WO2020246538A1 - 発泡砂用界面活性剤組成物 - Google Patents

発泡砂用界面活性剤組成物 Download PDF

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Publication number
WO2020246538A1
WO2020246538A1 PCT/JP2020/022084 JP2020022084W WO2020246538A1 WO 2020246538 A1 WO2020246538 A1 WO 2020246538A1 JP 2020022084 W JP2020022084 W JP 2020022084W WO 2020246538 A1 WO2020246538 A1 WO 2020246538A1
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WO
WIPO (PCT)
Prior art keywords
mass
group
component
sand
mold
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.)
Ceased
Application number
PCT/JP2020/022084
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English (en)
French (fr)
Japanese (ja)
Inventor
紀宏 菅谷
博之 小宮
宗宏 山田
浩庸 渡邉
尚吾 泉
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.)
NOF Corp
Toyota Motor Corp
Original Assignee
NOF Corp
Toyota Motor 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 NOF Corp, Toyota Motor Corp filed Critical NOF Corp
Priority to JP2021524898A priority Critical patent/JP7113142B2/ja
Priority to CN202080039493.3A priority patent/CN113905837B/zh
Priority to EP20819378.9A priority patent/EP3981525A4/en
Priority to BR112021023515A priority patent/BR112021023515A2/pt
Priority to US17/615,385 priority patent/US12152189B2/en
Publication of WO2020246538A1 publication Critical patent/WO2020246538A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions 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
    • B22C1/18—Compositions 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 inorganic agents
    • B22C1/186—Compositions 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 inorganic agents contaming ammonium or metal silicates, silica sols
    • B22C1/188—Alkali metal silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions 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
    • B22C1/10—Compositions 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions 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
    • B22C1/18—Compositions 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 inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/04—Sulfonates or sulfuric acid ester salts derived from polyhydric alcohols or amino alcohols or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/08—Sulfation or sulfonation products of fats, oils, waxes, or higher fatty acids or esters thereof with monovalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/18—Quaternary ammonium compounds

