用粘結剤が開示されている。また、特許文献２には、酸硬化性化合物とフェノール誘導体と水とを特定比率で含有する鋳物砂用粘結剤組成物が開示されている。また、特許文献３には、酸硬化性樹脂からなる結合剤を主体とする鋳型製造用粘結剤組成物に、特定の硬化促進剤を含有させることが開示されている。また、特許文献４には、フルフリルアルコールを主成分として重縮合して得られる鋳型製造用粘結剤組成物に、特定の硬化促進剤を含有させることが開示されている。
上記の通り、自硬性鋳型用の粘結剤として用いられるフラン樹脂は、通常、フルフリルアルコールに、尿素やホルムアルデヒドを共縮合して得られるが、鋳型製造時の作業環境改善の点から、フラン樹脂中のホルムアルデヒド濃度を低減することが望ましい。この目的には、フラン樹脂製造工程中に未反応ホルムアルデヒドを低減することが考えられるが、工程が複雑になり、工業的に適当とは言い難い。また、尿素やレゾルシンなどの、ホルムアルデヒド捕捉剤を配合することも考えられるが、これらの化合物は溶解性や安定性が悪いため、粘結剤に濁りや沈殿が生ずる。 As described above, furan resins used as binders for self-hardening molds are usually obtained by co-condensing furfuryl alcohol with urea or formaldehyde. From the viewpoint of improving the working environment during mold production, It is desirable to reduce the formaldehyde concentration in the resin. For this purpose, it is conceivable to reduce unreacted formaldehyde during the furan resin production process, but the process becomes complicated and is not industrially suitable. In addition, it is conceivable to add a formaldehyde scavenger such as urea or resorcin, but these compounds have poor solubility and stability, so that the binder becomes cloudy and precipitates.
本発明の課題は、フルフリルアルコールを主成分として得られるフラン樹脂組成物において、保存安定性を損なうことなく、作業環境を改善できる鋳型製造用のフラン樹脂組成物を提供することである。 The subject of this invention is providing the furan resin composition for mold manufacture which can improve a working environment in the furan resin composition obtained by making a furfuryl alcohol into a main component, without impairing storage stability.
本発明は、一般式（１）〜（４）で表される化合物の１種又は２種以上を含有する鋳型製造用フラン樹脂組成物に関する。 The present invention relates to a furan resin composition for mold production containing one or more of the compounds represented by the general formulas (1) to (4).
〔式中、Ｒ1、Ｒ2は、それぞれ、炭素数１〜５の直鎖もしくは分岐鎖の脂肪族炭化水素基、又は炭素数６〜１０の芳香族炭化水素基、Ｘは水素原子、炭素数１〜５の直鎖もしくは分岐鎖の脂肪族炭化水素基、又は炭素数６〜１０の芳香族炭化水素基を示す。〕 [Wherein, R 1 and R 2 are each a linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X is a hydrogen atom, carbon A linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is shown. ]
また、本発明は、上記本発明の鋳型製造用フラン樹脂組成物を含有する鋳型製造用粘結剤組成物、及び、該鋳型製造用粘結剤組成物を用いる鋳型の製造方法に関する。 Moreover, this invention relates to the manufacturing method of the casting_mold | template using the binder composition for mold manufacture containing the furan resin composition for mold manufacture of the said invention, and this binder composition for mold manufacture.
本発明によれば、沈殿の生成等の保存安定性を損なうことなく、作業環境を改善できる、鋳型製造用フラン樹脂組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the furan resin composition for casting_mold | template manufacture which can improve a work environment, without impairing storage stability, such as the production | generation of precipitation, is provided.
