CN116234647A - Adhesive composition for casting mold - Google Patents

Adhesive composition for casting mold Download PDF

Info

Publication number
CN116234647A
CN116234647A CN202080105309.0A CN202080105309A CN116234647A CN 116234647 A CN116234647 A CN 116234647A CN 202080105309 A CN202080105309 A CN 202080105309A CN 116234647 A CN116234647 A CN 116234647A
Authority
CN
China
Prior art keywords
mass
component
binder composition
content
composition
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.)
Pending
Application number
CN202080105309.0A
Other languages
Chinese (zh)
Inventor
山口大典
松尾俊树
田中大喜
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
Publication of CN116234647A publication Critical patent/CN116234647A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

The present invention provides a binder composition for mold shaping, which contains furanmethanol (component A), dimethylolfuran (component B), resin (component C) and water (component D) and satisfies the following conditions (1) to (5). Condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less; condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less; condition (3): the content of the component B in the binder composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C; condition (4): the nitrogen content in the component C is 2.7 mass% or more and 22.0 mass% or less; condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied: 2.97x+15.2.ltoreq.y (1). According to the present invention, a binder composition having a low content of monomeric furanmethanol, which can greatly improve the mold strength in a low-temperature environment, can be provided.

Description

铸模造型用粘结剂组合物Binder composition for casting mold

技术领域Technical Field

本发明涉及一种铸模造型用粘结剂组合物。The present invention relates to a binder composition for casting molds.

背景技术Background Art

一般而言,酸固化性铸模通过如下方式制造:向硅砂等耐火性粒子中添加含有酸固化性树脂的铸模造型用粘结剂组合物及含有磺酸、硫酸、磷酸等的固化剂组合物,将这些进行混炼后,将所获得的混炼砂填充至木模等原模,使酸固化性树脂固化。酸固化性树脂使用呋喃树脂、酚树脂等,呋喃树脂使用呋喃甲醇-尿素-甲醛树脂、呋喃甲醇-甲醛树脂、呋喃甲醇-苯酚-甲醛树脂、其他公知的改性呋喃树脂等。这种铸模的制造方法可进行自由度高的造型作业,另外,铸模的热性能优异,因此可制造高品质的铸件,因此广泛用于铸造机械部件、建筑机械部件、或者汽车用部件等铸件。Generally speaking, acid curing casting mold is manufactured in the following manner: adding a casting mold molding binder composition containing acid curing resin and a curing agent composition containing sulfonic acid, sulfuric acid, phosphoric acid, etc. to refractory particles such as silica sand, after these are mixed, the mixed sand obtained is filled into the original mold such as wooden mold to solidify the acid curing resin. Acid curing resin uses furan resin, phenol resin, etc., and furan resin uses furan methanol-urea-formaldehyde resin, furan methanol-formaldehyde resin, furan methanol-phenol-formaldehyde resin, other known modified furan resins, etc. The manufacturing method of this casting mold can carry out a high degree of freedom molding operation, and in addition, the thermal performance of the casting mold is excellent, so high-quality castings can be manufactured, so it is widely used in castings such as casting machinery parts, construction machinery parts, or automotive parts.

制造铸模的一个重要条件是改善铸模制造时(树脂固化时)的作业环境,尤其是,为了减少制造铸模时挥发的呋喃甲醇,期望减少呋喃树脂中的单体状的呋喃甲醇。An important condition for manufacturing a mold is to improve the working environment during mold manufacturing (during resin curing). In particular, in order to reduce furan carbinol volatilized during mold manufacturing, it is desirable to reduce monomeric furan carbinol in furan resin.

例如,日本特表2014-501175号公报中公开有如下内容:通过使用单体状的呋喃甲醇的含量少的粘结剂组合物,可减少混炼时、铸模造型时呋喃甲醇及甲醛的释放。For example, Japanese Patent Publication No. 2014-501175 discloses that the release of furanol and formaldehyde during kneading and molding can be reduced by using a binder composition having a low content of monomeric furanol.

另外,日本特开昭56-61420号公报中公开有一种单体状的呋喃甲醇的含量少的铸模造型用苯酚-呋喃甲醇-甲醛树脂的制造方法,该制造方法通过充分地进行反应来将呋喃甲醇骨架以高的比例导入至树脂结构中。Japanese Patent Application Laid-Open No. 56-61420 discloses a method for producing a phenol-furancarbinol-formaldehyde resin for mold making having a low content of monomeric furancarbinol, wherein the furancarbinol skeleton is introduced into the resin structure at a high ratio by sufficiently reacting the resin.

进而,日本特开2013-151019号公报中公开有如下内容:通过使用含有5-羟甲基糠醛、2,5-双羟甲基呋喃来代替呋喃甲醇的粘结剂组合物,可在相同可使用时间下缩短脱模时间,从而提高铸模生产性,且提高固化速度及铸模强度。Furthermore, Japanese Patent Application Laid-Open No. 2013-151019 discloses that by using a binder composition containing 5-hydroxymethylfurfural and 2,5-bishydroxymethylfuran instead of furanol, the mold release time can be shortened at the same usable time, thereby improving mold productivity, and increasing the curing speed and mold strength.

发明内容Summary of the invention

本发明是一种铸模造型用粘结剂组合物,其含有呋喃甲醇(成分A)、双羟甲基呋喃(成分B)、树脂(成分C)及水(成分D),且The present invention is a binder composition for casting, which contains furanol (component A), bishydroxymethyl furan (component B), resin (component C) and water (component D), and

满足下述条件(1)~(5)。The following conditions (1) to (5) are met.

条件(1):上述铸模造型用粘结剂组合物中的上述成分A的含量为30.0质量%以下Condition (1): The content of the component A in the binder composition for casting molds is 30.0% by mass or less

条件(2):上述铸模造型用粘结剂组合物中的上述成分D的含量为25.0质量%以下Condition (2): The content of the component D in the mold-forming binder composition is 25.0% by mass or less

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the binder composition for casting molds is 39.0 mass % or more and 95.0 mass % or less relative to the total content of the component B and the component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

另外,本发明是一种铸模造型用组合物,其含有上述铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。The present invention also provides a composition for casting molds, comprising the above-mentioned binder composition for casting molds and a curing agent composition containing a curing agent for curing the binder composition for casting molds.

另外,本发明是一种铸模用组合物,其含有耐火性粒子、上述铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。The present invention also provides a casting mold composition comprising refractory particles, the above-mentioned casting mold binder composition, and a curing agent composition containing a curing agent for curing the casting mold binder composition.

另外,本发明是一种铸模的制造方法,其包括:混合工序,其将耐火性粒子、上述铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物混合,获得铸模用组合物;及固化工序,其将上述铸模用组合物装入模框,并使该铸模用组合物固化。In addition, the present invention is a method for manufacturing a casting mold, which includes: a mixing step, in which refractory particles, the above-mentioned binder composition for casting mold shaping, and a curing agent composition containing a curing agent that cures the binder composition for casting mold shaping are mixed to obtain a casting mold composition; and a curing step, in which the above-mentioned casting mold composition is loaded into a mold frame and the casting mold composition is cured.

具体实施方式DETAILED DESCRIPTION

关于以往提出的单体状的呋喃甲醇的含量少的粘结剂组合物,其铸模强度、尤其是低温(例如5℃以下)环境下的铸模强度不充分,有改善的余地。Conventionally proposed binder compositions containing a small amount of monomeric furanol have insufficient mold strength, particularly mold strength in a low temperature environment (eg, 5° C. or less), and there is room for improvement.

本发明提供一种可大幅提高低温环境下的铸模强度且单体状的呋喃甲醇的含量少的铸模造型用粘结剂组合物、铸模造型用组合物、及铸模用组合物、以及铸模的制造方法。The present invention provides a binder composition for mold making, a composition for mold making, a composition for mold making, and a method for producing a mold, which can significantly improve the mold strength in a low temperature environment and have a low content of furanol as a single substance.

本发明是一种铸模造型用粘结剂组合物,其含有呋喃甲醇(成分A)、双羟甲基呋喃(成分B)、树脂(成分C)及水(成分D),且The present invention is a binder composition for casting, which contains furanol (component A), bishydroxymethyl furan (component B), resin (component C) and water (component D), and

满足下述条件(1)~(5)。The following conditions (1) to (5) are met.

条件(1):上述铸模造型用粘结剂组合物中的上述成分A的含量为30.0质量%以下Condition (1): The content of the component A in the binder composition for casting molds is 30.0% by mass or less

条件(2):上述铸模造型用粘结剂组合物中的上述成分D的含量为25.0质量%以下Condition (2): The content of the component D in the mold-forming binder composition is 25.0% by mass or less

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the above-mentioned binder composition for casting molds is 39.0 mass % or more and 95.0 mass % or less relative to the total content of the above-mentioned component B and the above-mentioned component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

另外,本发明是一种铸模造型用组合物,其含有上述铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。The present invention also provides a composition for casting molds, comprising the above-mentioned binder composition for casting molds and a curing agent composition containing a curing agent for curing the binder composition for casting molds.

另外,本发明是一种铸模用组合物,其含有耐火性粒子、上述铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。The present invention also provides a casting mold composition comprising refractory particles, the above-mentioned casting mold binder composition, and a curing agent composition containing a curing agent for curing the casting mold binder composition.

另外,本发明是一种铸模的制造方法,其包括:混合工序,其将耐火性粒子、上述铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物混合,获得铸模用组合物;及固化工序,其将上述铸模用组合物装入模框,并使该铸模用组合物固化。In addition, the present invention is a method for manufacturing a casting mold, which includes: a mixing step, in which refractory particles, the above-mentioned binder composition for casting mold shaping, and a curing agent composition containing a curing agent that cures the binder composition for casting mold shaping are mixed to obtain a casting mold composition; and a curing step, in which the above-mentioned casting mold composition is loaded into a mold frame and the casting mold composition is cured.

根据本发明,可提供一种可大幅提高低温环境下的铸模强度且单体状的呋喃甲醇的含量少的铸模造型用粘结剂组合物、铸模造型用组合物、及铸模用组合物、以及铸模的制造方法。According to the present invention, a binder composition for mold making, a composition for mold making, a composition for mold making, and a method for producing a mold can be provided, which can significantly improve the mold strength in a low temperature environment and have a low content of furanol as a single substance.

以下,对本发明的一个实施方式进行说明。Hereinafter, one embodiment of the present invention will be described.

<铸模造型用粘结剂组合物><Binder composition for casting mold>

本实施方式的铸模造型用粘结剂组合物(以下,也简称为粘结剂组合物)含有呋喃甲醇(成分A)、双羟甲基呋喃(成分B)、树脂(成分C)及水(成分D),且满足下述条件(1)~(5)。The binder composition for casting molds of the present embodiment (hereinafter also referred to simply as the binder composition) contains furanol (component A), bishydroxymethylfuran (component B), a resin (component C) and water (component D), and satisfies the following conditions (1) to (5).