Definitions

  • the present invention relates to a surfactant composition for foamed sand, which is excellent in quick foaming property of foamed sand and further improves the strength of the mold when manufacturing a mold such as sand core using foamed sand.
  • Patent Document 1 is known as a conventional technique for a mold molding apparatus.
  • Patent Document 1 describes a mold molding apparatus for molding a mold by press-fitting and filling a cavity of a heated mold with a foamy mixture obtained by stirring a particulate aggregate, a water-soluble binder and water, and the mold molding apparatus used therein.
  • the mold device is disclosed. This provides a molding apparatus capable of effectively utilizing the foamed mixture and sufficiently ensuring the filling of the mold cavity with the flowing sand, and also provides an apparatus capable of significantly shortening the curing time of the foamed mixture. Is.
  • An object of the present invention is to provide a surfactant composition for foamed sand, which is excellent in quick foaming property of foamed sand and further improves the strength of the mold at the time of producing a mold such as sand core using foamed sand. is there.
  • the present inventors have made a specific ratio of a specific polyoxyethylene alkyl ether sulfate ester salt, a specific alkyl sulfate ester salt, and a specific amphoteric surfactant, respectively. It has been found that the surfactant composition for foamed sand contained in the above is excellent in quick foaming property of foamed sand and further exerts an effect of improving the strength of the mold, and has completed the present invention.
  • the compound (A) represented by the following formula (1) is 80 to 99.8% by mass
  • the compound (B) represented by the following formula (2) is 0.1 to 10% by mass
  • amphoteric A surfactant composition for foamed sand, which comprises 0.1 to 10% by mass of the surfactant (C).
  • R 1 represents a hydrocarbon group having 6 to 22 carbon atoms.
  • EO is an oxyethylene group n is the average number of moles of the oxyethylene group added, and n is 1 to 10.
  • M 1 is an alkali metal, alkaline earth metal, ammonium or organic ammonium.
  • R 2 O-SO 3 M 2 ... (2) In equation (2), R 2 is a hydrocarbon group having 6 to 22 carbon atoms.
  • M 2 is an alkali metal, alkaline earth metal, ammonium or organic ammonium.
  • a binder, sand, a surfactant composition, water and the like can be sufficiently foamed by kneading for a short time, and a high-strength mold can be produced.
  • the surfactant composition for foamed sand of the present invention contains a component (A), a component (B) and a component (C).
  • the total mass ratio of the components (A), (B), and (C) is 100% by mass.
  • each component will be described.
  • the numerical range indicated by “1 to 10" or the like includes the numerical values of the upper limit and the lower limit, and means 1 or more and 10 or less.
  • the component (A) used in the present invention is a polyoxyethylene alkyl ether sulfate ester salt represented by the following formula (1).
  • R 1 is a hydrocarbon group having 6 to 22 carbon atoms, preferably a hydrocarbon group having 6 to 20 carbon atoms.
  • the hydrocarbon group may be a saturated hydrocarbon group or a hydrocarbon group having a carbon-carbon double bond (particularly preferably an alkenyl group).
  • the hydrocarbon group is an unsaturated hydrocarbon group having a carbon-carbon double bond, the number of double bonds is preferably 3 or less, and more preferably 2 or less.
  • Examples of such a hydrocarbon group include a capryl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group, a behenyl group and the like.
  • a hydrocarbon group derived from a mixed fatty acid containing two or more kinds of hydrocarbon groups is also used, and for example, a coconut oil hydrocarbon group or a palm kernel oil hydrocarbon group can also be used.
  • a lauryl group, a myristyl group, a coconut oil hydrocarbon group, and a palm kernel oil hydrocarbon group are preferable, and a myristyl group is more preferable.
  • n indicates the average number of moles of oxyethylene groups added, and n is 1 to 10, preferably 2 to 6, and more preferably 3 to 4.
  • M 1 is an alkali metal, alkaline earth metal, ammonium or organic ammonium.
  • alkali metal include lithium, sodium, potassium and the like, and sodium is preferable.
  • alkaline earth metal include calcium, strontium, barium and the like, and calcium is preferable.
  • Ammonium is NH 4 +.
  • organic ammonium examples include alkanolamines derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and alkylammoniums derived from alkylamines such as diethylamine and triethylamine.
  • one type or two or more types of the component (A) can be appropriately selected and used.
  • the content of the component (A) is 80 to 99.8% by mass. If the content of the component (A) is less than 80% by mass, the strength of the mold is lowered. Therefore, the content is 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more. Further, when the content of the component (A) exceeds 99.8% by mass, the quick foaming property is lowered, so the content is 99.8% by mass or less, preferably 97% by weight or less, more preferably 95% or less. ..
  • Component (B) The component (B) used in the present invention is an alkyl sulfate ester salt represented by the following formula (2). R 2 O-SO 3 M 2 ... (2)
  • R 2 is a hydrocarbon group having 6 to 22 carbon atoms, preferably a hydrocarbon group having 6 to 20 carbon atoms.
  • the hydrocarbon group may be a saturated hydrocarbon group or a hydrocarbon group having an unsaturated bond having a carbon-carbon double bond (particularly preferably an alkenyl group).
  • the hydrocarbon group is an unsaturated hydrocarbon group having a carbon-carbon double bond, the number of double bonds is preferably 3 or less, and more preferably 2 or less.
  • hydrocarbon group examples include a capryl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group, a behenyl group and the like.
  • a hydrocarbon group derived from a mixed fatty acid containing two or more kinds of hydrocarbon groups is also used, and for example, a coconut oil hydrocarbon group or a palm kernel oil hydrocarbon group can also be used. Of these, coconut oil hydrocarbon groups and palm kernel oil hydrocarbon groups are preferred.
  • M 2 is an alkali metal, alkaline earth metal, ammonium or organic ammonium.
  • alkali metal include lithium, sodium, potassium and the like, and sodium is preferable.
  • alkaline earth metal include calcium, strontium, barium and the like, and calcium is preferable.
  • organic ammonium include alkanolamines derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and alkylammoniums derived from alkylamines such as diethylamine and triethylamine. In the present invention, one type or two or more types of the component (B) can be appropriately selected and used.
  • the content of the component (B) is 0.1 to 10% by mass.
  • the content of the component (B) is less than 0.1% by mass, the quick foaming property is lowered, so the content is 0.1% by mass or more, but more preferably 0.5% by mass or more. If the content of the component (B) exceeds 10% by mass, the strength of the mold may decrease. Therefore, the content is 10% by mass or less, more preferably 7% by mass or less, and 5% by mass or less. More preferred.