本発明に係る鋳型製造用フラン樹脂組成物は、フルフリルアルコールを主成分として重縮合して得られるものである。例えば、「第４版鋳型造型法」（平成８年１１月１８日、社団法人日本鋳造技術協会発行）の１３５頁等に記載されている通り、フルフリルアルコールと尿素とアルデヒド類とを主成分として、重縮合して得られるものである。アルデヒド類としては、ホルムアルデヒド、グリオキザール、フルフラール等の従来公知のアルデヒド化合物を使用することができる。特に、本発明においては、ホルムアルデヒドを使用するのが好ましい。フルフリルアルコール、尿素、及びアルデヒド類を重縮合させると、各成分の配合割合にもよるが、フルフリルアルコールの縮合物、フルフリルアルコールとアルキロール尿素との重縮合物、尿素とアルデヒド類の縮合物、各縮合物が更に重縮合した重縮合物、各成分の未反応物、水等の混合物が得られる。 The furan resin composition for mold production according to the present invention is obtained by polycondensation containing furfuryl alcohol as a main component. For example, as described on page 135 of “4th edition mold making method” (November 18, 1996, issued by Japan Foundry Technology Association), etc., furfuryl alcohol, urea and aldehydes are the main components. Are obtained by polycondensation. As aldehydes, conventionally known aldehyde compounds such as formaldehyde, glyoxal, and furfural can be used. In particular, it is preferable to use formaldehyde in the present invention. When polycondensation of furfuryl alcohol, urea, and aldehydes, depending on the blending ratio of each component, condensate of furfuryl alcohol, polycondensation product of furfuryl alcohol and alkylol urea, urea and aldehydes A mixture of a condensate, a polycondensate obtained by further polycondensation of each condensate, an unreacted product of each component, water and the like is obtained.
本発明は、一般式（１）〜（４）で表される化合物をフラン樹脂組成物に含有させることに特徴があり、これらの化合物を含有することにより、フラン樹脂組成物の保存安定性が向上し、また、作業環境（フラン樹脂組成物中のホルムアルデヒドの低減）を改善できる。本発明の効果が発現する理由は定かではないが、本発明の一般式（１）〜（４）で表される化合物が活性メチレン基を有する構造である等によって、フラン樹脂組成物中のホルムアルデヒドの低減に寄与するために本発明の効果が発現するものと考えられる。一般式（１）〜（４）で表される化合物の具体例としては、アセト酢酸エチル、マロン酸ジエチル、マロン酸ジメチル、マロン酸ジ−ｔ−ブチル、マロン酸ジベンジル、グルコール酸エチル、メトキシ酢酸メチルエステル、メトキシ酢酸エチルエステル、アセチルアセトン等が例示される。好ましくはアセト酢酸エチル、マロン酸ジエチル、アセチルアセトンである。 The present invention is characterized in that the compounds represented by the general formulas (1) to (4) are contained in the furan resin composition. By containing these compounds, the storage stability of the furan resin composition is improved. And the working environment (reduction of formaldehyde in the furan resin composition) can be improved. The reason why the effects of the present invention are manifested is not clear, but the formaldehyde in the furan resin composition depends on the compounds represented by the general formulas (1) to (4) of the present invention having a structure having an active methylene group. It is considered that the effect of the present invention is manifested in order to contribute to the reduction of the above. Specific examples of the compounds represented by the general formulas (1) to (4) include ethyl acetoacetate, diethyl malonate, dimethyl malonate, di-t-butyl malonate, dibenzyl malonate, ethyl glycolate, methoxyacetic acid Examples include methyl ester, methoxyacetic acid ethyl ester, acetylacetone and the like. Preferred are ethyl acetoacetate, diethyl malonate, and acetylacetone.
本発明のフラン樹脂組成物中の一般式（１）〜（４）で表される化合物の含有量は、１〜１０重量％、更に２〜６重量％が好ましい。 The content of the compounds represented by the general formulas (1) to (4) in the furan resin composition of the present invention is preferably 1 to 10% by weight, more preferably 2 to 6% by weight.
本発明のフラン樹脂組成物により、これを含有する鋳型製造用粘結剤を提供できる。更に本発明のフラン樹脂組成物と硬化剤とを併用することで、鋳型製造用粘結剤を構成することができる。本発明に係るフラン樹脂組成物を用いて鋳型を製造する場合、この樹脂組成物を硬化させるための硬化剤としては、従来公知の燐酸系化合物やスルホン酸系化合物等の硬化剤を使用することができる。また、粘結剤における硬化剤の比率は、フラン樹脂組成物１００重量部に対して１０〜６０重量部が好ましく、１５〜４０重量部が好ましい。 The furan resin composition of the present invention can provide a binder for producing a mold containing the same. Furthermore, the binder for mold manufacture can be comprised by using together the furan resin composition of this invention, and a hardening | curing agent. When producing a mold using the furan resin composition according to the present invention, a conventionally known curing agent such as a phosphoric acid compound or a sulfonic acid compound should be used as a curing agent for curing the resin composition. Can do. Moreover, 10-60 weight part is preferable with respect to 100 weight part of furan resin compositions, and, as for the ratio of the hardening | curing agent in a binder, 15-40 weight part is preferable.