条件(1):上述铸模造型用粘结剂组合物中的上述成分A的含量为30.0质量%以下Condition (1): The content of the component A in the binder composition for casting molds is 30.0% by mass or less

条件(2):上述铸模造型用粘结剂组合物中的上述成分D的含量为25.0质量%以下Condition (2): The content of the component D in the mold-forming binder composition is 25.0% by mass or less

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the binder composition for casting molds is 39.0 mass % or more and 95.0 mass % or less relative to the total content of the component B and the component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

根据上述粘结剂组合物,可提供一种可大幅提高低温环境下的铸模强度且单体状的呋喃甲醇的含量少的粘结剂组合物。上述粘结剂组合物发挥这种效果的原因仍不确定,但可认为如下。The binder composition can provide a binder composition that can significantly improve mold strength in a low temperature environment and has a low content of furanol as a single substance. The reason why the binder composition exhibits such an effect is still unclear, but it is considered as follows.

双羟甲基呋喃(成分B)与树脂(成分C)相比,与呋喃甲醇(成分A)的反应性优异,且降低上述粘结剂组合物的粘度。若双羟甲基呋喃(成分B)的含量增加,则反应性提高,粘结剂组合物的粘度也降低,与耐火性粒子的混炼性也提高,因此铸模强度提高。另一方面,由于双羟甲基呋喃(成分B)的熔点高,因此若含量增加,则保存稳定性变差(条件(3))。另外,若树脂中的氮含量增加,则交联反应推进,铸模强度提高。另一方面,若树脂中的氮含量增加,则粘结剂组合物的粘度变高,与耐火性粒子的混炼性变差,强度降低(条件(4))。因此,认为随着树脂中的氮含量增加,增加相对于双羟甲基呋喃(成分B)与树脂(成分C)的含量的合计的双羟甲基呋喃(成分B)的含量而降低粘度,由此可提高铸模强度(条件(5))。Compared with resin (ingredient C), bishydroxymethyl furan (ingredient B) has excellent reactivity with furan methanol (ingredient A) and reduces the viscosity of the above-mentioned binder composition. If the content of bishydroxymethyl furan (ingredient B) increases, the reactivity is improved, the viscosity of the binder composition is also reduced, and the compatibility with refractory particles is also improved, so the mold strength is improved. On the other hand, since the melting point of bishydroxymethyl furan (ingredient B) is high, if the content increases, the storage stability deteriorates (condition (3)). In addition, if the nitrogen content in the resin increases, the crosslinking reaction is promoted and the mold strength is improved. On the other hand, if the nitrogen content in the resin increases, the viscosity of the binder composition becomes higher, the compatibility with refractory particles deteriorates, and the strength decreases (condition (4)). Therefore, it is believed that as the nitrogen content in the resin increases, the content of bishydroxymethyl furan (ingredient B) relative to the total content of bishydroxymethyl furan (ingredient B) and the resin (ingredient C) is increased to reduce the viscosity, thereby improving the mold strength (condition (5)).

[呋喃甲醇(成分A)][Furanol (ingredient A)]

基于改善作业环境的观点而言,上述粘结剂组合物中的上述成分A的含量为30.0质量%以下,优选为25.0质量%以下,更优选为20.0质量%以下,进一步优选为15.0质量%以下。基于提高铸模强度的观点而言,上述粘结剂组合物中的上述成分A的含量优选为超过0质量%,更优选为5.0质量%以上,进一步优选为10.0质量%以上,再进一步优选为15.0质量%以上,再进一步优选为20.0质量%以上。需要说明的是,成分A的含量可通过实施例中记载的方法进行测定。Based on the viewpoint of improving working environment, the content of the above-mentioned component A in the above-mentioned binder composition is 30.0 mass % or less, preferably 25.0 mass % or less, more preferably 20.0 mass % or less, and more preferably 15.0 mass % or less.Based on the viewpoint of improving mold strength, the content of the above-mentioned component A in the above-mentioned binder composition is preferably more than 0 mass %, more preferably 5.0 mass % or more, more preferably 10.0 mass % or more, more preferably 15.0 mass % or more, and more preferably 20.0 mass % or more.It should be noted that the content of component A can be measured by the method described in the embodiment.

[双羟甲基呋喃(成分B)][Bis(hydroxymethyl)furan (ingredient B)]

基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述成分B优选为2,5-双羟甲基呋喃和/或3,4-双羟甲基呋喃,更优选为2,5-双羟甲基呋喃。From the viewpoint of reducing the content of monomeric furanol and significantly improving the mold strength in a low-temperature environment, the component B is preferably 2,5-bishydroxymethylfuran and/or 3,4-bishydroxymethylfuran, and more preferably 2,5-bishydroxymethylfuran.

基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述粘结剂组合物中的上述成分B的含量优选为18.0质量%以上,更优选为20.0质量%以上,进一步优选为21.0质量%以上,再进一步优选为22.0质量%以上,再进一步优选为39.0质量%以上,再进一步优选为51.0质量%以上,再进一步优选为63.0质量%以上。基于提高保存稳定性的观点而言,上述粘结剂组合物中的上述成分B的含量优选为70.0质量%以下,更优选为68.0质量%以下,进一步优选为65.0质量%以下,再进一步优选为63.0质量%以下。需要说明的是,成分B的含量可通过实施例中记载的方法进行测定。Based on the viewpoint of reducing the content of monomeric furan methanol and greatly improving the casting strength under low temperature environment, the content of the above-mentioned component B in the above-mentioned binder composition is preferably 18.0 mass % or more, more preferably 20.0 mass % or more, more preferably 21.0 mass % or more, further preferably 22.0 mass % or more, further preferably 39.0 mass % or more, further preferably 51.0 mass % or more, further preferably 63.0 mass % or more. Based on the viewpoint of improving storage stability, the content of the above-mentioned component B in the above-mentioned binder composition is preferably 70.0 mass % or less, more preferably 68.0 mass % or less, further preferably 65.0 mass % or less, further preferably 63.0 mass % or less. It should be noted that the content of component B can be measured by the method described in the embodiment.

[树脂(成分C)][Resin (component C)]

上述成分C只要为用作铸模造型用粘结剂的树脂,则可以没有特别限定地使用。作为用作铸模造型用粘结剂的树脂,可例示酸固化性树脂,作为该酸固化性树脂,可例示选自呋喃树脂、三聚氰胺与醛类的缩合物、尿素与醛类的缩合物、及亚乙基脲与醛类的缩合物中的一种以上。基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述成分C优选含有呋喃树脂。需要说明的是,上述成分C不包括呋喃甲醇。As long as the component C is a resin used as a binder for casting molds, it can be used without particular limitation. As the resin used as a binder for casting molds, an acid curable resin can be exemplified, and as the acid curable resin, one or more selected from furan resin, condensates of melamine and aldehydes, condensates of urea and aldehydes, and condensates of ethylene urea and aldehydes can be exemplified. Based on the viewpoint of reducing the content of monomeric furan carbinol and greatly improving the strength of the mold under low temperature environment, the component C preferably contains furan resin. It should be noted that the component C does not include furan carbinol.

上述呋喃树脂是使含有呋喃甲醇的单体组合物聚合而获得的,只要可用于铸模造型用粘结剂,则可以没有特别限定地使用。基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述呋喃树脂优选含有选自以下缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上:呋喃甲醇与尿素的缩合物;呋喃甲醇与三聚氰胺的缩合物;呋喃甲醇与亚乙基脲的缩合物;呋喃甲醇、尿素及醛类的缩合物(尿素改性呋喃树脂);呋喃甲醇、三聚氰胺及醛类的缩合物;呋喃甲醇、亚乙基脲及醛类的缩合物;呋喃甲醇缩合物;呋喃甲醇与醛类的缩合物;及呋喃甲醇、酚类及醛类的缩合物,上述呋喃树脂更优选含有选自尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上。The furan resin is obtained by polymerizing a monomer composition containing furanol, and any resin can be used without particular limitation as long as it can be used as a binder for casting molds. From the viewpoint of reducing the content of monomeric furan carbinol and significantly improving the casting strength in a low temperature environment, the above-mentioned furan resin preferably contains one or more selected from the following condensates, and one or more selected from two or more co-condensates selected from them: a condensate of furan carbinol and urea; a condensate of furan carbinol and melamine; a condensate of furan carbinol and ethylene urea; a condensate of furan carbinol, urea and aldehydes (urea-modified furan resin); a condensate of furan carbinol, melamine and aldehydes; a condensate of furan carbinol, ethylene urea and aldehydes; a condensate of furan carbinol; a condensate of furan carbinol and aldehydes; and a condensate of furan carbinol, phenols and aldehydes. The above-mentioned furan resin more preferably contains one or more selected from urea-modified furan resins, furan carbinol condensates and condensates of furan carbinol and aldehydes, and one or more selected from two or more co-condensates selected from them.

作为上述醛类,可举出:甲醛、乙醛、乙二醛、糠醛、对苯二甲醛、羟甲基糠醛等,可适当使用这些中的一种以上。基于提高铸模强度的观点而言,优选使用甲醛,基于减少造型时的甲醛产生量的观点而言,优选使用糠醛、对苯二甲醛、羟甲基糠醛。Examples of the aldehydes include formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde, hydroxymethylfurfural, and the like, and one or more of these may be used appropriately. From the perspective of improving mold strength, formaldehyde is preferably used, and from the perspective of reducing the amount of formaldehyde generated during molding, furfural, terephthalaldehyde, and hydroxymethylfurfural are preferably used.

作为上述酚类,可举出:苯酚、甲酚、间苯二酚、双酚A、双酚C、双酚E、双酚F等,可使用这些中的一种以上。Examples of the phenols include phenol, cresol, resorcinol, bisphenol A, bisphenol C, bisphenol E, and bisphenol F, and one or more of these may be used.

上述呋喃树脂可通过公知的方法制造。例如,在上述呋喃树脂为尿素改性呋喃树脂的情况下,尿素改性呋喃树脂可通过使尿素0.6~30.0质量份及多聚甲醛0.4~50.0质量份与呋喃甲醇100.0质量份进行反应来获得。The furan resin can be produced by a known method. For example, when the furan resin is a urea-modified furan resin, the urea-modified furan resin can be obtained by reacting 0.6 to 30.0 parts by mass of urea and 0.4 to 50.0 parts by mass of paraformaldehyde with 100.0 parts by mass of furan alcohol.

基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述呋喃树脂中的选自上述尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上的含量的合计优选为90质量%以上,更优选为95质量%以上,进一步优选为98质量%以上,进一步优选实质上为100质量%,再进一步优选为100质量%。需要说明的是,在本说明书中,“实质上”是指可含有杂质程度的量。From the viewpoint of reducing the content of monomeric furan carbinol and greatly improving the casting strength in a low temperature environment, the total content of one or more selected from the above-mentioned urea-modified furan resin, furan carbinol condensate and condensate of furan carbinol and aldehydes, and one or more selected from two or more co-condensates selected therefrom in the above-mentioned furan resin is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, further preferably substantially 100% by mass, and further preferably 100% by mass. It should be noted that in this specification, "substantially" refers to an amount that can contain impurities.

基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述成分C中的呋喃树脂的含量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,进一步优选为98质量%以上,进一步优选实质上为100质量%,再进一步优选为100质量%。From the viewpoint of reducing the content of monomeric furan carbinol and significantly improving the casting strength in a low-temperature environment, the content of the furan resin in the above-mentioned component C is preferably 80 mass % or more, more preferably 90 mass % or more, further preferably 95 mass % or more, further preferably 98 mass % or more, further preferably substantially 100 mass %, and further preferably 100 mass %.