  • the component (C) used in the present invention is an amphoteric surfactant, and examples thereof include a surfactant having a structure having an N-acyl group or an N-alkyl group, a cationic group, and an anionic group. Be done. Specifically, for example, alkylbetaine, alkylamide betaine, alkylhydroxysulfobetaine, alkylamide hydroxysulfobetaine, alkylcarboxymethylhydroxyethyl imidazolinium betaine, alkylamide hydroxyethyl amino acid type amphoteric surfactant, alkyliminodiacetic acid. Examples include salt.
  • the acyl group contained in the above amphoteric surfactant is, for example, a linear or branched fatty acid residue having 6 to 22 carbon atoms.
  • the fatty acid in this fatty acid residue include saturated fatty acids such as caproic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, and behenic acid, palmitoleic acid, and oleic acid.
  • lauric acid, coconut oil fatty acid, and palm kernel oil fatty acid are preferable. Particularly preferred is lauric acid.
  • the alkyl group contained in the above amphoteric surfactant is, for example, a hydrocarbon group having 6 to 22 carbon atoms, and also includes an alkyl group derived from a mixed fatty acid.
  • alkyl groups such as caproyl group, caprylyl group, capryl group, lauryl group, myristyl group, palmitic group, stearyl group and oleyl group, mixed alkyl group such as coconut oil alkyl group, palm kernel oil alkyl group and beef tallow alkyl group can be used.
  • a lauryl group, a coconut oil alkyl group, and a palm kernel oil alkyl group are preferable. Particularly preferred is a lauryl group.
  • amphoteric surfactant of the component (C) include lauryl betaine, coconut oil fatty acid amide propyl betaine, palm kernel oil fatty acid amide propyl betaine, lauryl dimethylaminoacetic acid betaine, lauryl hydroxysulfobetaine and the like.
  • one type or two or more types of the component (C) can be appropriately selected and used.
  • the content of the component (C) is 0.1 to 10% by mass.
  • the content of the component (C) is less than 0.1% by mass, the strength of the mold is lowered, so the content is 0.1% by mass or more, more preferably 3% by mass or more, and further 5% by mass or more. preferable.
  • the content of the component (C) exceeds 10% by mass, the quick foaming property is lowered, so the content is set to 10% by mass or less.
  • the surfactant composition for foamed sand of the present invention may contain additives in addition to the above components as long as the effects of the present invention are not impaired.
  • additives include organic or inorganic salts, pH regulators, bactericides, chelating agents, pigments, fragrances and the like.
  • Examples 1 to 8 and Comparative Examples 1 to 9 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. All the raw materials of Examples 1 to 8 and Comparative Examples 1 to 9 shown in Tables 4 and 5 were put into a beaker and stirred at 50 ° C. for 1 hour using a magnetic stirrer to compose a surfactant composition for foamed sand. I adjusted things. The blending amount in the table is mass%, and "-" means 0 mass%.
  • Step 1 Prepare artificial sand as a particulate aggregate, water glass, a surfactant for evaluation, and water as a water-soluble binder. These materials are added to the kneading apparatus by weight ratio of artificial sand 100, water glass solid content 0.5 to 2.5, surfactant active ingredient 0.01 to 0.05, and water 2 to 4. Step 2 The above materials are kneaded for 120 seconds using a kneading device to make an effervescent mixture. Step 3 The foamed kneaded product is put into the kinematic viscosity measuring device as shown in FIG. Step 4 As shown in FIG.
  • Measurement time is less than 2.00 seconds
  • Measurement time is 2.00 seconds or more and less than 2.20 seconds
  • Measurement time is 2.20 seconds or more
  • Step 1 Prepare artificial sand as a particulate aggregate, water glass, a surfactant for evaluation, and water as a water-soluble binder. These materials are added to the kneading apparatus by weight ratio of artificial sand 100, water glass solid content 0.5 to 2.5, surfactant active ingredient 0.01 to 0.05, and water 2 to 4. Step 2 These materials are kneaded for 300 seconds using a kneading device to prepare an effervescent mixture. Step 3 The foamed mixture prepared above is put into a molding die using a test piece molding device for strength measurement.
  • the mold test piece (10 mm ⁇ 30 mm ⁇ 85 mm) is formed by firing in a molding die at 200 to 300 ° C. for 30 to 120 seconds.
  • Step 4 The mold test piece that has been molded and taken out is cooled to room temperature.
  • Step 5 As shown in FIG. 2, a test piece was set in a mold bending strength tester, and the bending strength of the test piece was measured to obtain the mold strength.
  • the unit of mold strength is kg / cm 2 .
  • Mold strength is 31 or more ⁇ : Mold strength is 30.5 or more and less than 31 ⁇ : Mold strength is 30 or more and less than 30.5 ⁇ : Mold strength is less than 30
  • the surfactant compositions for foamed sand according to Examples 1 to 8 according to the present invention contain the component (A), the component (B) and the component (C) in a specific ratio, the foamed sand is quickly foamed. The results were excellent in properties and the mold strength was also good.
  • Comparative Example 1 since the component (B) and the component (C) were not contained, the quick foaming property and the mold strength were low. In Comparative Example 2, since the component (A) and the component (C) were not contained, the mold strength was low. In Comparative Example 3, since the component (B) and the component (C) were not contained, the quick foaming property was low. In Comparative Example 4, since the component (B) and the component (C) were not contained, the quick foaming property and the mold strength were low. In Comparative Example 5, since the component (B) and the component (C) were not contained, the quick foaming property was low. In Comparative Example 6, since the component (A) was not contained, the mold strength was low.
  • Comparative Example 7 since the content of the component (C) exceeded the upper limit of the specified range of the claims, the quick foaming property was lowered. In Comparative Example 8, since the content of the component (B) exceeded the upper limit of the specified range of the claims, the casting strength was lowered. In Comparative Example 9, since the component (C) was not contained, the mold strength was low.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mold Materials And Core Materials (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2020/022084 2019-06-07 2020-06-04 発泡砂用界面活性剤組成物 Ceased WO2020246538A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2021524898A JP7113142B2 (ja) 2019-06-07 2020-06-04 発泡砂用界面活性剤組成物
CN202080039493.3A CN113905837B (zh) 2019-06-07 2020-06-04 发泡砂用表面活性剂组合物
EP20819378.9A EP3981525A4 (en) 2019-06-07 2020-06-04 SURFACTANT COMPOSITION FOR FOAMING SAND
BR112021023515A BR112021023515A2 (pt) 2019-06-07 2020-06-04 Composição de tensoativo para areia espumante
US17/615,385 US12152189B2 (en) 2019-06-07 2020-06-04 Surfactant composition for foaming sand