燐酸系化合物としては、燐酸、縮合燐酸、メチル燐酸やエチル燐酸等の燐酸エステル、燐酸カリウムや燐酸水素カリウム等の燐酸塩等が用いられる。また、スルホン酸系化合物としては、メタンスルホン酸やエタンスルホン酸等の脂肪族スルホン酸、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、フェノールスルホン酸等の芳香族スルホン酸、硫酸等の無機酸等が用いられる。 Examples of the phosphoric acid compound include phosphoric acid, condensed phosphoric acid, phosphoric acid esters such as methyl phosphoric acid and ethyl phosphoric acid, and phosphoric acid salts such as potassium phosphate and potassium hydrogen phosphate. Examples of the sulfonic acid compounds include aliphatic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, and phenolsulfonic acid, and inorganic acids such as sulfuric acid. Etc. are used.
上記の通り、本発明のフラン樹脂組成物は、硬化剤と併用して粘結剤組成物として用いることができるが、下記一般式（５）で表される化合物、〔以下、硬化促進剤（５）という〕及び、水酸基に対してオルト位又はパラ位の電荷密度を高める置換基を有するフェノール誘導体〔以下、硬化促進剤（６）という〕からなる群より選ばれる少なくとも１種の硬化促進剤を更に使用することで、鋳型強度、硬化速度などの硬化特性を損なうことのない鋳型製造用粘結剤組成物が得られる。 As described above, the furan resin composition of the present invention can be used as a binder composition in combination with a curing agent. However, a compound represented by the following general formula (5), [hereinafter, a curing accelerator ( 5)] and at least one curing accelerator selected from the group consisting of phenol derivatives having a substituent that increases the charge density at the ortho or para position relative to the hydroxyl group (hereinafter referred to as curing accelerator (6)). By further using, a binder composition for mold production that does not impair the curing properties such as mold strength and curing speed can be obtained.
〔式中、Ｘ1及びＸ2は、それぞれ水素原子、ＣＨ3又はＣ2Ｈ5の何れかを表す。〕
[Wherein, X 1 and X 2 each represent a hydrogen atom, CH 3 or C 2 H 5 . ]
硬化促進剤（５）としては、２，５−ビスヒドロキシメチルフラン、２，５−ビスメトキシメチルフラン、２，５−ビスエトキシメチルフラン、２−ヒドロキシメチル−５−メトキシメチルフラン、２−ヒドロキシメチル−５−エトキシメチルフラン、２−メトキシメチル−５−エトキシメチルフランが挙げられる。中でも、２，５−ビスヒドロキシメチルフランを使用するのが好ましい。２，５−ビスヒドロキシメチルフランは、２，５−ビスメトキシメチルフラン又は２，５−ビスエトキシメチルフランに比べて、反応性が高く、フルフリルアルコールを主成分として重縮合されてなるフラン樹脂の硬化反応を促進させるからである。２，５−ビスヒドロキシメチルフランの反応性が高い理由は、水酸基が硬化反応に寄与するからである。硬化促進剤（５）は、樹脂１００重量部に対して０．５〜１５重量部、更に１〜１０重量部、特に２〜５重量部含有されることが、鋳型の初期強度の向上効果と硬化促進剤（５）の粘結剤組成物への溶解性の点から、好ましい。 As the curing accelerator (5), 2,5-bishydroxymethylfuran, 2,5-bismethoxymethylfuran, 2,5-bisethoxymethylfuran, 2-hydroxymethyl-5-methoxymethylfuran, 2-hydroxy Examples include methyl-5-ethoxymethylfuran and 2-methoxymethyl-5-ethoxymethylfuran. Among these, 2,5-bishydroxymethylfuran is preferably used. 2,5-bishydroxymethylfuran has higher reactivity than 2,5-bismethoxymethylfuran or 2,5-bisethoxymethylfuran, and is a furan resin obtained by polycondensation with furfuryl alcohol as a main component. This is because it accelerates the curing reaction. The reason why the reactivity of 2,5-bishydroxymethylfuran is high is that the hydroxyl group contributes to the curing reaction. The hardening accelerator (5) is contained in an amount of 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, particularly 2 to 5 parts by weight, based on 100 parts by weight of the resin. From the viewpoint of solubility of the curing accelerator (5) in the binder composition, it is preferable.