基于提高树脂的交联密度而大幅提高低温环境下的铸模强度的观点而言,上述成分C中的氮含量(在本说明书中,氮含量是指氮原子的含量)为2.7质量%以上,优选为2.8质量%以上,更优选为3.7质量%以上,进一步优选为4.6质量%以上。基于维持与耐火性骨材的良好混炼性,抑制铸模强度降低的观点而言,上述成分C中的氮含量为22.0质量%以下,优选为21.0质量%以下,更优选为17.0质量%以下,进一步优选为13.9质量%以下。需要说明的是,成分C中的氮含量可通过实施例中记载的方法进行测定。Based on improving the crosslinking density of the resin and greatly improving the mold strength under low temperature environment, the nitrogen content (in this specification, nitrogen content refers to the content of nitrogen atoms) in the above-mentioned component C is more than 2.7 mass %, preferably more than 2.8 mass %, more preferably more than 3.7 mass %, and more preferably more than 4.6 mass %. Based on maintaining good mixability with refractory aggregate, for the viewpoint of suppressing mold strength reduction, the nitrogen content in the above-mentioned component C is below 22.0 mass %, preferably below 21.0 mass %, more preferably below 17.0 mass %, and more preferably below 13.9 mass %. It should be noted that the nitrogen content in component C can be measured by the method described in the embodiment.

基于提高树脂的交联密度而大幅提高低温环境下的铸模强度的观点而言,上述粘结剂组合物中的上述成分C的含量优选为5.0质量%以上,更优选为6.0质量%以上,进一步优选为7.0质量%以上。基于维持与耐火性骨材的良好混炼性,抑制铸模强度降低的观点而言,上述粘结剂组合物中的上述成分C的含量优选为45.0质量%以下,更优选为43.0质量%以下,进一步优选为42.0质量%以下。Based on the viewpoint of increasing the crosslinking density of the resin and greatly improving the mold strength under low temperature environment, the content of the above-mentioned component C in the above-mentioned binder composition is preferably 5.0 mass % or more, more preferably 6.0 mass % or more, and further preferably 7.0 mass % or more. Based on maintaining good kneading property with refractory aggregates and suppressing the viewpoint of reducing mold strength, the content of the above-mentioned component C in the above-mentioned binder composition is preferably 45.0 mass % or less, more preferably 43.0 mass % or less, and further preferably 42.0 mass % or less.

基于提高树脂的交联密度而大幅提高低温环境下的铸模强度的观点而言,上述粘结剂组合物中的氮含量优选为0.1质量%以上,更优选为0.2质量%以上。基于维持与耐火性骨材的良好混炼性,抑制铸模强度降低的观点而言,上述粘结剂组合物中的氮含量优选为3.5质量%以下,更优选为3.2质量%以下,进一步优选为3.0质量%以下。需要说明的是,粘结剂组合物中的氮含量可通过实施例中记载的方法进行测定。Based on the viewpoint of greatly improving the mold strength under low temperature environment by increasing the crosslinking density of the resin, the nitrogen content in the above-mentioned binder composition is preferably more than 0.1% by mass, more preferably more than 0.2% by mass. Based on maintaining good kneading property with refractory aggregate, the viewpoint of suppressing the reduction of mold strength, the nitrogen content in the above-mentioned binder composition is preferably less than 3.5% by mass, more preferably less than 3.2% by mass, and further preferably less than 3.0% by mass. It should be noted that the nitrogen content in the binder composition can be measured by the method described in the embodiment.

基于提高树脂的交联密度而大幅提高低温环境下的铸模强度的观点而言,上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0质量%以上,优选为51.0质量%以上,更优选为63.0质量%以上。基于提高保存稳定性的观点而言,上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为95.0质量%以下,优选为92.0质量%以下,更优选为90.0质量%以下,进一步优选为78.0质量%以下。Based on the viewpoint of increasing the crosslinking density of the resin and greatly improving the casting strength in a low temperature environment, the content of the above-mentioned component B in the above-mentioned binder composition is 39.0 mass % or more relative to the total content of the above-mentioned component B and the above-mentioned component C, preferably 51.0 mass % or more, and more preferably 63.0 mass % or more. Based on the viewpoint of improving storage stability, the content of the above-mentioned component B in the above-mentioned binder composition is 95.0 mass % or less relative to the total content of the above-mentioned component B and the above-mentioned component C, preferably 92.0 mass % or less, more preferably 90.0 mass % or less, and further preferably 78.0 mass % or less.

当将上述粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,上述粘结剂组合物满足上述式(1)。When the content of the component B in the binder composition is y and the nitrogen content of the component C is x, the binder composition satisfies the formula (1) from the viewpoint of reducing the content of monomeric furanol and significantly improving the mold strength in a low temperature environment.

在上述粘结剂组合物中,基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,优选上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0~95.0质量%,且上述成分C中的氮含量为2.7~22.0质量%,且满足上述式(1)。In the above-mentioned binder composition, from the viewpoint of reducing the content of monomeric furanol and significantly improving the casting strength in a low temperature environment, it is preferred that the content of the above-mentioned component B in the above-mentioned binder composition is 39.0 to 95.0 mass % relative to the total content of the above-mentioned component B and the above-mentioned component C, and the nitrogen content in the above-mentioned component C is 2.7 to 22.0 mass %, and satisfies the above-mentioned formula (1).

在上述粘结剂组合物中,基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,优选上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为51.0~95.0质量%,且上述成分C中的氮含量为2.7~22.0质量%,且满足上述式(1)。In the above-mentioned binder composition, from the viewpoint of reducing the content of monomeric furanol and significantly improving the casting strength in a low temperature environment, it is preferred that the content of the above-mentioned component B in the above-mentioned binder composition is 51.0 to 95.0 mass % relative to the total content of the above-mentioned component B and the above-mentioned component C, and the nitrogen content in the above-mentioned component C is 2.7 to 22.0 mass %, and satisfies the above-mentioned formula (1).

在上述粘结剂组合物中,基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,更优选上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为63.0~95.0质量%,且上述成分C中的氮含量为2.7~22.0质量%,且满足上述式(1)。In the above-mentioned binder composition, from the viewpoint of reducing the content of monomeric furanol and significantly improving the casting strength in a low temperature environment, it is more preferred that the content of the above-mentioned component B in the above-mentioned binder composition is 63.0 to 95.0 mass % relative to the total content of the above-mentioned component B and the above-mentioned component C, and the nitrogen content in the above-mentioned component C is 2.7 to 22.0 mass %, and satisfies the above-mentioned formula (1).

在上述粘结剂组合物中,基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,进一步优选上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为63.0~95.0质量%,且上述成分C中的氮含量为3.7~17.0质量%,且满足上述式(1)。In the above-mentioned binder composition, from the viewpoint of reducing the content of monomeric furanol and significantly improving the casting strength in a low temperature environment, it is further preferred that the content of the above-mentioned component B in the above-mentioned binder composition is 63.0 to 95.0 mass % relative to the total content of the above-mentioned component B and the above-mentioned component C, and the nitrogen content in the above-mentioned component C is 3.7 to 17.0 mass %, and satisfies the above-mentioned formula (1).

在上述粘结剂组合物中,基于降低单体状的呋喃甲醇的含量且大幅提高低温环境下的铸模强度的观点而言,再进一步优选上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为63.0~95.0质量%,且上述成分C中的氮含量为4.6~13.9质量%,且满足下述式(2)。In the above-mentioned binder composition, from the viewpoint of reducing the content of monomeric furanol and significantly improving the casting strength in a low temperature environment, it is further preferred that the content of the above-mentioned component B in the above-mentioned binder composition is 63.0 to 95.0 mass % relative to the total content of the above-mentioned component B and the above-mentioned component C, and the nitrogen content in the above-mentioned component C is 4.6 to 13.9 mass %, and satisfies the following formula (2).

1.32x+57.4≤y (2)1.32x+57.4≤y (2)

在上述粘结剂组合物中,基于提高保存稳定性的观点而言,再进一步优选上述粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为63.0~78.0质量%,且上述成分C中的氮含量为4.6~13.9质量%,且满足上述式(2)。In the above-mentioned adhesive composition, from the viewpoint of improving storage stability, it is further preferred that the content of the above-mentioned component B in the above-mentioned adhesive composition is 63.0-78.0 mass % relative to the total content of the above-mentioned component B and the above-mentioned component C, and the nitrogen content in the above-mentioned component C is 4.6-13.9 mass %, and satisfies the above-mentioned formula (2).

[水(成分D)][Water (ingredient D)]

基于提高铸模强度的观点而言,上述粘结剂组合物中的上述成分D的含量为25.0质量%以下,优选为20.0质量%以下。基于调节上述粘结剂组合物的粘度的观点而言,上述粘结剂组合物中的上述成分D的含量优选为5.0质量%以上,更优选为8.0质量%以上,进一步优选为10.0质量%以上。需要说明的是,成分D的含量可通过实施例中记载的方法进行测定。Based on the viewpoint of improving mold strength, the content of the above-mentioned component D in the above-mentioned binder composition is 25.0 mass % or less, preferably 20.0 mass % or less. Based on the viewpoint of adjusting the viscosity of the above-mentioned binder composition, the content of the above-mentioned component D in the above-mentioned binder composition is preferably 5.0 mass % or more, more preferably 8.0 mass % or more, and further preferably 10.0 mass % or more. It should be noted that the content of component D can be measured by the method described in the embodiment.

[固化促进剂][Curing accelerator]

基于提高铸模强度的观点而言,上述粘结剂组合物也可包含固化促进剂。基于提高铸模强度的观点而言,固化促进剂优选为选自酚衍生物、芳香族二醛及单宁类中的一种以上。From the viewpoint of improving the strength of the mold, the binder composition may contain a curing accelerator. From the viewpoint of improving the strength of the mold, the curing accelerator is preferably one or more selected from phenol derivatives, aromatic dialdehydes, and tannins.

作为上述酚衍生物,例如可举出:间苯二酚、甲酚、对苯二酚、间苯三酚、亚甲基双酚等。基于提高铸模强度的观点而言,上述粘结剂组合物中的上述酚衍生物的含量优选为1~25质量%,更优选为2~15质量%,进一步优选为3~10质量%。Examples of the phenol derivatives include resorcinol, cresol, hydroquinone, phloroglucinol, methylene bisphenol, etc. From the viewpoint of improving mold strength, the content of the phenol derivative in the binder composition is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, and further preferably 3 to 10% by mass.

作为上述芳香族二醛,可举出:对苯二甲醛、邻苯二甲醛及间苯二甲醛等、以及这些的衍生物等。这些的衍生物是指在作为基本骨架的具有两个甲酰基的芳香族化合物的芳香环上具有烷基等取代基的化合物等。基于使芳香族二醛充分溶解于呋喃树脂的观点、及抑制芳香族二醛本身的臭味的观点而言,上述粘结剂组合物中的芳香族二醛的含量优选为0.1~15质量%,更优选为0.5~10质量%,进一步优选为1~5质量%。As the above-mentioned aromatic dialdehyde, there can be mentioned: terephthalaldehyde, o-phthalaldehyde and isophthalaldehyde, and derivatives thereof. These derivatives refer to compounds having substituents such as alkyl groups on the aromatic ring of an aromatic compound having two formyl groups as a basic skeleton. From the viewpoint of fully dissolving the aromatic dialdehyde in the furan resin and suppressing the odor of the aromatic dialdehyde itself, the content of the aromatic dialdehyde in the above-mentioned binder composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass.