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-106698 2019-06-07
JP2019106698 2019-06-07

Publications (1)

Publication Number Publication Date
WO2020246538A1 true WO2020246538A1 (ja) 2020-12-10

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PCT/JP2020/022084 Ceased WO2020246538A1 (ja) 2019-06-07 2020-06-04 発泡砂用界面活性剤組成物

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US (1) US12152189B2 (https=)
EP (1) EP3981525A4 (https=)
JP (1) JP7113142B2 (https=)
CN (1) CN113905837B (https=)
BR (1) BR112021023515A2 (https=)
WO (1) WO2020246538A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023112733A1 (https=) * 2021-12-17 2023-06-22
US20240042513A1 (en) * 2021-03-23 2024-02-08 Sintokogio, Ltd. Sand mold-forming additive, sand mold-forming composition, sand mold manufacturing method, and sand mold

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Publication number Priority date Publication date Assignee Title
JPS63115649A (ja) * 1986-10-31 1988-05-20 Sintokogio Ltd 中空中子の造型方法
JP2001314939A (ja) * 2000-04-28 2001-11-13 Hodogaya Ashland Kk ガス硬化性鋳型用粘結剤組成物
WO2005089984A1 (ja) 2004-03-23 2005-09-29 Sintokogio, Ltd. 鋳型造型装置およびそれに使用する金型装置

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GB2107327B (en) 1981-10-02 1985-05-30 Politechnika Slaska Im Wincent Moulding and core sand compositions
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JP5734818B2 (ja) * 2011-11-28 2015-06-17 トヨタ自動車株式会社 砂型造型方法及び砂型
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JPS63115649A (ja) * 1986-10-31 1988-05-20 Sintokogio Ltd 中空中子の造型方法
JP2001314939A (ja) * 2000-04-28 2001-11-13 Hodogaya Ashland Kk ガス硬化性鋳型用粘結剤組成物
WO2005089984A1 (ja) 2004-03-23 2005-09-29 Sintokogio, Ltd. 鋳型造型装置およびそれに使用する金型装置

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See also references of EP3981525A4

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240042513A1 (en) * 2021-03-23 2024-02-08 Sintokogio, Ltd. Sand mold-forming additive, sand mold-forming composition, sand mold manufacturing method, and sand mold
JPWO2023112733A1 (https=) * 2021-12-17 2023-06-22
WO2023112733A1 (ja) * 2021-12-17 2023-06-22 日油株式会社 発泡砂用界面活性剤組成物
CN117062680A (zh) * 2021-12-17 2023-11-14 日油株式会社 发泡砂用表面活性剂组合物
JP7554939B2 (ja) 2021-12-17 2024-09-20 日油株式会社 発泡砂用界面活性剤組成物
CN117062680B (zh) * 2021-12-17 2025-09-12 日油株式会社 发泡砂用表面活性剂组合物

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JP7113142B2 (ja) 2022-08-04
EP3981525A4 (en) 2022-07-20
JPWO2020246538A1 (https=) 2020-12-10
CN113905837A (zh) 2022-01-07
US12152189B2 (en) 2024-11-26
BR112021023515A2 (pt) 2022-01-18
CN113905837B (zh) 2023-05-30
US20220228067A1 (en) 2022-07-21
EP3981525A1 (en) 2022-04-13

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