また、硬化促進剤（６）は、フェノールの水酸基に対して、オルト位又はパラ位の電荷密度を高める置換基を有する化合物であり、例えばレゾルシノール、クレゾール、ヒドロキノン、フロログルシノール、メチレンビスフェノール等が挙げられる。なかでも、レゾルシノール、フロログルシノールが好ましい。硬化促進剤（６）は、樹脂１００重量部に対して０．２〜１０重量部、更に０．５〜５重量部、特に１〜３重量部含有されることが、鋳型の初期強度の向上効果と硬化促進剤（６）の粘結剤組成物への溶解性の点から、好ましい。 The curing accelerator (6) is a compound having a substituent that increases the charge density at the ortho-position or para-position with respect to the hydroxyl group of phenol. For example, resorcinol, cresol, hydroquinone, phloroglucinol, methylene bisphenol, etc. Can be mentioned. Of these, resorcinol and phloroglucinol are preferable. The hardening accelerator (6) is contained in an amount of 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, particularly 1 to 3 parts by weight, based on 100 parts by weight of the resin. From the point of the effect and the solubility to the binder composition of a hardening accelerator (6), it is preferable.
上記した粘結剤組成物と、硬化剤とを耐火性粒状材料に混練して混練砂（鋳型製造用砂組成物）を得る。耐火性粒状材料としては、石英質を主成分とする珪砂、クロマイト砂、ジルコン砂、オリビン砂、アルミナ砂、ムライト砂、合成ムライト砂等の新砂又は再生砂等の従来公知のものを用いることができる。再生砂としては、通常の機械的磨耗式、或いは焙焼式で得られるものを使用するが、磨耗式で再生されたものの方が収率も高く、経済的に優れ、一般的であり好ましい。 The above-mentioned binder composition and curing agent are kneaded into a refractory granular material to obtain kneaded sand (sand composition for mold production). As the refractory granular material, conventionally known materials such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, synthetic mullite sand, etc., mainly composed of quartz are used. it can. As the reclaimed sand, those obtained by a normal mechanical wear type or roasting type are used, but those regenerated by the wear type have a higher yield, are economically superior, are general and preferred.
また、混練砂（鋳型製造用砂組成物）を得る際に、粘結剤組成物及び硬化剤の他に、得られる鋳型強度をより向上させる目的で、シランカップリング剤を添加してもよい。シランカップリング剤としては、例えばγ−（２−アミノ）アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン等が挙げられる。また、シランカップリング剤は、予め粘結剤組成物中に含有させておいて使用してもよい。 Moreover, when obtaining kneaded sand (sand composition for mold production), in addition to the binder composition and the curing agent, a silane coupling agent may be added for the purpose of further improving the obtained mold strength. . Examples of the silane coupling agent include γ- (2-amino) aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like. . Further, the silane coupling agent may be used by previously containing it in the binder composition.
このようにして得られた鋳型製造用砂組成物を用いて、一般的に自硬性鋳型製造法で鋳型を製造することができる。即ち、鋳型製造用砂組成物を所定の型に充填し、配合混練されている鋳型製造用粘結剤組成物を、硬化剤の作用によって硬化させ、鋳型を得ることができる。なお、混練、鋳型の製造、硬化温度等は、特に加熱や冷却の必要はなく、雰囲気温度で行って差し支えない。 A mold can be generally produced by a self-hardening mold production method using the sand composition for mold production thus obtained. In other words, a mold can be obtained by filling a predetermined mold with the mold-producing sand composition and curing the compounded binder composition for mold production by the action of a curing agent. The kneading, mold production, curing temperature and the like are not particularly required to be heated or cooled, and may be performed at ambient temperature.