作为上述单宁类,可举出缩合单宁、水解型单宁。作为这些缩合单宁、水解型单宁的例子,可举出具有邻苯三酚骨架、间苯二酚骨架的单宁。另外,也可添加含有这些单宁类的树皮萃取物、从源自植物的叶、果实、种子、及寄生于植物的虫瘿等天然物萃取的萃取物。基于提高固化速度的观点及提高铸模强度的观点而言,上述粘结剂组合物中的单宁类的含量优选为0.2~10质量%,更优选为1.0~7质量%,进一步优选为1.9~5质量%。As the above-mentioned tannins, condensed tannins and hydrolyzed tannins can be mentioned. As examples of these condensed tannins and hydrolyzed tannins, tannins having a pyrogallol skeleton and a resorcinol skeleton can be mentioned. In addition, bark extracts containing these tannins, extracts extracted from natural materials such as leaves, fruits, seeds, and galls parasitic on plants, etc. can also be added. From the viewpoint of increasing the curing speed and the viewpoint of increasing the mold strength, the content of tannins in the above-mentioned binder composition is preferably 0.2 to 10% by mass, more preferably 1.0 to 7% by mass, and further preferably 1.9 to 5% by mass.

基于制造铸模用组合物时及制造铸模时的作业性的观点而言,上述粘结剂组合物在25℃下的粘度优选为70mPa·s以下,更优选为50mPa·s以下。需要说明的是,粘结剂组合物在25℃下的粘度可通过实施例中记载的方法进行测定。From the viewpoint of workability when manufacturing the mold composition and the mold, the viscosity of the binder composition at 25° C. is preferably 70 mPa·s or less, more preferably 50 mPa·s or less. The viscosity of the binder composition at 25° C. can be measured by the method described in Examples.

上述粘结剂组合物中也可还包含硅烷偶联剂等添加剂。例如,若上述粘结剂组合物中包含硅烷偶联剂,则可进一步提高所获得的铸模的最终强度,因此优选。作为硅烷偶联剂,可使用:N-β-(氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷等氨基硅烷;3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷、3-缩水甘油氧基丙基甲基二甲氧基硅烷、3-缩水甘油氧基丙基甲基二乙氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷等环氧硅烷;脲基硅烷、巯基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、丙烯酰氧基硅烷等。优选为氨基硅烷、环氧硅烷、脲基硅烷。更优选为氨基硅烷、环氧硅烷。在氨基硅烷中,优选为N-β-(氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷。在环氧硅烷中,优选为3-缩水甘油氧基丙基甲基二甲氧基硅烷。The above-mentioned adhesive composition may also include additives such as silane coupling agents. For example, if the above-mentioned adhesive composition includes a silane coupling agent, the final strength of the obtained casting mold can be further improved, so it is preferred. As a silane coupling agent, aminosilanes such as N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, and 3-aminopropyltrimethoxysilane can be used; 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane and other epoxysilanes; urea silane, mercaptosilane, sulfosilane, methacryloxysilane, acryloxysilane, etc. can be used. Preferred are aminosilane, epoxysilane, and ureidosilane. More preferred are aminosilane and epoxysilane. Among aminosilanes, preferred is N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane. Among epoxysilanes, preferred is 3-glycidyloxypropylmethyldimethoxysilane.

基于提高铸模强度的观点而言,上述粘结剂组合物中的硅烷偶联剂的含量优选为0.01质量%以上,更优选为0.05质量%以上。基于相同的观点而言,上述粘结剂组合物中的硅烷偶联剂的含量优选为5质量%以下,更优选为3质量%以下,进一步优选为1质量%以下,进一步优选为0.5质量%以下。From the viewpoint of improving the mold strength, the content of the silane coupling agent in the above-mentioned binder composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. From the same viewpoint, the content of the silane coupling agent in the above-mentioned binder composition is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, further preferably 0.5% by mass or less.

本实施方式的铸模造型用粘结剂组合物适宜用于自固性铸模的造型。此处,自固性铸模是如下铸模:当在砂中混合粘结剂组合物及固化剂时,随着时间推移而聚合反应推进,铸模固化。作为此时使用的砂的温度,为-20℃~50℃的范围,优选为0℃~40℃。对于这种温度的砂,选择适合其的量的固化剂添加至砂中,由此可使铸模适当地固化。The binder composition for mold molding of the present embodiment is suitable for molding a self-hardening mold. Here, the self-hardening mold is a mold as follows: when the binder composition and the curing agent are mixed in the sand, the polymerization reaction proceeds over time and the mold is cured. The temperature of the sand used at this time is in the range of -20°C to 50°C, preferably 0°C to 40°C. For sand at this temperature, a curing agent of an appropriate amount is selected and added to the sand, thereby allowing the mold to be properly cured.

<铸模造型用组合物><Molding composition>

本实施方式的铸模造型用组合物含有上述粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。本实施方式的铸模造型用组合物具有与上述粘结剂组合物相同的效果。The casting mold making composition of the present embodiment contains the above-mentioned binder composition and a curing agent composition containing a curing agent for curing the casting mold making binder composition. The casting mold making composition of the present embodiment has the same effects as the above-mentioned binder composition.

[固化剂组合物][Curing agent composition]

上述固化剂组合物只要含有使上述粘结剂组合物固化的固化剂,则可以没有特别限定地使用。作为该固化剂,可例示酸系固化剂,可使用一种以上的下述固化剂等以往公知的固化剂:二甲苯磺酸(尤其是间二甲苯磺酸)、甲苯磺酸(尤其是对甲苯磺酸)、甲磺酸等磺酸系化合物;磷酸、酸性磷酸酯等磷酸系化合物;硫酸。基于操作性的观点而言,这些化合物优选为水溶液。进而,固化剂组合物中可含有选自醇类、醚醇类及酯类中的一种以上的溶剂、羧酸类。The curing agent composition can be used without particular limitation as long as it contains a curing agent that cures the binder composition. As the curing agent, an acid curing agent can be exemplified, and one or more of the following curing agents and the like, such as sulfonic acid compounds such as xylenesulfonic acid (especially m-xylenesulfonic acid), toluenesulfonic acid (especially p-toluenesulfonic acid), and methanesulfonic acid can be used; phosphoric acid compounds such as phosphoric acid and acidic phosphate esters; sulfuric acid. From the viewpoint of operability, these compounds are preferably aqueous solutions. Furthermore, the curing agent composition may contain one or more solvents selected from alcohols, ether alcohols, and esters, and carboxylic acids.

上述固化剂组合物中的上述溶剂的含量可根据作业环境的温度或耐火性粒子的温度,为了获得所需的反应速度及铸模强度而适当调节,一般而言,基于使固化剂组合物溶解的观点而言,优选为5质量%以上,更优选为10质量%以上,进一步优选为20质量%以上。基于提高铸模强度的观点而言,上述固化剂组合物中的上述溶剂的含量优选为90质量%以下,更优选为80质量%以下,进一步优选为70质量%以下。The content of the above-mentioned solvent in the above-mentioned curing agent composition can be appropriately adjusted according to the temperature of the working environment or the temperature of the refractory particles in order to obtain the desired reaction speed and mold strength. Generally speaking, based on the viewpoint of dissolving the curing agent composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. Based on the viewpoint of improving mold strength, the content of the above-mentioned solvent in the above-mentioned curing agent composition is preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably 70% by mass or less.

基于提高铸模强度的观点而言,上述固化剂组合物中的上述固化剂的含量优选为10质量%以上,更优选为20质量%以上,进一步优选为30质量%以上。基于使固化剂组合物溶解的观点而言,上述固化剂组合物中的上述固化剂的含量优选为95质量%以下,更优选为90质量%以下,进一步优选为80质量%以下。From the viewpoint of improving mold strength, the content of the above-mentioned curing agent in the above-mentioned curing agent composition is preferably 10 mass % or more, more preferably 20 mass % or more, and further preferably 30 mass % or more. From the viewpoint of dissolving the curing agent composition, the content of the above-mentioned curing agent in the above-mentioned curing agent composition is preferably 95 mass % or less, more preferably 90 mass % or less, and further preferably 80 mass % or less.

关于上述粘结剂组合物与上述固化剂的质量比,基于提高固化速度,提高铸模强度的观点而言,相对于上述粘结剂组合物100质量份,上述固化剂优选为10~60质量份,更优选为10~40质量份,进一步优选为10~30质量份。Regarding the mass ratio of the above-mentioned adhesive composition to the above-mentioned curing agent, from the viewpoint of increasing the curing speed and improving the mold strength, the above-mentioned curing agent is preferably 10 to 60 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 10 to 30 parts by mass relative to 100 parts by mass of the above-mentioned adhesive composition.

[铸模用组合物][Mold composition]

本实施方式的铸模用组合物含有耐火性粒子、上述粘结剂组合物及上述固化剂组合物。本实施方式的铸模用组合物具有与上述粘结剂组合物相同的效果。The casting composition of this embodiment contains refractory particles, the above-mentioned binder composition, and the above-mentioned curing agent composition. The casting composition of this embodiment has the same effects as those of the above-mentioned binder composition.

[耐火性粒子][Refractory particles]

作为上述耐火性粒子,可使用一种或两种以上的硅砂、铬砂、锆砂、橄榄石砂、氧化铝砂、莫来石砂、合成莫来石砂等以往公知的耐火性粒子,另外,也可使用将使用过的耐火性粒子回收所获得的物质、进行再生处理所获得的物质等。其中,优选包含硅砂。As the refractory particles, one or more of silica sand, chrome sand, zircon sand, olivine sand, alumina sand, mullite sand, synthetic mullite sand and other conventionally known refractory particles can be used, and in addition, materials obtained by recycling used refractory particles or materials obtained by regenerating the used refractory particles can also be used. Among them, silica sand is preferably included.

在上述铸模用组合物中,上述耐火性粒子、上述粘结剂组合物及上述固化剂的质量比可适当设定,基于提高固化速度,提高铸模强度的观点而言,相对于上述耐火性粒子100质量份,上述粘结剂组合物优选为0.5~1.5质量份,上述固化剂优选为0.07~1质量份的范围。In the above-mentioned casting mold composition, the mass ratio of the above-mentioned refractory particles, the above-mentioned binder composition and the above-mentioned curing agent can be appropriately set. From the viewpoint of increasing the curing speed and improving the casting mold strength, the above-mentioned binder composition is preferably in the range of 0.5 to 1.5 mass parts, and the above-mentioned curing agent is preferably in the range of 0.07 to 1 mass part relative to 100 mass parts of the above-mentioned refractory particles.

<铸模的制造方法><Method for manufacturing casting mold>

本实施方式的铸模的制造方法包括:混合工序,其将耐火性粒子、上述粘结剂组合物及上述固化剂组合物混合,获得铸模用组合物;及固化工序,其将上述铸模用组合物装入模框,并使该铸模用组合物固化。该铸模的制造方法具有与上述粘结剂组合物相同的效果。The method for manufacturing a mold of the present embodiment includes: a mixing step of mixing refractory particles, the binder composition and the curing agent composition to obtain a mold composition; and a curing step of placing the mold composition into a mold frame and curing the mold composition. The method for manufacturing a mold has the same effect as the binder composition.

在上述混合工序中,添加、混合上述粘结剂组合物及上述固化剂组合物以及耐火性粒子的顺序并无特别限定,可将上述粘结剂组合物与上述固化剂组合物混合而制造铸模造型用组合物后,将该铸模造型用组合物与耐火性粒子混合,也可分别添加、混合上述粘结剂组合物、上述固化剂组合物及耐火性粒子,但基于保存稳定性及铸模的生产性的观点而言,优选将上述粘结剂组合物、上述固化剂组合物及耐火性粒子混合而获得铸模用组合物。另外,基于提高铸模强度的观点而言,优选向耐火性粒子中添加固化剂组合物并进行混合,接下来添加粘结剂组合物并进行混合。另外,在使用两种以上固化剂组合物的情况下,可将各固化剂组合物混合后添加,也可分别添加各固化剂组合物。In the above-mentioned mixing process, the order of adding and mixing the above-mentioned binder composition and the above-mentioned curing agent composition and refractory particles is not particularly limited, after the above-mentioned binder composition can be mixed with the above-mentioned curing agent composition to manufacture the composition for casting mold, the composition for casting mold can be mixed with refractory particles, and the above-mentioned binder composition, the above-mentioned curing agent composition and refractory particles can also be added and mixed respectively, but based on the viewpoint of storage stability and the productivity of the mold, the above-mentioned binder composition, the above-mentioned curing agent composition and refractory particles are preferably mixed to obtain the composition for casting mold. In addition, based on the viewpoint of improving the strength of the mold, it is preferred to add a curing agent composition to the refractory particles and mix, then add a binder composition and mix. In addition, when using two or more curing agent compositions, each curing agent composition can be added after mixing, and each curing agent composition can also be added respectively.

在上述混合工序中,作为混合各原料的方法,可使用公知的一般方法,例如可举出通过分批混合机添加各原料并进行混炼的方法、及向连续混合机供给各原料并进行混炼的方法。In the mixing step, as a method for mixing the raw materials, a known general method can be used, and examples thereof include a method of adding and kneading the raw materials using a batch mixer and a method of supplying and kneading the raw materials using a continuous mixer.

在本实施方式的铸模的制造方法中,除了该混合工序以外,可直接利用以往的铸模的制造工艺来制造铸模。In the method for manufacturing a casting mold according to the present embodiment, the casting mold can be manufactured by utilizing the conventional casting mold manufacturing process as it is, except for the mixing step.

对于上述实施方式,本发明还公开以下组合物、制造方法或用途。For the above embodiments, the present invention further discloses the following compositions, manufacturing methods or uses.

<1>一种铸模造型用粘结剂组合物,其含有呋喃甲醇(成分A)、双羟甲基呋喃(成分B)、树脂(成分C)及水(成分D),且<1> A binder composition for casting, comprising furanol (component A), bishydroxymethylfuran (component B), a resin (component C) and water (component D), and

满足下述条件(1)~(5)。The following conditions (1) to (5) are met.

条件(1):上述铸模造型用粘结剂组合物中的上述成分A的含量为30.0质量%以下Condition (1): The content of the component A in the binder composition for casting molds is 30.0% by mass or less

条件(2):上述铸模造型用粘结剂组合物中的上述成分D的含量为25.0质量%以下Condition (2): The content of the component D in the mold-forming binder composition is 25.0% by mass or less

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the binder composition for casting molds is 39.0 mass % or more and 95.0 mass % or less relative to the total content of the component B and the component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

<2>如<1>所记载的铸模造型用粘结剂组合物,其含有呋喃甲醇(成分A)、双羟甲基呋喃(成分B)、树脂(成分C)及水(成分D),且<2> The binder composition for casting according to <1>, comprising furanol (component A), bishydroxymethylfuran (component B), a resin (component C) and water (component D), and

满足下述条件(1)~(5)。The following conditions (1) to (5) are met.

条件(1):上述铸模造型用粘结剂组合物中的上述成分A的含量为5.0质量%以上且30.0质量%以下Condition (1): The content of the component A in the binder composition for casting molds is 5.0 mass % or more and 30.0 mass % or less

条件(2):上述铸模造型用粘结剂组合物中的上述成分D的含量为5.0质量%以上且25.0质量%以下Condition (2): The content of the component D in the binder composition for casting molds is 5.0 mass % or more and 25.0 mass % or less

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为39.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the binder composition for casting molds is 39.0 mass % or more and 95.0 mass % or less relative to the total content of the component B and the component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

<3>如<1>或<2>所记载的铸模造型用粘结剂组合物,其中,上述成分A的含量为10.0质量%以上且30.0质量%以下。<3> The binder composition for casting molds according to <1> or <2>, wherein the content of the component A is 10.0 mass % to 30.0 mass %.

<4>如<1>至<3>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分A的含量为15.0质量%以上且30.0质量%以下。<4> The binder composition for casting molds according to any one of <1> to <3>, wherein the content of the component A is 15.0 mass % to 30.0 mass %.

<5>如<1>至<4>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分D的含量为8.0质量%以上且25.0质量%以下。<5> The binder composition for casting molds according to any one of <1> to <4>, wherein the content of the component D is 8.0 mass % or more and 25.0 mass % or less.

<6>如<1>至<5>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分D的含量为10.0质量%以上且20.0质量%以下。<6> The binder composition for casting molds according to any one of <1> to <5>, wherein the content of the component D is 10.0 mass % to 20.0 mass %.

<7>如<1>至<6>中任一项所记载的铸模造型用粘结剂组合物,其满足下述条件(3)~(5)。<7> The binder composition for casting molds according to any one of <1> to <6>, which satisfies the following conditions (3) to (5).

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为51.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the binder composition for casting molds is 51.0 mass % or more and 95.0 mass % or less relative to the total content of the component B and the component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

<8>如<1>至<7>中任一项所记载的铸模造型用粘结剂组合物,其满足下述条件(3)~(5)。<8> The binder composition for casting molds according to any one of <1> to <7>, which satisfies the following conditions (3) to (5).

条件(3):上述铸模造型用粘结剂组合物中上述成分B的含量相对于上述成分B与上述成分C的含量的合计为63.0质量%以上且95.0质量%以下Condition (3): The content of the component B in the above-mentioned binder composition for casting molds is 63.0 mass % or more and 95.0 mass % or less relative to the total content of the above-mentioned component B and the above-mentioned component C.

条件(4):上述成分C中的氮含量为2.7质量%以上且22.0质量%以下Condition (4): The nitrogen content in the above-mentioned component C is 2.7 mass % or more and 22.0 mass % or less

条件(5):当将上述铸模造型用粘结剂组合物中的上述成分B的含量设为y,将上述成分C的氮含量设为x时,满足下式(1)Condition (5): When the content of the component B in the above-mentioned binder composition for casting molds is y and the nitrogen content of the above-mentioned component C is x, the following formula (1) is satisfied:

2.97x+15.2≤y (1)2.97x+15.2≤y (1)

<9>如<1>至<8>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分C含有呋喃树脂,且上述成分C中的上述呋喃树脂的含量为80质量%以上。<9> The binder composition for casting molds according to any one of <1> to <8>, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 80% by mass or more.

<10>如<1>至<9>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分C含有呋喃树脂,且上述成分C中的上述呋喃树脂的含量为90质量%以上。<10> The binder composition for casting molds according to any one of <1> to <9>, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 90% by mass or more.

<11>如<1>至<10>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分C含有呋喃树脂,且上述成分C中的上述呋喃树脂的含量为95质量%以上。<11> The binder composition for casting molds according to any one of <1> to <10>, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 95% by mass or more.

<12>如<1>至<11>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分C含有呋喃树脂,且上述成分C中的上述呋喃树脂的含量为98质量%以上。<12> The binder composition for casting molds according to any one of <1> to <11>, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 98% by mass or more.

<13>如<1>至<12>中任一项所记载的铸模造型用粘结剂组合物,其中,上述成分C含有呋喃树脂,且上述成分C中的上述呋喃树脂的含量实质上为100质量%。<13> The binder composition for casting molds according to any one of <1> to <12>, wherein the component C contains a furan resin, and the content of the furan resin in the component C is substantially 100% by mass.

<14>如<9>至<13>中任一项所记载的铸模造型用粘结剂组合物,其中,上述呋喃树脂含有选自尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上。<14> A binder composition for casting molds as described in any one of <9> to <13>, wherein the furan resin contains one or more selected from urea-modified furan resins, furan methanol condensates and condensates of furan methanol and aldehydes, and one or more co-condensates selected from two or more thereof.

<15>如<14>所记载的铸模造型用粘结剂组合物,其中,上述呋喃树脂中的选自上述尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上的含量的合计为90质量%以上。<15> A binder composition for casting molds as described in <14>, wherein the total content of one or more selected from the above-mentioned urea-modified furan resin, furan methanol condensate and condensate of furan methanol and aldehydes, and one or more selected from co-condensates of two or more selected from them in the above-mentioned furan resin is 90% by mass or more.

<16>如<14>或<15>所记载的铸模造型用粘结剂组合物,其中,上述呋喃树脂中的选自上述尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上的含量的合计为95质量%以上。<16> A binder composition for casting mold forming as described in <14> or <15>, wherein the total content of one or more selected from the above-mentioned urea-modified furan resin, furan methanol condensate and condensate of furan methanol and aldehydes, and one or more selected from co-condensates of two or more selected from them in the above-mentioned furan resin is 95% by mass or more.

<17>如<14>至<16>中任一项所记载的铸模造型用粘结剂组合物,其中,上述呋喃树脂中的选自上述尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上的含量的合计为98质量%以上。<17> A binder composition for casting molds as described in any one of <14> to <16>, wherein the total content of one or more selected from the above-mentioned urea-modified furan resin, furan methanol condensate and condensate of furan methanol and aldehydes, and one or more co-condensates selected from two or more selected from them in the above-mentioned furan resin is 98% by mass or more.

<18>如<14>至<17>中任一项所记载的铸模造型用粘结剂组合物,其中,上述呋喃树脂中的选自上述尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上的含量的合计实质上为100质量%。<18> A binder composition for casting molds as described in any one of <14> to <17>, wherein the total content of one or more selected from the above-mentioned urea-modified furan resin, furanmethanol condensate and condensate of furanmethanol and aldehydes in the above-mentioned furan resin, and one or more selected from co-condensates of two or more selected therefrom is substantially 100% by mass.

<19>一种铸模造型用组合物,其含有如<1>至<18>中任一项所记载的铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。<19> A casting mold making composition comprising the casting mold making binder composition according to any one of <1> to <18> and a curing agent composition containing a curing agent for curing the casting mold making binder composition.

<20>一种铸模用组合物,其含有耐火性粒子、如<1>至<18>中任一项所记载的铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物。<20> A casting mold composition comprising refractory particles, the casting mold binder composition according to any one of <1> to <18>, and a curing agent composition containing a curing agent that cures the casting mold binder composition.

<21>如<20>所记载的铸模用组合物,其中,相对于上述耐火性粒子100质量份,上述粘结剂组合物为0.5~1.5质量份,上述固化剂为0.07~1质量份。<21> The casting composition according to <20>, wherein the amount of the binder composition is 0.5 to 1.5 parts by mass, and the amount of the curing agent is 0.07 to 1 part by mass, based on 100 parts by mass of the refractory particles.