２５℃、５０％ＲＨの条件下で、フリーマントル珪砂の新砂１００重量部に対し、硬化剤組成物（硫酸／m−キシレン−４−スルホン酸／水＝４／２６／７０）を０．４重量部加え、次いで表１に示した組成のフラン樹脂組成物０．８重量部を添加混合して得られた混練砂をテストピース枠に充填し、直径５０ｍｍ、高さ５０ｍｍの円柱形のテストピースを作成した。ＪＩＳ Ｚ ２６０４−１９７６に記載された方法で、３０分および２４時間後のテストピースの圧縮強度（ＭＰａ）を測定したところ、表１に示すとおりであった。また、鋳物材料ＦＣ−２５（Ｓ／Ｍ＝３．５）によりステップコーンを造型、鋳込みをしたときの、造型時の臭気（刺激）についての評価結果、並びに、フラン樹脂組成物を３５℃で１ヶ月保存（密閉系）した後の外観を目視で観察した結果（安定性）も表１に併せて示す。 Under the conditions of 25 ° C. and 50% RH, the hardener composition (sulfuric acid / m-xylene-4-sulfonic acid / water = 4/26/70) is 0.4 per 100 parts by weight of fresh mantle silica sand. The test piece frame was filled with kneaded sand obtained by adding 0.8 parts by weight of the furan resin composition having the composition shown in Table 1 and mixing them, and testing the cylindrical shape with a diameter of 50 mm and a height of 50 mm. Created a piece. When the compressive strength (MPa) of the test piece after 30 minutes and 24 hours was measured by the method described in JIS Z 2604-1976, it was as shown in Table 1. Moreover, the evaluation result about the odor (stimulation) at the time of molding, and the furan resin composition at 35 ° C. when the step cone was molded and cast with the casting material FC-25 (S / M = 3.5). Table 1 also shows the results (stability) of visual observation of the appearance after storage for 1 month (sealed system).
表中、硬化剤組成物の重量部は、フリーマントル珪砂（新砂）１００重量部に対する比率である。また、フラン樹脂は、フルフリルアルコール５０．３重量％、フルフリルアルコール／ホルムアルデヒド重縮合物１２．５重量％、尿素／ホルムアルデヒド重縮合物１０．２重量％を含有する。 In the table, parts by weight of the curing agent composition is a ratio to 100 parts by weight of Fremantle quartz sand (fresh sand). The furan resin contains 50.3% by weight of furfuryl alcohol, 12.5% by weight of furfuryl alcohol / formaldehyde polycondensate, and 10.2% by weight of urea / formaldehyde polycondensate.
Claims (5)
下記一般式（５）で表される化合物〔以下、硬化促進剤（５）という〕、及び、水酸基に対してオルト位又はパラ位の電荷密度を高める置換基を有するフェノール誘導体〔以下、硬化促進剤（６）という〕からなる群より選ばれる少なくとも１種の硬化促進剤、
を含有する鋳型製造用粘結剤組成物。
〔式中、Ｒ1、Ｒ2は、それぞれ、炭素数１〜５の直鎖もしくは分岐鎖の脂肪族炭化水素基、又は炭素数６〜１０の芳香族炭化水素基、Ｘは水素原子、炭素数１〜５の直鎖もしくは分岐鎖の脂肪族炭化水素基、又は炭素数６〜１０の芳香族炭化水素基を示す。〕
〔式中、Ｘ1及びＸ2は、それぞれ水素原子、ＣＨ3又はＣ2Ｈ5の何れかを表す。〕 A furan resin composition for mold production containing one or more of the compounds represented by the general formulas (1) to (4), and
A compound represented by the following general formula (5) [hereinafter referred to as a curing accelerator (5)] and a phenol derivative having a substituent that increases the charge density at the ortho-position or para-position relative to the hydroxyl group [hereinafter referred to as curing acceleration] At least one curing accelerator selected from the group consisting of] (referred to as agent (6)),
A binder composition for producing a mold, comprising:
[Wherein, R 1 and R 2 are each a linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X is a hydrogen atom, carbon A linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is shown. ]
[Wherein, X 1 and X 2 each represent a hydrogen atom, CH 3 or C 2 H 5 . ]
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| KR101175837B1 (en) | 2009-11-05 | 2012-08-24 | 코오롱인더스트리 주식회사 | Furan resin composition, furan resin-hardener composition, and foundry sand molds of the same |
| KR101444046B1 (en) * | 2010-12-14 | 2014-09-23 | 카오카부시키가이샤 | Binder composition for mold making purposes |
| MY180869A (en) | 2010-12-27 | 2020-12-10 | Kao Corp | Binder composition for making foundry molds |
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