<22>一种铸模的制造方法,其包括:混合工序,其将耐火性粒子、如<1>至<18>中任一项所记载的铸模造型用粘结剂组合物、及包含使该铸模造型用粘结剂组合物固化的固化剂的固化剂组合物混合,获得铸模用组合物;及固化工序,其将上述铸模用组合物装入模框,并使该铸模用组合物固化。<22> A method for manufacturing a casting mold, comprising: a mixing step of mixing refractory particles, a binder composition for casting mold shaping as described in any one of <1> to <18>, and a curing agent composition containing a curing agent for curing the binder composition for casting mold shaping to obtain a casting mold composition; and a curing step of loading the above-mentioned casting mold composition into a mold frame and curing the casting mold composition.

实施例Example

以下,对具体示出本发明的实施例等进行说明。Hereinafter, embodiments and the like which specifically illustrate the present invention will be described.

<物性的测定方法><Measurement methods of physical properties>

[水的含量][Water content]

使用自动水分测定装置(平沼产业株式会社制造,AQV-2200A),基于JIS K 0068所示的卡氏法进行测定。The measurement was performed using an automatic water content meter (manufactured by Hiranuma Sangyo Co., Ltd., AQV-2200A) in accordance with the Karl Fischer method in accordance with JIS K 0068.

[呋喃甲醇及双羟甲基呋喃的含量][Content of furanol and bis(hydroxymethylfuran)]

使用气相色谱仪(岛津制作所株式会社制造,GC-2014S),通过下述条件的气相色谱分析进行测定。The measurement was performed by gas chromatography analysis under the following conditions using a gas chromatograph (GC-2014S manufactured by Shimadzu Corporation).

·标准曲线:使用呋喃甲醇及双羟甲基呋喃制成。·Standard curve: prepared using furanol and bis(hydroxymethylfuran).

·内部标准溶液:1,6-己二醇Internal standard solution: 1,6-hexanediol

·柱:PEG-20M Chromosorb WAW DMCS 60/80目(GL Science公司制造)Column: PEG-20M Chromosorb WAW DMCS 60/80 mesh (manufactured by GL Science)

·柱温:80~200℃(8℃/min)Column temperature: 80~200℃(8℃/min)

·注入温度:210℃Injection temperature: 210℃

·检测器温度:250℃载气:50mL/min(He)Detector temperature: 250℃ Carrier gas: 50mL/min (He)

[氮含量][Nitrogen content]

基于JIS K 6451-2所示的凯氏法进行测定。The measurement was carried out based on the Kjeldahl method shown in JIS K 6451-2.

[粘度][Viscosity]

使用E型粘度计(RE-80R,东机产业株式会社制造),在25℃下,使用标准转子(锥角:1°34',锥半径:24mm),以转速100rpm测定粘度。The viscosity was measured using an E-type viscometer (RE-80R, manufactured by Toki Sangyo Co., Ltd.) at 25° C. and a rotation speed of 100 rpm using a standard rotor (cone angle: 1°34′, cone radius: 24 mm).

<树脂的制造方法><Resin production method>

[尿素改性呋喃树脂][Urea modified furan resin]

向三口烧瓶中投入呋喃甲醇609g、25质量%氢氧化钠水溶液0.7g、92质量%多聚甲醛188g、尿素140g,在常压下在100℃下反应45分钟。然后,投入戊二酸1.4g,进一步在100℃下反应45分钟。然后,添加尿素52g,在70℃下反应30分钟。反应后,用25质量%氢氧化钠水溶液将pH值调节为10。对于所获得的组合物,使用旋转蒸发器,在110℃、内部气压5mmHg的条件下进行减压蒸馏,去除水及一部分呋喃甲醇。所获得的反应物的组成为尿素改性呋喃树脂71.9质量%、呋喃甲醇28.1质量%。另外,所获得的反应物的氮含量为14.5质量%,尿素改性呋喃树脂的氮含量为20.2质量%。Into a three-necked flask, 609g of furan methanol, 0.7g of 25% by mass sodium hydroxide aqueous solution, 188g of 92% by mass paraformaldehyde, and 140g of urea were added, and the mixture was reacted at 100°C for 45 minutes under normal pressure. Then, 1.4g of glutaric acid was added, and the mixture was further reacted at 100°C for 45 minutes. Then, 52g of urea was added, and the mixture was reacted at 70°C for 30 minutes. After the reaction, the pH value was adjusted to 10 with a 25% by mass sodium hydroxide aqueous solution. For the obtained composition, a rotary evaporator was used to perform reduced pressure distillation at 110°C and an internal pressure of 5mmHg to remove water and a portion of furan methanol. The composition of the obtained reactant was 71.9% by mass of urea-modified furan resin and 28.1% by mass of furan methanol. In addition, the nitrogen content of the obtained reactant was 14.5% by mass, and the nitrogen content of the urea-modified furan resin was 20.2% by mass.

[呋喃甲醇缩合物][Furan methanol condensate]

向三口烧瓶中投入呋喃甲醇492g、戊二酸8g,在常压下在100℃下反应5小时。然后,用25质量%氢氧化钠水溶液将pH值调节为10。对于所获得的组合物,使用旋转蒸发器,在110℃、内部气压为5mmHg的条件下进行减压蒸馏,去除水及一部分呋喃甲醇。所获得的反应物的组成为呋喃甲醇缩合物79.0质量%、呋喃甲醇21.0质量%。492 g of furan methanol and 8 g of glutaric acid were added to a three-necked flask and reacted at 100° C. for 5 hours under normal pressure. Then, the pH value was adjusted to 10 with a 25% by mass sodium hydroxide aqueous solution. The obtained composition was subjected to reduced pressure distillation at 110° C. and an internal pressure of 5 mmHg using a rotary evaporator to remove water and a portion of furan methanol. The composition of the obtained reactant was 79.0% by mass of furan methanol condensate and 21.0% by mass of furan methanol.

[2,5-双羟甲基呋喃(BHMF)][2,5-Bis(hydroxymethyl)furan(BHMF)]

向三口烧瓶中投入呋喃甲醇615g、92质量%多聚甲醛205g、戊二酸41g,在常压下在100℃下反应3小时。其后,用48%氢氧化钠水溶液将pH值调节为10。对于所获得的组合物,使用旋转蒸发器,在110℃、内部气压为5mmHg的条件下进行减压蒸馏,由此去除呋喃甲醇及水分。使所获得的残留物完全溶解于加热至40℃的氯仿中后,在5℃下进行冷却,由此获得BHMF的晶体。然后,反复进行两次同样的操作。所获得的晶体的纯度为100质量%。Into a three-necked flask, 615 g of furan methanol, 205 g of 92% by mass paraformaldehyde, and 41 g of glutaric acid were added, and the mixture was reacted at 100° C. for 3 hours under normal pressure. Thereafter, the pH value was adjusted to 10 with a 48% aqueous sodium hydroxide solution. For the obtained composition, a rotary evaporator was used to perform reduced pressure distillation at 110° C. and an internal pressure of 5 mmHg to remove furan methanol and water. After the obtained residue was completely dissolved in chloroform heated to 40° C., it was cooled at 5° C. to obtain crystals of BHMF. Then, the same operation was repeated twice. The purity of the obtained crystals was 100% by mass.

<粘结剂组合物的制造例><Production Example of Adhesive Composition>

[制造例1][Production Example 1]

以日本特开2013-151019号公报的0055段<缩合物1的制造>中记载的步骤获得树脂a。对该树脂a的未反应呋喃甲醇及水分进行测定,根据该测定结果,使用上述树脂a、呋喃甲醇、水及硅烷偶联剂,以呋喃甲醇的含量成为50质量%,水的含量成为10质量%,硅烷偶联剂的含量成为0.15质量%的方式制备,获得制造例1的粘结剂组合物。Resin a was obtained by the procedure described in paragraph 0055 of <Production of Condensate 1> of Japanese Patent Application Laid-Open No. 2013-151019. The unreacted furan carbinol and water content of the resin a were measured, and based on the measurement results, the resin a, furan carbinol, water and silane coupling agent were used to prepare a binder composition of Production Example 1 in such a manner that the furan carbinol content was 50% by mass, the water content was 10% by mass and the silane coupling agent content was 0.15% by mass.

[制造例2][Production Example 2]

使用上述树脂a、呋喃甲醇、水及硅烷偶联剂,以呋喃甲醇的含量成为50质量%,水的含量成为20质量%,硅烷偶联剂的含量成为0.15质量%的方式制备,获得制造例2的粘结剂组合物。The above resin a, furancarbinol, water and a silane coupling agent were used to prepare an adhesive composition of Production Example 2 such that the furancarbinol content was 50 mass %, the water content was 20 mass % and the silane coupling agent content was 0.15 mass %.

[制造例3][Production Example 3]

向三口烧瓶中投入呋喃甲醇587g、25质量%氢氧化钠水溶液1.0g、92质量%多聚甲醛159g、戊二酸29g,在常压下在125℃下反应3小时。然后,冷却至90℃,加入尿素35g,后升温至105℃,在同一温度下反应2小时。反应后,冷却至75℃,加入尿素7g,在同一温度下反应20分钟,获得树脂b。树脂b中的呋喃甲醇为20.0质量%,BHMF为29.5质量%,水为6.8质量%,以及氮含量为2.4质量%。向上述树脂b中加入硅烷偶联剂1.5g、呋喃甲醇36g、水145g并进行混合,获得制造例3的粘结剂组合物。制造例3的粘结剂组合物中的呋喃甲醇的含量为20.0质量%,BHMF的含量为24.1质量%,呋喃树脂的含量为32.9质量%,水的含量为20.0质量%,呋喃树脂中的氮含量为6.0质量%。Into a three-necked flask, 587g of furan methanol, 1.0g of 25% by mass sodium hydroxide aqueous solution, 159g of 92% by mass polyformaldehyde, and 29g of glutaric acid were added, and the mixture was reacted at 125°C for 3 hours under normal pressure. Then, the mixture was cooled to 90°C, 35g of urea was added, and the mixture was heated to 105°C and reacted at the same temperature for 2 hours. After the reaction, the mixture was cooled to 75°C, 7g of urea was added, and the mixture was reacted at the same temperature for 20 minutes to obtain resin b. The furan methanol in resin b was 20.0% by mass, the BHMF was 29.5% by mass, the water was 6.8% by mass, and the nitrogen content was 2.4% by mass. 1.5g of silane coupling agent, 36g of furan methanol, and 145g of water were added to the above resin b and mixed to obtain the binder composition of Manufacturing Example 3. The binder composition of Production Example 3 contained 20.0 mass % furanol, 24.1 mass % BHMF, 32.9 mass % furan resin, 20.0 mass % water, and 6.0 mass % nitrogen in the furan resin.

[制造例4][Production Example 4]

向三口烧瓶中投入呋喃甲醇588g、25质量%氢氧化钠水溶液1.0g、92质量%多聚甲醛159g、苯甲酸29g,在常压下在125℃下反应2小时。其后,冷却至90℃,投入92质量%多聚甲醛10g、尿素50g,升温至105℃,在同一温度下反应2小时。反应后,冷却至75℃,加入尿素11g,在同一温度下反应20分钟,获得树脂c。上述树脂c中的呋喃甲醇为22.0质量%,BHMF为26.4质量%,水为7.4质量%,以及氮含量为3.3质量%。向上述树脂c中加入硅烷偶联剂1.5g、呋喃甲醇13g、水138g并进行混合,获得制造例4的粘结剂组合物。制造例4的粘结剂组合物中的呋喃甲醇的含量为20.0质量%,BHMF的含量为22.4质量%,呋喃树脂的含量为34.6质量%,水的含量为20.0质量%,呋喃树脂中的氮含量为8.1质量%。Into a three-necked flask, 588g of furan methanol, 1.0g of 25% by mass sodium hydroxide aqueous solution, 159g of 92% by mass polyformaldehyde, and 29g of benzoic acid were added, and the mixture was reacted at 125°C for 2 hours under normal pressure. Thereafter, the mixture was cooled to 90°C, 10g of 92% by mass polyformaldehyde and 50g of urea were added, the mixture was heated to 105°C, and the mixture was reacted at the same temperature for 2 hours. After the reaction, the mixture was cooled to 75°C, 11g of urea was added, and the mixture was reacted at the same temperature for 20 minutes to obtain resin c. The furan methanol in the above resin c was 22.0% by mass, the BHMF was 26.4% by mass, the water was 7.4% by mass, and the nitrogen content was 3.3% by mass. 1.5g of silane coupling agent, 13g of furan methanol, and 138g of water were added to the above resin c and mixed to obtain the binder composition of manufacturing example 4. The binder composition of Production Example 4 contained 20.0 mass % furanol, 22.4 mass % BHMF, 34.6 mass % furan resin, 20.0 mass % water, and 8.1 mass % nitrogen in the furan resin.

[制造例5][Production Example 5]

向三口烧瓶中加入359g的上述树脂c、121g的呋喃甲醇、173g的水、345g的BHMF、1.5g的硅烷偶联剂,在40℃下搅拌30分钟,获得制造例5的粘结剂组合物。制造例5的粘结剂组合物中的呋喃甲醇的含量为20.0质量%,BHMF的含量为44.0质量%,呋喃树脂的含量为14.7质量%,水的含量为20.0质量%,呋喃树脂中的氮含量为8.1质量%。359 g of the above resin c, 121 g of furan carbinol, 173 g of water, 345 g of BHMF, and 1.5 g of a silane coupling agent were added to a three-necked flask, and stirred at 40° C. for 30 minutes to obtain an adhesive composition of Manufacturing Example 5. The furan carbinol content in the adhesive composition of Manufacturing Example 5 was 20.0% by mass, the BHMF content was 44.0% by mass, the furan resin content was 14.7% by mass, the water content was 20.0% by mass, and the nitrogen content in the furan resin was 8.1% by mass.

[制造例6][Production Example 6]

向三口烧瓶中投入呋喃甲醇569g、25质量%氢氧化钠水溶液0.9g、92质量%多聚甲醛154g、戊二酸28g,在常压下在125℃下反应3小时。然后,冷却至90℃,加入亚乙基脲58g,后升温至105℃,在同一温度下反应3小时。反应后,冷却至75℃,加入尿素8g,在同一温度下反应20分钟,获得树脂d。树脂d中的呋喃甲醇为20.6质量%,BHMF为28.0质量%,水为6.5质量%,以及氮含量为2.8质量%。向上述树脂d中加入硅烷偶联剂1.5g、呋喃甲醇31g、水147g并进行混合,获得制造例6的粘结剂组合物。制造例6的粘结剂组合物中的呋喃甲醇的含量为20.0质量%,BHMF的含量为23.0质量%,呋喃树脂的含量为34.1质量%,水的含量为20.0质量%,呋喃树脂中的氮含量为6.7质量%。Into a three-necked flask, 569g of furan methanol, 0.9g of 25% by mass sodium hydroxide aqueous solution, 154g of 92% by mass polyformaldehyde, and 28g of glutaric acid were added, and the mixture was reacted at 125°C for 3 hours under normal pressure. Then, the mixture was cooled to 90°C, 58g of ethylene urea was added, and the mixture was heated to 105°C and reacted at the same temperature for 3 hours. After the reaction, the mixture was cooled to 75°C, 8g of urea was added, and the mixture was reacted at the same temperature for 20 minutes to obtain resin d. The furan methanol in resin d was 20.6% by mass, the BHMF was 28.0% by mass, the water was 6.5% by mass, and the nitrogen content was 2.8% by mass. 1.5g of silane coupling agent, 31g of furan methanol, and 147g of water were added to the above resin d and mixed to obtain the binder composition of manufacturing example 6. The binder composition of Production Example 6 contained 20.0 mass % furanol, 23.0 mass % BHMF, 34.1 mass % furan resin, 20.0 mass % water, and 6.7 mass % nitrogen in the furan resin.

[制造例7][Production Example 7]

向三口烧瓶中投入呋喃甲醇587g、25质量%氢氧化钠水溶液1.0g、92质量%多聚甲醛195g、戊二酸29g,在常压下在125℃下反应2小时。然后,冷却至90℃,加入三聚氰胺28g,后升温至105℃,在同一温度下反应2小时。反应后,冷却至75℃,加入尿素8g,在同一温度下反应20分钟,获得树脂e。树脂e中的呋喃甲醇为19.3质量%,BHMF为27.5质量%,水为7.3质量%,以及氮含量为2.8质量%。向上述树脂e中加入硅烷偶联剂1.5g、呋喃甲醇43g、水141g并进行混合,获得制造例7的粘结剂组合物。制造例7的粘结剂组合物中的呋喃甲醇的含量为20.0质量%,BHMF的含量为22.4质量%,呋喃树脂的含量为34.6质量%,水的含量为20.0质量%,呋喃树脂中的氮含量为6.6质量%。Into a three-necked flask, 587g of furan methanol, 1.0g of 25% by mass sodium hydroxide aqueous solution, 195g of 92% by mass polyformaldehyde, and 29g of glutaric acid were added, and the mixture was reacted at 125°C for 2 hours under normal pressure. Then, the mixture was cooled to 90°C, 28g of melamine was added, and the mixture was heated to 105°C and reacted at the same temperature for 2 hours. After the reaction, the mixture was cooled to 75°C, 8g of urea was added, and the mixture was reacted at the same temperature for 20 minutes to obtain resin e. The furan methanol in resin e was 19.3% by mass, the BHMF was 27.5% by mass, the water was 7.3% by mass, and the nitrogen content was 2.8% by mass. 1.5g of silane coupling agent, 43g of furan methanol, and 141g of water were added to the above resin e and mixed to obtain the adhesive composition of manufacturing example 7. The binder composition of Production Example 7 contained 20.0 mass % furanol, 22.4 mass % BHMF, 34.6 mass % furan resin, 20.0 mass % water, and 6.6 mass % nitrogen in the furan resin.

[制造例8][Production Example 8]

根据日本特表2014-501175记载的KH-Y的制造法,以下述步骤制造制造例6的粘结剂组合物。向三口烧瓶中投入呋喃甲醇197g、92质量%多聚甲醛196g、苯甲酸4.7g,在常压下在110℃下反应1小时。向该反应物中进而加入呋喃甲醇394g、苯甲酸9.4g,升温至135℃,回流5小时。反应结束后的温度为125℃。然后,投入尿素60g,历时约40分钟冷却至60℃,获得树脂f。上述树脂f中的呋喃甲醇为23.2质量%,BHMF为14.8质量%,水为7.3质量%,以及氮含量为3.3质量%。向上述树脂f中加入硅烷偶联剂1.5g、水137g并进行混合,获得制造例8的粘结剂组合物。制造例8的粘结剂组合物中的呋喃甲醇的含量为20.0质量%,BHMF的含量为12.7质量%,呋喃树脂的含量为45.7质量%,水的含量为20.0质量%,呋喃树脂中的氮含量为6.1质量%。According to the manufacturing method of KH-Y described in Japanese Patent Table 2014-501175, the adhesive composition of Manufacturing Example 6 was manufactured in the following steps. 197g of furan methanol, 196g of 92% by mass paraformaldehyde, and 4.7g of benzoic acid were added to a three-necked flask and reacted at 110°C for 1 hour under normal pressure. 394g of furan methanol and 9.4g of benzoic acid were further added to the reactant, the temperature was raised to 135°C, and refluxed for 5 hours. The temperature after the reaction was 125°C. Then, 60g of urea was added and cooled to 60°C for about 40 minutes to obtain resin f. The furan methanol in the above resin f was 23.2% by mass, BHMF was 14.8% by mass, water was 7.3% by mass, and the nitrogen content was 3.3% by mass. 1.5g of silane coupling agent and 137g of water were added to the above resin f and mixed to obtain the adhesive composition of Manufacturing Example 8. The binder composition of Production Example 8 contained 20.0 mass % furanol, 12.7 mass % BHMF, 45.7 mass % furan resin, 20.0 mass % water, and 6.1 mass % nitrogen in the furan resin.

<实施例1~21及比较例1~9><Examples 1 to 21 and Comparative Examples 1 to 9>

[铸模造型用粘结剂组合物的制造][Manufacturing of Binder Composition for Casting Molds]

使用上述制造例中所获得的尿素改性呋喃树脂、呋喃甲醇-甲醛树脂、BHMF、呋喃甲醇、水及硅烷偶联剂,在40℃下混合30分钟,获得实施例1~16及比较例1~8的铸模造型用粘结剂组合物。实施例17~21、比较例9及参考例1、2的铸模造型用粘结剂组合物分别使用上述所示的制造例1~8的组合物。The urea-modified furan resin, furan carbinol-formaldehyde resin, BHMF, furan carbinol, water and silane coupling agent obtained in the above-mentioned preparation examples were mixed at 40° C. for 30 minutes to obtain the binder compositions for casting molds of Examples 1 to 16 and Comparative Examples 1 to 8. The binder compositions for casting molds of Examples 17 to 21, Comparative Example 9 and Reference Examples 1 and 2 used the compositions of Preparation Examples 1 to 8 shown above, respectively.

[铸模用组合物的制造][Manufacturing of casting mold composition]

在5℃、55%RH的条件下,在呋喃再生硅砂100质量份中添加固化剂组合物,其次添加表1所示的铸模造型用粘结剂组合物0.8质量份,将这些混合,获得铸模用组合物。需要说明的是,固化剂组合物使用二甲苯磺酸/硫酸系固化剂(Kao Lightener US-3、KaoLightener C-21:Kao-Quaker公司制造)。固化剂组合物的添加量相对于呋喃再生硅砂100质量份为0.32质量份,调节Kao Lightener US-3与Kao Lightener C-21的比例,使下述试样的压缩强度成为0.20~0.35MPa/30分钟。另外,在添加量为0.32质量份时不满足上述压缩强度的情况下,仅使用Kao Lightener US-3,且增加添加量,使其满足上述压缩强度。Under the conditions of 5°C and 55% RH, a curing agent composition is added to 100 parts by mass of furan regenerated silica sand, and then 0.8 parts by mass of a binder composition for mold shaping shown in Table 1 is added, and these are mixed to obtain a composition for mold. It should be noted that the curing agent composition uses a xylenesulfonic acid/sulfuric acid curing agent (Kao Lightener US-3, Kao Lightener C-21: manufactured by Kao-Quaker). The amount of the curing agent composition added is 0.32 parts by mass relative to 100 parts by mass of furan regenerated silica sand, and the ratio of Kao Lightener US-3 to Kao Lightener C-21 is adjusted so that the compressive strength of the following sample becomes 0.20 to 0.35 MPa/30 minutes. In addition, when the above-mentioned compressive strength is not satisfied when the addition amount is 0.32 parts by mass, only Kao Lightener US-3 is used, and the addition amount is increased so that it satisfies the above-mentioned compressive strength.

[铸模压缩强度的评价][Evaluation of mold compression strength]

将刚混炼后的铸模用组合物立即填充到直径50mm、高度50mm的圆柱形试样框中,经过30分钟后进行脱模,用JIS Z2604-1976中记载的方法测定压缩强度(MPa),将该强度作为“30分钟后的压缩强度”。将“30分钟后的压缩强度”作为固化速度的标准,确认到固化剂量合适。另外,另将铸模用组合物同样地填充到试样框中,经过2小时后进行脱模,填充后24小时后,用JIS Z2604-1976中记载的方法测定压缩强度(MPa),作为“24小时后的压缩强度”。数值越高,表示铸模强度越高。将评价结果示于表1及表2。The mold composition just after kneading is immediately filled into a cylindrical sample frame with a diameter of 50 mm and a height of 50 mm. After 30 minutes, demoulding is performed, and the compressive strength (MPa) is measured by the method described in JIS Z2604-1976, and this strength is used as the "compressive strength after 30 minutes". The "compressive strength after 30 minutes" is used as a standard for the curing speed to confirm that the curing dosage is appropriate. In addition, the mold composition is similarly filled into the sample frame, demoulding is performed after 2 hours, and 24 hours after filling, the compressive strength (MPa) is measured by the method described in JIS Z2604-1976 as the "compressive strength after 24 hours". The higher the value, the higher the mold strength. The evaluation results are shown in Tables 1 and 2.

[表1][Table 1]

Figure BDA0004131594570000231
Figure BDA0004131594570000231

[表2][Table 2]

Figure BDA0004131594570000241
Figure BDA0004131594570000241

Claims (7)

1.一种铸模造型用粘结剂组合物,其含有呋喃甲醇即成分A、双羟甲基呋喃即成分B、树脂即成分C、以及水即成分D,1. A binder composition for mold molding, which contains furan methanol as component A, bismethylolfuran as component B, resin as component C, and water as component D, 所述铸模造型用粘结剂组合物满足下述条件(1)~(5):The binder composition for mold molding satisfies the following conditions (1) to (5): 条件(1):所述铸模造型用粘结剂组合物中的所述成分A的含量为30.0质量%以下;Condition (1): The content of the component A in the binder composition for casting molding is 30.0% by mass or less; 条件(2):所述铸模造型用粘结剂组合物中的所述成分D的含量为25.0质量%以下;Condition (2): The content of the component D in the binder composition for casting molding is 25.0% by mass or less; 条件(3):所述铸模造型用粘结剂组合物中所述成分B的含量相对于所述成分B与所述成分C的含量的合计为39.0质量%以上且95.0质量%以下;Condition (3): The content of the component B in the binder composition for casting molding is 39.0 mass% or more and 95.0 mass% or less with respect to the total content of the component B and the component C; 条件(4):所述成分C中的氮含量为2.7质量%以上且22.0质量%以下;Condition (4): The nitrogen content in the component C is not less than 2.7% by mass and not more than 22.0% by mass; 条件(5):当将所述铸模造型用粘结剂组合物中的所述成分B的含量设为y,将所述成分C的氮含量设为x时,满足下式(1):Condition (5): When the content of the component B in the casting mold molding binder composition is y, and the nitrogen content of the component C is x, the following formula (1) is satisfied: 2.97x+15.2≤y (1)。2.97x+15.2≤y (1). 2.根据权利要求1所述的铸模造型用粘结剂组合物,其中,所述成分C含有呋喃树脂,所述成分C中的所述呋喃树脂的含量为80质量%以上。2. The binder composition for casting molding according to claim 1, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 80% by mass or more. 3.根据权利要求2所述的铸模造型用粘结剂组合物,其中,所述呋喃树脂含有选自尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上。3. The casting mold molding binder composition according to claim 2, wherein the furan resin contains one selected from urea-modified furan resin, furan methanol condensate and furan methanol and aldehyde condensate One or more of the above, and two or more cocondensates selected from them. 4.根据权利要求3所述的铸模造型用粘结剂组合物,其中,所述呋喃树脂中的选自所述尿素改性呋喃树脂、呋喃甲醇缩合物及呋喃甲醇与醛类的缩合物中的一种以上、以及选自从它们中选择的两种以上的共缩合物中的一种以上的含量的合计为90质量%以上。4. The binder composition for casting molding according to claim 3, wherein, in the furan resin, the selected from the urea-modified furan resin, furan methanol condensate and furan methanol and aldehyde condensate The total content of one or more kinds of cocondensates selected from these and two or more kinds of cocondensates selected from them is 90% by mass or more. 5.一种铸模造型用组合物,其含有权利要求1~4中任一项所述的铸模造型用粘结剂组合物、及固化剂组合物,所述固化剂组合物包含使该铸模造型用粘结剂组合物固化的固化剂。5. A composition for molding a mold, comprising the binder composition for molding a mold according to any one of claims 1 to 4, and a curing agent composition comprising A curing agent that cures with a binder composition. 6.一种铸模用组合物,其含有耐火性粒子、权利要求1~4中任一项所述的铸模造型用粘结剂组合物、及固化剂组合物,所述固化剂组合物包含使该铸模造型用粘结剂组合物固化的固化剂。6. A composition for casting, which contains refractory particles, the binder composition for casting molding according to any one of claims 1 to 4, and a curing agent composition, the curing agent composition comprising A curing agent for curing the binder composition for casting. 7.一种铸模的制造方法,其包括以下工序:7. A method for manufacturing a mold, comprising the following steps: 混合工序,其将耐火性粒子、权利要求1~4中任一项所述的铸模造型用粘结剂组合物、及固化剂组合物混合,获得铸模用组合物,所述固化剂组合物包含使该铸模造型用粘结剂组合物固化的固化剂;及a mixing step of mixing the refractory particles, the binder composition for molding molding according to any one of claims 1 to 4, and a curing agent composition to obtain a molding composition, the curing agent composition comprising a curing agent for curing the binder composition for molding; and 固化工序,其将所述铸模用组合物装入模框,并使该铸模用组合物固化。A curing step of putting the molding composition into a mold frame and curing the molding composition.
CN202080105309.0A 2020-11-13 2020-11-13 Adhesive composition for casting mold Pending CN116234647A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2020/042460 WO2022102089A1 (en) 2020-11-13 2020-11-13 Binder composition for forming mold

Publications (1)

Publication Number Publication Date
CN116234647A true CN116234647A (en) 2023-06-06

Family

ID=81601831

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080105309.0A Pending CN116234647A (en) 2020-11-13 2020-11-13 Adhesive composition for casting mold

Country Status (4)

Country Link
JP (1) JP7102639B1 (en)
CN (1) CN116234647A (en)
TW (1) TW202229492A (en)
WO (1) WO2022102089A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119923298A (en) * 2022-11-29 2025-05-02 花王株式会社 Binder composition for casting mold making

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4376745A (en) * 1981-06-15 1983-03-15 Washington State University Research Foundation Particle board process using furan resin/isocyanate binder
CN1155856A (en) * 1994-08-19 1997-07-30 花王株式会社 Binder composition for mold production and method for producing mold
CN1366472A (en) * 2000-04-27 2002-08-28 阿什兰公司 Furan no-bake foundry binders and their use
US20050090578A1 (en) * 2003-09-18 2005-04-28 Chang Ken K. Heat-cured furan binder system
JP2018024004A (en) * 2016-08-12 2018-02-15 花王株式会社 Binder composition for mold making
WO2020035923A1 (en) * 2018-08-16 2020-02-20 花王株式会社 Binding agent composition for foundry molding

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3114516B2 (en) * 1994-08-19 2000-12-04 花王株式会社 Binder composition for mold production and method for producing mold
JP5486241B2 (en) * 2009-08-26 2014-05-07 花王株式会社 Binder composition for mold making
JP5563875B2 (en) * 2010-04-16 2014-07-30 花王株式会社 Kit for producing a mold composition
TWI564317B (en) * 2010-12-16 2017-01-01 哈登斯 雅伯特斯化學威基有限公司 Low-emission cold-setting binder for the foundry industry
JP6010426B2 (en) * 2011-10-31 2016-10-19 花王株式会社 Binder composition for mold making
DE102017112681A1 (en) * 2017-06-08 2018-12-13 Ask Chemicals Gmbh Process for the preparation of three-dimensionally layered shaped bodies
JP7175822B2 (en) * 2019-03-28 2022-11-21 群栄化学工業株式会社 Sand composition, method for producing same, and method for producing mold

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4376745A (en) * 1981-06-15 1983-03-15 Washington State University Research Foundation Particle board process using furan resin/isocyanate binder
CN1155856A (en) * 1994-08-19 1997-07-30 花王株式会社 Binder composition for mold production and method for producing mold
CN1366472A (en) * 2000-04-27 2002-08-28 阿什兰公司 Furan no-bake foundry binders and their use
US20050090578A1 (en) * 2003-09-18 2005-04-28 Chang Ken K. Heat-cured furan binder system
JP2018024004A (en) * 2016-08-12 2018-02-15 花王株式会社 Binder composition for mold making
WO2020035923A1 (en) * 2018-08-16 2020-02-20 花王株式会社 Binding agent composition for foundry molding

Also Published As

Publication number Publication date
JPWO2022102089A1 (en) 2022-05-19
WO2022102089A1 (en) 2022-05-19
JP7102639B1 (en) 2022-07-19
TW202229492A (en) 2022-08-01

Similar Documents

Publication Publication Date Title
CN104220504B (en) For manufacturing the adhesive composition of casting mold
CN104245183B (en) Making molds curing agent composition, its purposes and its manufacture method and the manufacture method of casting mold
JP6010426B2 (en) Binder composition for mold making
CN105848805B (en) Making molds with composition, from the manufacture method of solidity casting mold and from solidity making molds external member
CN105689636B (en) Set for casting
JP5683941B2 (en) Method for producing binder composition for mold making
CN116234647A (en) Adhesive composition for casting mold
JP6097135B2 (en) Binder composition for mold making
JP7516667B2 (en) Method for producing binder resin for casting
CN112512722B (en) Binder composition for mold molding
CN108348986B (en) Casting mold molding kit
WO2020035922A1 (en) Binding agent composition for foundry molding
JP6971412B2 (en) Blotting agent composition for molding
JP5944259B2 (en) Binder composition for mold making
CN119923298A (en) Binder composition for casting mold making
JP6512983B2 (en) Binder composition for mold making
JP6063219B2 (en) Binder composition for mold making
JP2016107328A (en) Binder composition for molding mold
JP2021020240A (en) Binder composition for mold forming
JP2019107668A (en) Hardening accelerator for die molding
JP2016078106A (en) Composition for molding cast

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination