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WO2018169008A1 - Brittle material processing liquid - Google Patents

Brittle material processing liquid Download PDF

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Publication number
WO2018169008A1
WO2018169008A1 PCT/JP2018/010249 JP2018010249W WO2018169008A1 WO 2018169008 A1 WO2018169008 A1 WO 2018169008A1 JP 2018010249 W JP2018010249 W JP 2018010249W WO 2018169008 A1 WO2018169008 A1 WO 2018169008A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
component
processing liquid
brittle material
material processing
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/JP2018/010249
Other languages
French (fr)
Japanese (ja)
Inventor
友彦 北村
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.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
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 Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Priority to CN201880018018.0A priority Critical patent/CN110382673B/en
Publication of WO2018169008A1 publication Critical patent/WO2018169008A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B27/00Other grinding machines or devices
    • B24B27/06Grinders for cutting-off
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B55/00Safety devices for grinding or polishing machines; Accessories fitted to grinding or polishing machines for keeping tools or parts of the machine in good working condition
    • B24B55/02Equipment for cooling the grinding surfaces, e.g. devices for feeding coolant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28DWORKING STONE OR STONE-LIKE MATERIALS
    • B28D5/00Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor
    • B28D5/04Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor by tools other than rotary type, e.g. reciprocating tools
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/10Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M105/14Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms polyhydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18Ethers, e.g. epoxides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/06Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/08Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24Polyethers
    • C10M145/26Polyoxyalkylenes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a brittle material working fluid and a method for producing the brittle material working fluid.
  • wire saw processing is generally used for cutting silicon ingots from the viewpoint of processing accuracy and productivity.
  • Wire saw processing is also used for processing materials such as ceramics, quartz, sapphire, and glass.
  • a free abrasive grain method that performs processing while supplying free abrasive grains to a sliding portion between the wire and a workpiece, and a wire in which abrasive grains are fixed to the surface of the wire in advance
  • a fixed abrasive method in which processing is performed using
  • the fixed abrasive method is often used for the reason that the yield can be improved.
  • the processing fluid used in the above-mentioned applications includes an aqueous processing fluid containing mineral oil, animal and vegetable oils, synthetic oil, etc. as a main component and a compound having a surface active ability to provide water-soluble processing. Liquid. In recent years, a working fluid imparted with water solubility has been used from the viewpoint of safety during work and environmental problems.
  • Patent Document 1 discloses a water-soluble machining liquid composition for a fixed abrasive wire saw that is used for cutting work materials other than rare earth magnets, and contains glycols.
  • a liquid composition is disclosed.
  • Patent Document 2 discloses a water-soluble working fluid composition for fixed abrasive wire saws used for cutting rare earth magnets, which includes glycols, carboxylic acid, a compound that dissolves in water and exhibits basicity, water Are contained in a specific content (however, the total of these components is 100 parts by weight), and a water-soluble working liquid composition for a fixed abrasive wire saw is disclosed.
  • Patent Document 3 discloses an aqueous cutting fluid characterized by containing 0.01 to 20% by mass of acetylene glycol and / or its alkylene oxide adduct.
  • a multi-wire saw apparatus is used to cut out a plurality of silicon wafers from the above-described silicon ingot at a time.
  • the multi-wire saw device one wire is wound around each groove on two or more guide rollers having a plurality of grooves carved at a constant interval, and each wire is held in parallel with a constant tension.
  • each guide roller is rotated and the wire is run in one or both directions while the machining liquid discharged from the nozzle or the like is adhered to the wire, and the silicon ingot is pushed onto the wire to which the machining liquid is adhered. Cutting is applied.
  • the processing liquid used for the wire saw processing is put into a tank provided in the wire saw device, supplied from the tank to the processing chamber nozzle by a pump provided in the wire saw device, and discharged from the nozzle.
  • the machining fluid discharged from the nozzle is supplied aiming at the machining gap (gap between the wire and the silicon ingot), used for lubrication of the machining gap, etc., and then returns to the tank again.
  • the machining fluid circulates in the wire saw device.
  • the processing liquid may be violently scattered due to high-speed rotation of the guide roller accompanying the increase in the wire speed, which leads to bubbling of the processing liquid.
  • the processing liquid may flow down to a tank below the wire saw device, and the processing liquid in the tank may be foamed violently and overflow from the tank.
  • the problem that fine chips generated during the cutting process promote foaming of the processing liquid, and wire saws and cut wafers are significantly contaminated by the chips, and the load for cleaning them is large. There was a problem of becoming.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a brittle material processing liquid that is excellent in antifoaming properties and contamination suppression effects.
  • the present inventors have one or more selected from the group consisting of water, acetylene glycol satisfying a specific condition and an alkylene oxide adduct of acetylene glycol, and no acetylene group satisfying the specific condition. It has been found that a brittle material processing liquid that contains a nonionic surfactant and the content ratio of these components satisfies a specific range can solve the above-mentioned problems.
  • Each embodiment of the present invention has been completed based on such knowledge. That is, according to each embodiment of the present invention, the following [1] or [2] is provided.
  • the content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid
  • the content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid
  • the content of the component (A) and the component (B) A brittle material processing liquid in which the ratio [A / B] is 0.05 to 2.00 in terms of
  • a method for producing a brittle material processing liquid The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) The method for producing a brittle material processing liquid according to the
  • the brittle material processing fluid contains water, the following component (A) and component (B), and contains component (A).
  • the amount is 0.010% by mass or more and 0.200% by mass or less based on the total amount of 100% by mass of the brittle material processing liquid
  • Content of component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of brittle material processing liquid
  • content of component (A) and component (B) The ratio [A / B] is 0.05 to 2.00 in terms of mass ratio.
  • a nonionic surfactant that is an ethylene oxide adduct having an ethylene oxide addition mole number of 5 or more in the molecular structure and does not have an acetylene group. It is inferior in antifoaming property and pollution control effect.
  • the “HLB value” means a value of HLB (Hydrophilic-Lipophilic Balance) calculated by the Griffin method.
  • the lower limit value and upper limit value which were described in steps can be combined independently, respectively.
  • the description of the lower limit value “preferably 10 or more, more preferably 20 or more, more preferably 30 or more” and “preferably 90 or less, more preferably 80 or less, more preferably 60 or less”. Therefore, the preferable range can be set to “10 or more and 60 or less” by combining “preferable lower limit value (10)” and “more preferable upper limit value (60)”.
  • the “more preferable lower limit value (30)” and the “preferable upper limit value (90)” can be combined to set the preferable range to “30 or more and 90 or less”.
  • preferably 10 to 90, more preferably 20 to 80, still more preferably 30 to 60 can be used as “10 to 60”.
  • 10 to 90 is simply described as a preferable numerical range, it represents a range of 10 to 90.
  • each component contained in the processing liquid will be described.
  • Component (A) is at least one selected from the group consisting of acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12.
  • HLB value of the component (A) is less than 4, the solubility of the component (A) in water is poor. Moreover, the defoaming property of the said processing liquid and the contamination inhibitory effect will deteriorate that the HLB value of the said component (A) is more than 12.
  • the HLB value is preferably 4 or more and 10 or less, more preferably 4 or more and 9 or less, and still more preferably 4 or more and 8 or less.
  • alkylene oxide hereinafter also simply referred to as“ AO ”) adduct refers to not only a compound to which a single alkylene oxide is added, but also a plurality of alkylene oxides, In addition, a compound to which a polyalkylene oxide is added is also included.
  • EO ethylene oxide
  • PO propylene oxide
  • Examples of the acetylene glycol include compounds represented by the following general formula (1).
  • R 1 to R 4 each independently represents an alkyl group having 1 to 5 carbon atoms.
  • Specific examples of the alkyl group having 1 to 5 carbon atoms that can be taken by R 1 to R 4 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl.
  • R 1 and R 3 are preferably an isobutyl group or a 3-methylbutyl group.
  • R 2 and R 4 are preferably methyl groups.
  • the compound represented by the general formula (1) is preferably a compound having a structure in which R 1 and R 3 are the same as each other or a structure in which R 2 and R 4 are the same as each other, more preferably Is a compound having a structure in which R 1 and R 3 are identical to each other, and R 2 and R 4 are identical to each other.
  • the alkylene oxide adduct of acetylene glycol is preferably an alkylene oxide adduct of the compound represented by the general formula (1) in which AO is added to each hydroxyl group of the compound represented by the general formula (1). More preferably, an alkylene oxide adduct of the compound represented by the general formula (1) to which EO and / or PO is added, and more preferably an alkylene of the compound represented by the general formula (1) to which EO is added. It is an oxide adduct.
  • the suitable aspect of the acetylene glycol which forms the alkylene oxide adduct of the said acetylene glycol is the same as the suitable aspect of the compound represented by the aforementioned general formula (1).
  • the structure derived from EO for example, ethyleneoxy group or poly (oxyethylene) structure
  • the structure derived from PO for example, propyleneoxy group or poly (oxypropylene) structure
  • the structures may be bonded to each other in a random type, may be bonded in a block type, and preferably is a block type.
  • Component (A) includes 2,5,8,11-tetramethyl-6-dodecin-5,8-diol, 5,8-dimethyl-6-dodecin-5,8-diol, 2,4,7, 9-tetramethyl-5-dodecin-4,7-diol, 8-hexadecin-7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetramethyl-4-octyne 3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5
  • An acetylene glycol represented by the general formula (1) such as decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6-diol; and an acetylene represented by the
  • alkylene oxide examples include EO and / or PO. Of these, 2,5,8,11-tetramethyl-6-dodecin-5,8-diol, 5,8-dimethyl-6-dodecin-5,8-diol, 2,4,7, 9-tetramethyl-5-dodecin-4,7-diol, 8-hexadecin-7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetramethyl-4-octyne 3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5
  • One or more alkylene oxide adducts selected from the group consisting of decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6-d
  • Content of a component (A) is 0.010 mass% or more and 0.200 mass% or less on the basis of 100 mass% of the whole quantity of the said processing liquid.
  • the content of the component (A) is preferably 0.015% by mass or more, more preferably 0.020% by mass or more, and still more preferably 0.05% by mass or more based on the total amount of the processing liquid of 100% by mass. It is 040% by mass or more, and preferably 0.150% by mass or less, more preferably 0.100% by mass or less, and still more preferably 0.070% by mass or less.
  • Component (B) is an ethylene oxide adduct having an HLB value of 6 or more, an added mole number of ethylene oxide in the molecular structure of 5 or more, and a nonionic surfactant having no acetylene group. .
  • the processing liquid contains the component (B) so as to satisfy the content ratio [A / B], so that the processing liquid is excellent in antifoaming property and contamination suppression effect.
  • the number of moles of EO added to the component (B) is less than 5, the effect of suppressing contamination of the processing liquid is deteriorated.
  • the EO addition mole number is preferably 6 or more, more preferably 7 or more, still more preferably 10 or more, and still more preferably 20 or more.
  • the upper limit of the EO addition mole number is not particularly limited, but is preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less, from the viewpoint of obtaining a better defoaming property and contamination suppressing effect of the processing liquid. It is.
  • the solubility to the water of a component (B) is inferior that the HLB value of the said component (B) is less than 6. From such a viewpoint, the HLB value is preferably 7 or more, more preferably 8 or more.
  • the upper limit of the HLB value of the component (B) is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and still more preferably from the viewpoint of further improving the antifoaming property and the contamination suppressing effect of the processing liquid. 10 or less.
  • component (B) examples include a copolymer of ethylene oxide and alkylene oxide, an ester derivative of polyethylene glycol, and an ether derivative of polyethylene glycol.
  • Component (B) is preferably selected from the group consisting of block copolymers of EO and AO (ie, polyoxyethylene polyoxyalkylene block copolymers), polyoxyethylene alkyl ethers and polyoxyethylene alkylene alkyl ethers.
  • block copolymers of EO and AO ie, polyoxyethylene polyoxyalkylene block copolymers
  • polyoxyethylene alkyl ethers ie, polyoxyethylene alkyl ethers
  • polyoxyethylene alkylene alkyl ethers ie, polyoxyethylene alkylene alkyl ethers
  • One or more types more preferably a block copolymer of EO and AO.
  • the copolymer of EO and AO is a copolymer of EO and AO, which will be described later.
  • the addition mode of EO and AO may be either random addition or block addition, and random addition and block addition. Addition may be mixed, but a block-added copolymer is preferable, and a pluronic-type copolymer is more preferable.
  • the AO include alkylene oxides having 3 or 4 carbon atoms, such as propylene oxide (PO), oxetane, 1,2-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, and tetrahydrofuran. Can be mentioned.
  • the copolymer of EO and AO is more preferably a copolymer of EO and PO, still more preferably a block copolymer of EO and PO, and still more preferably a triblock of EO and PO.
  • the number average molecular weight (Mn) of the structural portion derived from AO is preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more. And preferably 5,000 or less, more preferably 3,000 or less, and still more preferably 2,000 or less.
  • the polyoxyethylene alkyl ether is preferably an EO adduct of a higher alcohol.
  • the higher alcohol include aliphatic alcohols having 6 to 24 carbon atoms.
  • the carbon number of the higher alcohol is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less.
  • the aliphatic alcohol is preferably a primary alcohol or a secondary alcohol, and more preferably a primary alcohol. Further, it may be linear, branched or cyclic.
  • aliphatic alcohol examples include octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, isotridecyl alcohol, myristyl alcohol, pentadecyl alcohol, palmityl alcohol, heptadecanol.
  • Saturated fatty alcohols such as stearyl alcohol, isostearyl alcohol, nonadecyl alcohol, eicosanol; octenyl alcohol, decenyl alcohol, dodecenyl alcohol, tridecenyl alcohol, tetradecenyl alcohol, palmitoleyl alcohol, Unsaturated aliphatic alcohols such as oleyl alcohol, gadrel alcohol, linoleyl alcohol; ethyl cyclohexyl alcohol, propyl cyclohexyl Alcohol, octylcyclohexyl alcohol, nonylcyclohexyl alcohol, cyclic aliphatic alcohols, such as adamantyl alcohol.
  • Unsaturated aliphatic alcohols such as oleyl alcohol, gadrel alcohol, linoleyl alcohol; ethyl cyclohexyl alcohol, propyl cyclohexyl Alcohol, octy
  • the polyoxyethylene alkylene alkyl ether is preferably an EO and AO adduct of a higher alcohol.
  • the higher alcohol is the same as that described for the polyoxyethylene alkyl ether.
  • AO other than EO include alkylene oxides having 3 or 4 carbon atoms, such as 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. 1,3-butylene oxide and tetrahydrofuran.
  • the polyoxyethylene alkyl ether and the polyoxyethylene alkylene alkyl ether can be synthesized by adding EO and / or AO to the higher alcohol, but the addition of EO and AO to the higher alcohol is known.
  • a component (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Content of a component (B) is 0.020 mass% or more and 0.500 mass% or less on the basis of 100 mass% of the whole quantity of the said processing liquid.
  • the content of the component (B) is preferably 0.030% by mass or more, more preferably 0.035% by mass or more, and still more preferably 0.00% by mass, based on the total amount of the machining fluid of 100% by mass. It is 060% by mass or more, and preferably 0.200% by mass or less, more preferably 0.175% by mass or less, and further preferably 0.120% by mass or less.
  • content ratio [A / B] of a component (A) and a component (B) in the said process liquid is 0.05 or more and 2.00 or less by mass ratio.
  • the content ratio is less than 0.05, the antifoaming property and the contamination suppressing effect of the processing liquid are deteriorated.
  • the content ratio exceeds 2.00, the antifoaming property and the contamination suppressing effect of the processing liquid are deteriorated.
  • the content ratio [A / B] is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more, and preferably by mass ratio. 0.90 or less, more preferably 0.80 or less, and still more preferably 0.75 or less.
  • the water is not particularly limited, and purified water such as distilled water and ion exchange water (deionized water); tap water; industrial water; and the like can be used, preferably purified water, more preferably ion exchange water ( Deionized water).
  • purified water such as distilled water and ion exchange water (deionized water); tap water; industrial water; and the like
  • purified water more preferably ion exchange water ( Deionized water).
  • the water content is based on the total amount of the machining fluid of 100% by mass, Preferably it is 50.000 mass% or more, More preferably, it is 75.000 mass% or more, More preferably, it is 95.000 mass% or more, More preferably, it is 96.000 mass% or more, More preferably, it is 96.500 mass% or more It is. And from a viewpoint of ensuring the amount of active ingredients in the processing fluid, it is preferably 99.970 mass% or less, more preferably 99.930 mass% or less, and still more preferably 99.900 mass% or less.
  • the “active ingredient” refers to all ingredients excluding water from the processing liquid.
  • the working fluid is composed of a polyhydric alcohol and a polyhydric alcohol derivative as the component (C) in addition to the aforementioned component (A), component (B) and water. It is preferable to contain at least one alcohol component selected from the group.
  • component (C) examples include ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, glycerin, and ester derivatives thereof. , These ether derivatives; polyethylene glycol, polypropylene glycol and the like.
  • Component (C) is preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, polyethylene glycol, glycerin, their ester derivatives and their ether derivatives, more preferably ethylene glycol , One or more selected from the group consisting of diethylene glycol, polyethylene glycol, glycerin, their ester derivatives and their ether derivatives, more preferably selected from the group consisting of diethylene glycol, glycerin, their ester derivatives, and their ether derivatives One or more.
  • a component (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the component (C) is preferably 0.010 based on the total amount of the processing liquid of 100% by mass from the viewpoint of improving water retention in the processing liquid.
  • % By mass, more preferably 0.030% by mass or more, more preferably 0.060% by mass or more, still more preferably 1.000% by mass or more, from the viewpoint of obtaining an effect commensurate with the content, Preferably it is 5.000 mass% or less, More preferably, it is 4.000 mass% or less, More preferably, it is 3.500 mass% or less, More preferably, it is 1.500 mass% or less.
  • the content ratio [C / A] of the component (A) and the component (C) in the working fluid is preferably 1.00 or more by mass ratio.
  • it is 1.20 or more, more preferably 1.40 or more, still more preferably 5.00 or more, and preferably 300 or less, more preferably 250 or less, still more preferably 230 or less, and even more preferably 10 0.0 or less.
  • the content ratio [C / B] of the component (B) and the component (C) in the working fluid is preferably 0.20 or more by mass ratio.
  • it is 0.30 or more, more preferably 0.50 or more, still more preferably 5.00 or more, and preferably 100 or less, more preferably 90.0 or less, still more preferably 87.0 or less, more More preferably, it is 10.0 or less.
  • the processing fluid further contains other additives as long as the object of the present invention is not impaired. You may contain.
  • Other additives include surfactants other than components (A) and (B), pH adjusters, antifoaming agents, metal deactivators, bactericides / preservatives, rust inhibitors, antioxidants, and the like. It is done. These additives may be used alone or in combination of two or more. Moreover, in these additives, 1 or more types chosen from the group which consists of surfactant other than a component (A) and (B) and a pH adjuster are preferable.
  • surfactants other than components (A) and (B) include anionic surfactants, cationic surfactants, nonionic surfactants other than components (A) and (B), and amphoteric surfactants. It is done.
  • anionic surfactant include alkyl benzene sulfonate and alpha olefin sulfonate.
  • cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts.
  • Nonionic surfactants other than components (A) and (B) include, for example, acetylene glycol having an HLB value of less than 4 and greater than 12, an alkylene oxide adduct of acetylene glycol having an HLB value of less than 4 and greater than 12, and molecules An ethylene oxide adduct in which the number of moles of ethylene oxide in the structure is less than 5, and a nonionic surfactant having no acetylene group, and an ethylene oxide adduct having an HLB of less than 6.
  • Nonionic surfactants having no acetylene group for example, polyoxyethylene alkyl ethers other than components (A) and (B), ethers such as polyoxyethylene alkylphenyl ethers other than components (A) and (B), Amides such as fatty acid alkanolamides).
  • amphoteric surfactants include alkyl betaines as betaines.
  • nonionic surfactants such as ethers other than components (A) and (B), more preferably acetylene glycol having an HLB value of less than 4 and more than 12, and an HLB value of less than 4 and more than 12
  • the pH adjuster is mainly used to adjust the pH of the processing liquid.
  • the pH adjuster include various acid components and base components, and the pH of the processing liquid can be appropriately adjusted by adjusting the content ratio of these components.
  • the acid component and the base component can react with each other to form a salt. Therefore, when an acid component and a base component are used as a pH adjuster, when a reaction product of the acid component and the base component exists in the processing liquid, as described above, the reaction product of the acid component and the base component is contained.
  • Each content of the acid component and the base component contributing to the reaction calculated from the amount can also be calculated. Moreover, it can replace with the said reaction material in that case, and can be considered that the said acid component and base component before reaction are contained.
  • Examples of the acid component used as a pH adjuster include various fatty acids such as lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, neodecanoic acid, isononanoic acid, capric acid, and isostearic acid; acetic acid, malic acid, and citric acid.
  • fatty acids such as lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, neodecanoic acid, isononanoic acid, capric acid, and isostearic acid
  • acetic acid malic acid, and citric acid
  • Examples thereof include carboxylic acids such as acids; polymer acids such as polyacrylic acid and salts thereof; and inorganic acids such as phosphoric acid.
  • fatty acids are preferable, fatty acids having 12 or less carbon atoms such as neodecanoic acid, isononanoic acid, capric acid, and dodecanedioic acid are more preferable, and a group consisting of neodecanoic acid, isononanoic acid, capric acid, and dodecanedioic acid. One or more selected are more preferable.
  • Examples of the base component used as a pH adjuster include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tri-n-propanolamine, tri-n-butanolamine, Isobutanolamine, tri-tert-butanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-cyclohexylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-cyclohexyldiethanolamine, Alkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine; methylamine, dimethylamine, ethylamine , Diethylamine, propylamine, alkyl amines such as dipropylamine; and the ammonia.
  • tertiary amines are preferable, and at least one selected from the group consisting of triethanolamine, triisopropanolamine, N-methyldiethanolamine, and N-cyclohexyldiethanolamine is more preferable.
  • Examples of the antifoaming agent include silicone oil, fluorosilicone oil, and fluoroalkyl ether.
  • Examples of the metal deactivator include imidazoline, pyrimidine derivatives, thiadiazole, and benzotriazole.
  • Examples of the disinfectant / preservative include p-oxybenzoates (parabens), benzoic acid, salicylic acid, sorbic acid, dehydroacetic acid, p-toluenesulfonic acid and salts thereof, and phenoxyethanol.
  • Examples of the rust inhibitor include alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, and polyhydric alcohol esters other than component (C).
  • Examples of the antioxidant include phenolic antioxidants and amine antioxidants.
  • the total content of other additives in the processing liquid is preferably 0.001% by mass or more, more preferably 0, based on the total amount of the processing liquid of 100% by mass. 0.002% by mass or more, more preferably 0.010% by mass or more, and preferably 0.200% by mass or less, more preferably 0.150% by mass or less, still more preferably 0.130% by mass or less, more More preferably, it is 0.100 mass% or less, More preferably, it is 0.050 mass% or less.
  • the ratio ((other additives) / A) between the amount of the other additives and the content of the component (A) in the processing liquid is preferably a mass ratio. 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.20 or more, and preferably 10.0 or less, more preferably 9.00 or less, further Preferably it is 5.00 or less, More preferably, it is 1.00 or less, More preferably, it is 0.50 or less.
  • the processing liquid contains other additives, water, component (A) and component (B), and if necessary, contained in the processing liquid
  • the total content of the component (C) is preferably 98.000% by mass or more, more preferably 99.000% by mass or more, and still more preferably 99.800% by mass or more, based on the total amount of the processing fluid of 100% by mass. , More preferably 99.900% by mass or more, and preferably 100% by mass or less, more preferably 99.999% by mass or less, still more preferably 99.998% by mass or less, and still more preferably 99.950. It is below mass%.
  • the total content (active ingredient amount) of (C) and other additives is preferably 0.030% by mass or more, more preferably 0.080% by mass or more, and still more preferably, based on the total amount of the processing liquid of 100% by mass. Is 0.100% by mass or more, and preferably 5.500% by mass or less, more preferably 3.500% by mass or less, further preferably 2.000% by mass or less, and still more preferably 1.000% by mass. Hereinafter, it is more preferably 0.500% by mass or less.
  • the pH of the working fluid is preferably 4 or more and 9 or less. It is preferable that the pH of the processing liquid is 4 or more because corrosion of the wire, processing apparatus, and the like can be suppressed. Moreover, it is preferable that the pH of the processing liquid is 9 or less because, for example, a large amount of hydrogen can be suppressed from chips when processing silicon or the like. From such a viewpoint, the pH of the processing liquid is more preferably 4 or more and 8 or less, and further preferably 5 or more and 8 or less.
  • the manufacturing method of the brittle material processing liquid is: At least with water, (A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and (B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group, A method for producing a brittle material processing liquid,
  • the content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid
  • the content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component
  • component (A) and component (B) are blended sequentially or simultaneously with water.
  • the component (B) may be blended and the mixture may be blended in water.
  • water, a component (A), and a component (B) may be mix
  • the blending order, blending method and the like of each component to be blended are not particularly limited.
  • water, a component (A), a component (B), a component (C), and other additives are respectively the same as what was mentioned above in the column of a brittle material processing liquid, The suitable aspect is also the same. Therefore, the detailed description is abbreviate
  • the preferred blending amount of water, component (A), component (B), component (C), and other additives and the preferred blending ratio between the components are also listed in the column of brittle material processing liquid, respectively. Since it is the same as each content and each content ratio in the said process liquid mentioned above, the detailed description is abbreviate
  • the brittle material processing liquid can be suitably used when wire sawing a workpiece made of a brittle material such as a silicon ingot using the wire saw described above, preferably a fixed abrasive wire saw. That is, the processing liquid can be suitably used when processing a workpiece made of a brittle material using a wire.
  • the brittle material include crystalline silicon, sapphire, gallium nitride, silicon carbide, neodymium magnet, zirconia, graphite, niobic acid, tantalate, quartz and glass.
  • the processing liquid can be more suitably used when processing crystalline silicon, sapphire, silicon carbide, neodymium magnet, crystal, or glass from the viewpoint of the contamination suppression effect, and processes crystalline silicon, sapphire, or silicon carbide. In this case, it can be used more suitably.
  • the brittle material processing liquid may be obtained, for example, by diluting a concentrated liquid obtained by reducing the amount of water in the processing liquid and concentrating it two to 700 times with water. That is, when the above-described processing is performed, the concentrated liquid of the processing liquid or the composition or stock solution for the processing liquid having the same composition as the concentrated liquid (hereinafter also simply referred to as “concentrated liquid”) is doubled with water. It can be diluted to 700 times or less and used as the brittle material processing liquid. Moreover, the said processing liquid can be concentrated so that it may become the concentrate shown below, and it can also be used as an aspect suitable for storage, transportation, etc.
  • the “concentrated liquid” is not limited to a concentrated liquid obtained by reducing the amount of water from the processing liquid as described above, but is prepared on the assumption that the processing liquid is diluted with water. Of the prepared composition or stock solution.
  • the concentrate for example, water and, (A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and (B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group, Including
  • the content of the component (A) is preferably 0.200% by mass or more, and preferably 30.000% by mass or less, based on 100% by mass of the total concentrated liquid of the brittle material processing liquid.
  • the content of the component (B) is preferably 0.300% by mass or more, and preferably 90.000% by mass or less, more preferably 75.000% by mass, based on 100% by mass of the total concentrated liquid of the brittle material processing liquid. %, And the content ratio [A / B] of the component (A) and the component (B) is 0.05 to 2.00 in terms of mass ratio. It is done.
  • the concentrate further contains component (C), preferably 5.000% by mass or more, more preferably 10.000% by mass or more, and preferably 95.000% by mass based on the total amount of the concentrate 100% by mass. % Or less.
  • the concentrated solution contains other additives in addition to water, component (A), component (B), and component (C) contained as necessary, as long as the object of the present invention is not impaired. It may be.
  • the content of water in the concentrated solution is preferably 0.100% by mass or more and less than 50000% by mass based on the total amount of the concentrated solution of 100% by mass.
  • water, a component (A), a component (B), a component (C), and other additives are respectively the same as what was mentioned above in the column of a brittle material processing liquid,
  • the suitable Since the aspect is also the same, detailed description thereof is omitted.
  • a component (A), a component (B), a component (C), and another additive The said concentrate is 2 with water.
  • each of the components is contained so as to satisfy the range of suitable contents of each component described above in the column of brittle material processing liquid.
  • the above-mentioned working fluids described above in the column of brittle material working fluid are also respectively used for suitable content ratios among water, component (A), component (B), component (C), and other additives. It is the same as the content ratio between each component in the inside, and the detailed description thereof is omitted.
  • the concentrated liquid can be used as a composition or a stock solution for preparing the processing liquid by mainly diluting with water. That is, as a method of using a concentrated liquid of brittle material processing liquid according to an embodiment of the present invention, for example, water and, (A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and (B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group, Including
  • the content of the component (A) is preferably 0.200% by mass or more, and preferably 30.000% by mass or less based on 100% by mass of the total amount of the concentrate.
  • the content of component (B) is preferably 0.300% by mass or more, and preferably 90.000% by mass or less, more preferably 75.000% by mass or less, based on 100% by mass of the total concentrate.
  • the content ratio [A / B] of a component (A) and a component (B) is 0.05 or more and 2.00 or less by mass ratio,
  • the concentrated liquid of a brittle material processing liquid The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
  • the content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B)
  • the brittle material working fluid is prepared by diluting with water so that the ratio [A / B] is 0.05 or more and 2.00 or less by mass ratio, This is a method for
  • the concentrated liquid and the processing liquid used in the method of use may each independently contain one or more selected from the group consisting of the component (C) and other additives as necessary.
  • water, a component (A), a component (B), a component (C), and other additives are respectively the same as what was mentioned above in the column of a brittle material processing liquid, The suitable aspect is also the same. Therefore, the detailed description is abbreviate
  • a component (A), a component (B), a component (C), and other additives in the concentrate used by the said usage method the content ratio between each component, and those suitable ranges Since each is the same as each content and each content ratio in the concentrated liquid described above, detailed description thereof is omitted.
  • the content of water, the component (A), the component (B), the component (C), and other additives in the working fluid used in the method of use, the content ratio between the components, and their preferred ranges Are the same as the respective contents and ratios described above in the column of brittle material processing liquid, and detailed description thereof will be omitted.
  • the concentrated liquid and the processing liquid are the same as the above-described concentrated liquid and the processing liquid, respectively, and the preferred embodiments including the respective components contained therein are also the same. Omitted.
  • water, the component (A), the component (B), the component (C), and other additives contained in the concentrated liquid and the processing liquid are the same as those described above in the column of the brittle material processing liquid. Since the preferred embodiment is the same, detailed description thereof is omitted.
  • the suitable content of each component of water, a component (A), a component (B), a component (C), and other additives and the content ratio between each component are also each in the column of a brittle material processing liquid. This is the same as the content ratio between the components in the processing liquid described above, and a detailed description thereof will be omitted.
  • the brittle material processing method is a method of processing a workpiece made of the brittle material such as a silicon ingot using the processing liquid.
  • the machining fluid is used by supplying the machining fluid to the workpiece and bringing it into contact with the workpiece.
  • the machining fluid lubricates between the workpiece and a processing tool such as the wire saw. Furthermore, it is used for removal of chips (chips), rust prevention of workpieces, cooling of tools and workpieces, and the like.
  • Specific examples of the processing of the brittle material performed using the processing liquid include various processing such as cutting, grinding, punching, polishing, drawing, drawing, rolling, and the like. Among them, cutting and grinding are preferable, and cutting is more preferable.
  • the brittle material as the workpiece include the materials described above. Note that, as described above, the processing liquid is preferably used as one used for cutting a silicon ingot.
  • the wire saw processing method of both the free abrasive grain method and the fixed abrasive grain method cuts a plurality of silicon wafers from the silicon ingot at a time.
  • one wire is wound around each groove on two or more guide rollers having a plurality of grooves carved at a constant interval, and each wire is held in parallel with a constant tension.
  • each guide roller is rotated and the wire is run in one or both directions while the machining liquid discharged from the nozzle or the like is adhered to the wire, and the silicon ingot is pushed onto the wire to which the machining liquid is adhered. Cutting is applied.
  • processing may be performed while applying a processing liquid to a workpiece itself such as a silicon ingot as necessary.
  • the processing liquid used for processing is stored in a tank or the like, and is transported from there to the aforementioned processing chamber nozzle by piping or the like.
  • the machining fluid used at the time of cutting is collected in a used machining fluid receiving tank or the like below the cutting device.
  • the processing liquid is more preferably used as a processing liquid used in such a brittle material processing method.
  • the processing liquid is further used as a processing liquid used in a processing method of cutting a silicon wafer from a silicon ingot with a fixed abrasive wire. It is preferably used and more preferably used by a processing method of cutting a silicon wafer from a silicon ingot using a multi-wire apparatus using a fixed abrasive wire saw.
  • the brittle material processing apparatus is a processing apparatus that uses the brittle material processing liquid according to an embodiment of the present invention, preferably a multi-wire cutting apparatus, and more preferably a fixed abrasive.
  • the “processing apparatus using a brittle material processing liquid according to an embodiment of the present invention” can also be referred to as “a processing apparatus filled with a brittle material processing liquid according to an embodiment of the present invention”.
  • the circulation rate was adjusted so that the flow rate of the working fluid at this time was 1.3 L / min.
  • the liquid level after 5 minutes from the start of circulation was measured.
  • the liquid level is compared with the unit “mL” using the scale of the graduated cylinder.
  • the liquid level height increases, that is, the value of “mL” increases. Therefore, the smaller the liquid level height value “mL”, the better the defoaming property.
  • Tables 1 and 2 The obtained results are shown in Tables 1 and 2 below.
  • Liquid level: fine powder A blend of fine powder (“graphite powder”, manufactured by Wako Pure Chemical Industries, Ltd., special grade) so as to have a concentration of 13 mass% in the evaluation liquid was prepared as an evaluation liquid.
  • liquid level height was measured by the method similar to the measuring method of the liquid level height "without fine powder", and the defoaming property of the processing liquid at the time of fine powder mixing was evaluated. The obtained results are shown in Tables 1 and 2 below.
  • Examples 1 to 9 Comparative Examples 1 to 9
  • Each component was blended so as to have the composition shown in Tables 1 and 2 below to prepare a brittle material processing liquid. According to the said evaluation method, the brittle material processing liquid of each Example and a comparative example was evaluated. The obtained results are shown in Tables 1 and 2 below.
  • each component shown in following Table 1 and 2 represents the following compounds, respectively.
  • Surfactant 5 block copolymer of
  • each of the brittle material working fluids of Examples 1 to 9 contains the component (A) and the component (B) and satisfies the predetermined content ratio [A / B]. It was confirmed that the foam was excellent in defoaming property, and there was little contamination due to the adhesion of fine powder, and the anti-contamination effect was excellent. On the other hand, as shown in Table 2, since the brittle material processing liquids of Comparative Examples 1, 4, 8 and 9 do not satisfy the predetermined content ratio [A / B], all of them are inferior in antifoaming properties. It was confirmed that there were many stains due to adhesion of fine powder.
  • the brittle material processing liquids of Comparative Examples 2, 3 and 5 do not contain the component (B), and the brittle material processing liquids of Comparative Examples 6 and 7 do not contain the component (A). For this reason, it was confirmed that all of them were inferior in antifoaming properties and that there were many stains due to adhesion of fine powder.
  • the brittle material processing liquid of Comparative Example 5 uses an EO adduct of a higher alcohol having an EO addition mole number of less than 5.
  • the brittle material working fluid of Comparative Example 6 uses an EO adduct of acetylene glycol having an HLB value exceeding 12.
  • the processing liquid is less foamed during processing and has excellent defoaming properties. Was confirmed. Further, it was confirmed that the contamination on the apparatus and the cut silicon wafer was slight and easy to clean.
  • the brittle material processing liquid according to one embodiment of the present invention is excellent in antifoaming properties. Therefore, for example, when cutting a workpiece made of a brittle material such as a silicon ingot, foaming of the processing liquid can be suppressed, and the processing liquid overflows from the tank that receives the processing liquid due to foaming. It is possible to prevent adverse effects such as a soaking (occurrence of overflow) failure or a reduction in processing accuracy caused by foaming. In addition, the brittle material processing liquid according to one embodiment of the present invention is excellent in the contamination suppressing effect.
  • the brittle material working fluid according to an embodiment of the present invention is preferably used as a material for cutting brittle materials such as silicon ingots, and more preferably, fixed abrasive.
  • a grain wire is used as a coolant for cutting a silicon wafer from a silicon ingot.

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Abstract

The present invention relates to a brittle material processing liquid which contains water, (A) one or more substances selected from the group consisting of acetylene glycols having an HLB value of from 4 to 12 (inclusive) and alkylene oxide addition products of the acetylene glycols having an HLB value of from 4 to 12 (inclusive), and (B) a nonionic surfactant which is an ethylene oxide addition product having an HLB value of 6 or more and a number of moles of added ethylene oxide in the molecular structure of 5 or more, and which does not have an acetylene group, and wherein: the content of the component (A) is from 0.010% by mass to 0.200% by mass (inclusive) based on 100% by mass of the total of the brittle material processing liquid; the content of the component (B) is from 0.020% by mass to 0.500% by mass (inclusive) based on 100% by mass of the total of the brittle material processing liquid; and the content ratio of the component (A) to the component (B), namely (A)/(B) is from 0.05 to 2.00 (inclusive) in terms of mass ratio. The present invention also relates to a method for producing this brittle material processing liquid.

Description

脆性材料加工液Brittle material processing fluid

 本発明は、脆性材料加工液、及び該脆性材料加工液の製造方法に関する。 The present invention relates to a brittle material working fluid and a method for producing the brittle material working fluid.

 半導体製品の製造では脆性材料であるシリコンインゴットを精度よく切削加工することが重要であり、シリコンインゴットの切削加工では、加工精度及び生産性の観点から、一般にワイヤソー加工が利用されている。
 また、ワイヤソー加工は、セラミックス、石英、サファイア、ガラス等の材料の加工でも利用されている。
 一般に、ワイヤソーを用いた加工方法としては、ワイヤと被加工物との摺動部に遊離砥粒を供給しながら加工を行う遊離砥粒方式と、ワイヤの表面に予め砥粒が固定されたワイヤを用いて加工を行う固定砥粒方式とが挙げられる。
 例えば、近年、前述のシリコンインゴットからシリコンウェハを生産する分野では、更なる生産性の向上が要求されており、遊離砥粒方式より短時間での切断が可能であり、また、より細いワイヤ工具を使用して歩留まりを向上できる等の理由から、固定砥粒方式がよく用いられるようになってきている。
In the manufacture of semiconductor products, it is important to accurately cut a silicon ingot, which is a brittle material, and wire saw processing is generally used for cutting silicon ingots from the viewpoint of processing accuracy and productivity.
Wire saw processing is also used for processing materials such as ceramics, quartz, sapphire, and glass.
Generally, as a processing method using a wire saw, a free abrasive grain method that performs processing while supplying free abrasive grains to a sliding portion between the wire and a workpiece, and a wire in which abrasive grains are fixed to the surface of the wire in advance And a fixed abrasive method in which processing is performed using
For example, in recent years, in the field of producing silicon wafers from the aforementioned silicon ingots, further improvement in productivity has been demanded, and cutting can be performed in a shorter time than a loose abrasive method, and a thinner wire tool For example, the fixed abrasive method is often used for the reason that the yield can be improved.

 また、両方式のワイヤソー加工では、切削加工時の加工効率の向上、被加工材と被加工材を加工する工具との摩擦抑制、加工により発生する熱の除去(冷却)、工具の寿命延長効果、切り屑の除去等を目的として加工液(クーラント)が使用されている。
 前述の用途等で用いられる加工液としては、鉱物油、動植物油、合成油などを主成分した油系の加工液と、界面活性能を持つ化合物を配合して水溶性を付与した水系の加工液とが含まれる。
 近年、作業時の安全性や環境問題の観点から水溶性を付与した加工液が用いられるようになってきている。
In both types of wire saw processing, the efficiency of cutting is improved, the friction between the workpiece and the tool that processes the workpiece is reduced, the heat generated by the processing is removed (cooling), and the life of the tool is extended. A machining fluid (coolant) is used for the purpose of removing chips.
The processing fluid used in the above-mentioned applications includes an aqueous processing fluid containing mineral oil, animal and vegetable oils, synthetic oil, etc. as a main component and a compound having a surface active ability to provide water-soluble processing. Liquid.
In recent years, a working fluid imparted with water solubility has been used from the viewpoint of safety during work and environmental problems.

 例えば、特許文献1には、希土類磁石以外の加工材料の切断に用いられる固定砥粒ワイヤソー用水溶性加工液組成物であって、グリコール類を含有することを特徴とする固定砥粒ワイヤソー用水溶性加工液組成物が開示されている。
 また、特許文献2には、希土類磁石の切断に用いられる固定砥粒ワイヤソー用水溶性加工液組成物であって、グリコール類と、カルボン酸と、水に溶解して塩基性を示す化合物と、水とを、それぞれ特定の含有量で含有してなる(但し、これらの成分の合計は100重量部である)ことを特徴とする固定砥粒ワイヤソー用水溶性加工液組成物が開示されている。
 また、特許文献3には、アセチレングリコール及び/又はそのアルキレンオキサイド付加物0.01~20質量%含むことを特徴とする水性切削液が開示されている。
For example, Patent Document 1 discloses a water-soluble machining liquid composition for a fixed abrasive wire saw that is used for cutting work materials other than rare earth magnets, and contains glycols. A liquid composition is disclosed.
Patent Document 2 discloses a water-soluble working fluid composition for fixed abrasive wire saws used for cutting rare earth magnets, which includes glycols, carboxylic acid, a compound that dissolves in water and exhibits basicity, water Are contained in a specific content (however, the total of these components is 100 parts by weight), and a water-soluble working liquid composition for a fixed abrasive wire saw is disclosed.
Patent Document 3 discloses an aqueous cutting fluid characterized by containing 0.01 to 20% by mass of acetylene glycol and / or its alkylene oxide adduct.

特開2003-82334号公報JP 2003-82334 A 特開2003-82335号公報JP 2003-82335 A 特開2011-12249号公報JP 2011-12249 A

 一般に、前述した両方式のワイヤソー加工方法は、前述のシリコンインゴットから、複数のシリコンウェハを一度に切り出すため、マルチワイヤソー装置が用いられている。マルチワイヤソー装置では、一定間隔で複数の溝が彫られた2以上のガイドローラー上の各溝に1本ずつワイヤを巻きつけ、各ワイヤが一定の張力で平行に保持されている。そして、切断加工時には、各ガイドローラーを回転させ、ノズル等から吐出した加工液をワイヤに付着させながら、該ワイヤを一方向又は双方向に走行させ、加工液が付着したワイヤにシリコンインゴットを押し当てて切断を行っている。
 当該ワイヤソー加工に使用される加工液は、ワイヤソー装置が備えるタンクに投入され、当該タンクからワイヤソー装置が備えるポンプによって加工室ノズルに供給され、当該ノズルから吐出される。ノズルから吐出された加工液は、加工間隙(ワイヤとシリコンインゴットとの間隙)を狙って供給されて、加工間隙の潤滑等に使用された後、再び前記タンクに戻る。このようにシリコンインゴットの切断中、加工液はワイヤソー装置内を循環している。
 当該切断加工時、ワイヤ高線速化に伴うガイドローラーの高速回転などにより加工液が激しく飛散する場合があり、加工液の泡立ちに繋がる。また、当該切断加工時、加工液がワイヤソー装置下部にあるタンクに流れ落ちることによって、タンク内の加工液が激しく泡立ち、タンクからオーバーフローする場合がある。更に、当該切断加工中に発生する微細な切粉が加工液の泡立ちを助長してしまう問題、並びにワイヤソー及び切断したウェハ等が当該切粉により著しく汚染され、それらを洗浄するための負荷が大きくなるといった問題があった。
Generally, in both the above-described wire saw processing methods, a multi-wire saw apparatus is used to cut out a plurality of silicon wafers from the above-described silicon ingot at a time. In the multi-wire saw device, one wire is wound around each groove on two or more guide rollers having a plurality of grooves carved at a constant interval, and each wire is held in parallel with a constant tension. During the cutting process, each guide roller is rotated and the wire is run in one or both directions while the machining liquid discharged from the nozzle or the like is adhered to the wire, and the silicon ingot is pushed onto the wire to which the machining liquid is adhered. Cutting is applied.
The processing liquid used for the wire saw processing is put into a tank provided in the wire saw device, supplied from the tank to the processing chamber nozzle by a pump provided in the wire saw device, and discharged from the nozzle. The machining fluid discharged from the nozzle is supplied aiming at the machining gap (gap between the wire and the silicon ingot), used for lubrication of the machining gap, etc., and then returns to the tank again. Thus, during the cutting of the silicon ingot, the machining fluid circulates in the wire saw device.
At the time of the cutting process, the processing liquid may be violently scattered due to high-speed rotation of the guide roller accompanying the increase in the wire speed, which leads to bubbling of the processing liquid. In addition, during the cutting process, the processing liquid may flow down to a tank below the wire saw device, and the processing liquid in the tank may be foamed violently and overflow from the tank. Furthermore, the problem that fine chips generated during the cutting process promote foaming of the processing liquid, and wire saws and cut wafers are significantly contaminated by the chips, and the load for cleaning them is large. There was a problem of becoming.

 このように、加工液を用いた際の泡立ちを抑制し、切粉の清浄性を向上することができれば、より安定した生産や加工精度の向上にも繋がる。また、加工装置及び加工物(ウェハ)の汚れを抑制することができれば、これらの洗浄負荷が低減できて作業効率も向上するため、生産性の向上に繋がる。
 そのため、加工時の泡立ちを抑制する効果(以下、単に「消泡性」ともいう。)並びに加工物及び加工装置等の切粉による汚染を抑制する効果(以下、単に「汚染抑制効果」ともいう。)に優れる加工液が求められている。
Thus, if foaming at the time of using a processing liquid is suppressed and the cleanliness of chips can be improved, it leads to more stable production and improvement of processing accuracy. Further, if contamination of the processing apparatus and the workpiece (wafer) can be suppressed, these cleaning loads can be reduced and work efficiency can be improved, leading to improvement in productivity.
Therefore, the effect of suppressing foaming during processing (hereinafter also simply referred to as “defoaming property”) and the effect of suppressing contamination by chips of processed products and processing devices (hereinafter also simply referred to as “contamination suppression effect”). )) Is required.

 本発明は、以上の問題点を鑑みてなされたものであり、本発明の課題は、消泡性及び汚染抑制効果に優れる脆性材料加工液を提供することである。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a brittle material processing liquid that is excellent in antifoaming properties and contamination suppression effects.

 本発明者らは、鋭意検討の結果、水と、特定の条件を満たすアセチレングリコール及びアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、特定の条件を満たすアセチレン基を有しない非イオン界面活性剤とを含有し、これら各成分の含有量比が特定の範囲を満たす脆性材料加工液が、前記課題を解決し得ることを見出した。本発明の各実施形態はかかる知見に基づいて完成したものである。すなわち、本発明の各実施形態によれば、以下の[1]又は[2]が提供される。
[1]水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを含み、
 成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下である、脆性材料加工液。
[2]少なくとも水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを配合する、脆性材料加工液の製造方法であって、
 成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下となるように配合して脆性材料加工液を得る、上記[1]に記載の脆性材料加工液の製造方法。
[3]ワイヤを用いて脆性材料からなる被加工材を加工するときに、上記[1]に記載の脆性材料加工液を該被加工材に供給し、該被加工材に接触させて用いる、脆性材料加工液の使用。
As a result of intensive studies, the present inventors have one or more selected from the group consisting of water, acetylene glycol satisfying a specific condition and an alkylene oxide adduct of acetylene glycol, and no acetylene group satisfying the specific condition. It has been found that a brittle material processing liquid that contains a nonionic surfactant and the content ratio of these components satisfies a specific range can solve the above-mentioned problems. Each embodiment of the present invention has been completed based on such knowledge. That is, according to each embodiment of the present invention, the following [1] or [2] is provided.
[1] water and
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
Including
The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) A brittle material processing liquid in which the ratio [A / B] is 0.05 to 2.00 in terms of mass ratio.
[2] At least with water,
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
A method for producing a brittle material processing liquid,
The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) The method for producing a brittle material processing liquid according to the above [1], wherein the brittle material processing liquid is obtained by blending the ratio [A / B] so as to be 0.05 to 2.00 in terms of mass ratio.
[3] When processing a workpiece made of a brittle material using a wire, the brittle material processing liquid according to [1] is supplied to the workpiece and used in contact with the workpiece. Use of brittle material processing fluid.

 本発明によれば、消泡性及び汚染抑制効果に優れる脆性材料加工液を提供することができる。 According to the present invention, it is possible to provide a brittle material processing liquid having excellent defoaming properties and contamination suppressing effects.

[脆性材料加工液]
 本発明の一実施形態に係る脆性材料加工液(以下、単に「加工液」ともいう。)は、水と、下記成分(A)及び成分(B)とを含有し、成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下である。
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤
 これらの要件を満たさない脆性材料加工液は、消泡性及び汚染抑制効果に劣る。
 また、本明細書中、当該「HLB値」は、グリフィン法により算出されるHLB(Hydrophilic-Lipophilic Balance)の値を意味する。
 なお、本明細書において、好ましい数値範囲(例えば、含有量等の範囲)について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、該当する数値範囲について「好ましくは10以上、より好ましくは20以上、更に好ましくは30以上」という下限値の記載と、「好ましくは90以下、より好ましくは80以下、更に好ましくは60以下」という記載から、「好ましい下限値(10)」と「更に好ましい上限値(60)」とを組み合わせて、好適範囲を「10以上、60以下」とすることもできる。同様に、「更に好ましい下限値(30)」と「好ましい上限値(90)」とを組み合わせて好適範囲を「30以上、90以下」とすることもできる。
 同様に、例えば、「好ましくは10~90、より好ましくは20~80、更に好ましくは30~60」という記載から、「10~60」、とすることもできる。
 なお、特に言及しない限り、好ましい数値範囲として単に「10~90」と記載する場合、10以上90以下の範囲を表す。
 以下、当該加工液に含有される各成分について説明する。
[Brittle material processing fluid]
The brittle material processing fluid according to one embodiment of the present invention (hereinafter also simply referred to as “processing fluid”) contains water, the following component (A) and component (B), and contains component (A). The amount is 0.010% by mass or more and 0.200% by mass or less based on the total amount of 100% by mass of the brittle material processing liquid,
Content of component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of brittle material processing liquid, and content of component (A) and component (B) The ratio [A / B] is 0.05 to 2.00 in terms of mass ratio.
(A): One or more selected from the group consisting of an acetylene glycol having an HLB value of 4 or more and 12 or less, and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 or more and 12 or less (B): an HLB value of 6 A nonionic surfactant that is an ethylene oxide adduct having an ethylene oxide addition mole number of 5 or more in the molecular structure and does not have an acetylene group. It is inferior in antifoaming property and pollution control effect.
Further, in the present specification, the “HLB value” means a value of HLB (Hydrophilic-Lipophilic Balance) calculated by the Griffin method.
In addition, in this specification, about the preferable numerical range (for example, range of content etc.), the lower limit value and upper limit value which were described in steps can be combined independently, respectively. For example, for the corresponding numerical range, the description of the lower limit value “preferably 10 or more, more preferably 20 or more, more preferably 30 or more” and “preferably 90 or less, more preferably 80 or less, more preferably 60 or less”. Therefore, the preferable range can be set to “10 or more and 60 or less” by combining “preferable lower limit value (10)” and “more preferable upper limit value (60)”. Similarly, the “more preferable lower limit value (30)” and the “preferable upper limit value (90)” can be combined to set the preferable range to “30 or more and 90 or less”.
Similarly, for example, “preferably 10 to 90, more preferably 20 to 80, still more preferably 30 to 60” can be used as “10 to 60”.
Unless otherwise specified, when “10 to 90” is simply described as a preferable numerical range, it represents a range of 10 to 90.
Hereinafter, each component contained in the processing liquid will be described.

<成分(A)>
 成分(A)は、HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上である。
 当該成分(A)のHLB値が4未満であると、成分(A)の水への溶解性が劣る。
 また、当該成分(A)のHLB値が12超えであると、前記加工液の消泡性及び汚染抑制効果が悪化する。
 このような観点から、当該HLB値は、好ましくは4以上10以下、より好ましくは4以上9以下、更に好ましくは4以上8以下である。
 なお、本明細書中、特に言及しない限り、「アルキレンオキサイド(以下、単に「AO」ともいう。)付加物」とは、単体のアルキレンオキサイドが付加した化合物だけでなく、複数のアルキレンオキサイド、すなわち、ポリアルキレンオキサイドが付加した化合物も含む。以下、「エチレンオキサイド(以下、単に「EO」ともいう。)付加物」、「プロピレンオキサイド(以下、単に「PO」ともいう。)付加物」も同様である。
<Component (A)>
Component (A) is at least one selected from the group consisting of acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12.
When the HLB value of the component (A) is less than 4, the solubility of the component (A) in water is poor.
Moreover, the defoaming property of the said processing liquid and the contamination inhibitory effect will deteriorate that the HLB value of the said component (A) is more than 12.
From such a viewpoint, the HLB value is preferably 4 or more and 10 or less, more preferably 4 or more and 9 or less, and still more preferably 4 or more and 8 or less.
In the present specification, unless otherwise specified, the “alkylene oxide (hereinafter also simply referred to as“ AO ”) adduct” refers to not only a compound to which a single alkylene oxide is added, but also a plurality of alkylene oxides, In addition, a compound to which a polyalkylene oxide is added is also included. The same applies to “ethylene oxide (hereinafter also simply referred to as“ EO ”) adduct” and “propylene oxide (hereinafter also simply referred to as“ PO ”) adduct”.

 前記アセチレングリコールとしては、例えば、下記一般式(1)で表される化合物が挙げられる。 Examples of the acetylene glycol include compounds represented by the following general formula (1).

Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001

 一般式(1)中、R~Rは、それぞれ独立に、炭素数1以上5以下のアルキル基を示す。
 R~Rが取り得る炭素数1以上5以下のアルキル基としては、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1,1-ジメチルプロピル基、1,2-ジメチルプロピル基、2,2-ジメチルプロピル基が挙げられる。
 これらの中でも、R及びRとしては、好ましくはイソブチル基又は3-メチルブチル基である。また、R及びRとしては、好ましくはメチル基である。
 また、一般式(1)で表される化合物としては、好ましくはR及びRとが互いに同一である構造又はR及びRとが互いに同一である構造を有する化合物であり、より好ましくはR及びRとが互いに同一であり、かつ、R及びRとが互いに同一である構造を有する化合物である。
In the general formula (1), R 1 to R 4 each independently represents an alkyl group having 1 to 5 carbon atoms.
Specific examples of the alkyl group having 1 to 5 carbon atoms that can be taken by R 1 to R 4 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group Is mentioned.
Among these, R 1 and R 3 are preferably an isobutyl group or a 3-methylbutyl group. R 2 and R 4 are preferably methyl groups.
Further, the compound represented by the general formula (1) is preferably a compound having a structure in which R 1 and R 3 are the same as each other or a structure in which R 2 and R 4 are the same as each other, more preferably Is a compound having a structure in which R 1 and R 3 are identical to each other, and R 2 and R 4 are identical to each other.

 また、前記アセチレングリコールのアルキレンオキサイド付加物としては、好ましくは、一般式(1)で表される化合物の各水酸基に、AOが付加した一般式(1)で表される化合物のアルキレンオキサイド付加物が挙げられ、より好ましくはEO及び/又はPOが付加した一般式(1)で表される化合物のアルキレンオキサイド付加物、更に好ましくはEOが付加した一般式(1)で表される化合物のアルキレンオキサイド付加物である。なお、当該アセチレングリコールのアルキレンオキサイド付加物を形成するアセチレングリコールの好適な態様は、前述の一般式(1)で表される化合物の好適な態様と同様である。
 なお、EOに由来する構造(例えば、エチレンオキシ基又はポリ(オキシエチレン)構造)及びPOに由来する構造(例えば、プロピレンオキシ基又はポリ(オキシプロピレン)構造)が結合した構造を含む場合、各構造は互いにランダム型で結合していてもよく、ブロック型で結合していてもよく、好ましくはブロック型である。
The alkylene oxide adduct of acetylene glycol is preferably an alkylene oxide adduct of the compound represented by the general formula (1) in which AO is added to each hydroxyl group of the compound represented by the general formula (1). More preferably, an alkylene oxide adduct of the compound represented by the general formula (1) to which EO and / or PO is added, and more preferably an alkylene of the compound represented by the general formula (1) to which EO is added. It is an oxide adduct. In addition, the suitable aspect of the acetylene glycol which forms the alkylene oxide adduct of the said acetylene glycol is the same as the suitable aspect of the compound represented by the aforementioned general formula (1).
In addition, when the structure derived from EO (for example, ethyleneoxy group or poly (oxyethylene) structure) and the structure derived from PO (for example, propyleneoxy group or poly (oxypropylene) structure) are included, The structures may be bonded to each other in a random type, may be bonded in a block type, and preferably is a block type.

 成分(A)としては、2,5,8,11-テトラメチル-6-ドデシン-5,8-ジオール、5,8-ジメチル-6-ドデシン-5,8-ジオール、2,4,7,9-テトラメチル-5-ドデシン-4,7-ジオール、8-ヘキサデシン-7,10-ジオール、7-テトラデシン-6,9-ジオール、2,3,6,7-テトラメチル-4-オクチン-3,6-ジオール、3,6-ジエチル-4-オクチン-3,6-ジオール、2,5-ジメチル-3-ヘキシン-2,5-ジオール、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、及び3,6-ジメチル-4-オクチン-3,6-ジオール等の一般式(1)で表されるアセチレングリコール;並びに一般式(1)で表されるアセチレングリコールのアルキレンオキサイド付加物;等が挙げられる。当該アルキレンオキサイドとしては、EO及び/又はPO等が挙げられる。
 これらの中では、好ましくは2,5,8,11-テトラメチル-6-ドデシン-5,8-ジオール、5,8-ジメチル-6-ドデシン-5,8-ジオール、2,4,7,9-テトラメチル-5-ドデシン-4,7-ジオール、8-ヘキサデシン-7,10-ジオール、7-テトラデシン-6,9-ジオール、2,3,6,7-テトラメチル-4-オクチン-3,6-ジオール、3,6-ジエチル-4-オクチン-3,6-ジオール、2,5-ジメチル-3-ヘキシン-2,5-ジオール、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール及び3,6-ジメチル-4-オクチン-3,6-ジオールからなる群より選ばれる1種以上のアルキレンオキサイド付加物、より好ましくは2,5,8,11-テトラメチル-6-ドデシン-5,8-ジオール、5,8-ジメチル-6-ドデシン-5,8-ジオール、2,4,7,9-テトラメチル-5-ドデシン-4,7-ジオール、8-ヘキサデシン-7,10-ジオール、7-テトラデシン-6,9-ジオール、2,3,6,7-テトラメチル-4-オクチン-3,6-ジオール、3,6-ジエチル-4-オクチン-3,6-ジオール、2,5-ジメチル-3-ヘキシン-2,5-ジオール、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール及び3,6-ジメチル-4-オクチン-3,6-ジオールからなる群より選ばれる1種以上のエチレンオキサイド付加物、更に好ましくは2,5,8,11-テトラメチル-6-ドデシン-5,8-ジオールのエチレンオキサイド付加物及び2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのエチレンオキサイド付加物からなる群より選ばれる1種以上である。
 なお、成分(A)は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
Component (A) includes 2,5,8,11-tetramethyl-6-dodecin-5,8-diol, 5,8-dimethyl-6-dodecin-5,8-diol, 2,4,7, 9-tetramethyl-5-dodecin-4,7-diol, 8-hexadecin-7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetramethyl-4-octyne 3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5 An acetylene glycol represented by the general formula (1) such as decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6-diol; and an acetylene represented by the general formula (1) Addition of alkylene oxide to glycol ; And the like. Examples of the alkylene oxide include EO and / or PO.
Of these, 2,5,8,11-tetramethyl-6-dodecin-5,8-diol, 5,8-dimethyl-6-dodecin-5,8-diol, 2,4,7, 9-tetramethyl-5-dodecin-4,7-diol, 8-hexadecin-7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetramethyl-4-octyne 3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5 One or more alkylene oxide adducts selected from the group consisting of decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6-diol, more preferably 2,5,8,11- Tetramethyl-6-dodecine 5,8-diol, 5,8-dimethyl-6-dodecin-5,8-diol, 2,4,7,9-tetramethyl-5-dodecin-4,7-diol, 8-hexadecine-7,10 -Diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6 One or more ethylene oxide adducts selected from the group consisting of diols, more preferably 2,5,8,11-tetramethyl-6-dodecine-5,8-diol ethylene oxide adducts and 2,4,4 7,9-Tetrame It is at least one selected from the group consisting of ethylene oxide adduct of-5-decyn-4,7-diol.
In addition, a component (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

 成分(A)の含有量は、前記加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下である。当該含有量が0.010質量%未満であると加工液の消泡性及び汚染抑制効果が悪化する。また、当該含有量が0.200質量%を超えると、成分(A)の水への溶解性が低下する。
 このような観点から、成分(A)の含有量は、前記加工液の全量100質量%基準で、好ましくは0.015質量%以上、より好ましくは0.020質量%以上、更に好ましくは0.040質量%以上であり、そして、好ましくは0.150質量%以下、より好ましくは0.100質量%以下、更に好ましくは0.070質量%以下である。
Content of a component (A) is 0.010 mass% or more and 0.200 mass% or less on the basis of 100 mass% of the whole quantity of the said processing liquid. When the content is less than 0.010% by mass, the antifoaming property and the contamination suppressing effect of the working fluid are deteriorated. Moreover, when the said content exceeds 0.200 mass%, the solubility to the water of a component (A) will fall.
From such a viewpoint, the content of the component (A) is preferably 0.015% by mass or more, more preferably 0.020% by mass or more, and still more preferably 0.05% by mass or more based on the total amount of the processing liquid of 100% by mass. It is 040% by mass or more, and preferably 0.150% by mass or less, more preferably 0.100% by mass or less, and still more preferably 0.070% by mass or less.

<成分(B)>
 成分(B)は、HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤である。
 前記加工液は、成分(B)を、含有量比〔A/B〕を満たすように含むことで、加工液の消泡性及び汚染抑制効果に優れる。
 当該成分(B)のEO付加モル数が5未満であると、加工液の汚染抑制効果が悪化する。このような観点から、当該EO付加モル数は、好ましくは6以上、より好ましくは7以上、更に好ましくは10以上、より更に好ましくは20以上である。また、当該EO付加モル数の上限は特に制限はないが、加工液のより良好な消泡性及び汚染抑制効果を得る観点から、好ましくは40以下、より好ましくは35以下、更に好ましくは30以下である。
 また、当該成分(B)のHLB値が6未満であると、成分(B)の水への溶解性が劣る。このような観点から、当該HLB値は、好ましくは7以上、より好ましくは8以上である。
 また、当該成分(B)のHLB値の上限は特に制限はないが、加工液の消泡性及び汚染抑制効果をより向上させる観点から、好ましくは20以下、より好ましくは15以下、更に好ましくは10以下である。
<Component (B)>
Component (B) is an ethylene oxide adduct having an HLB value of 6 or more, an added mole number of ethylene oxide in the molecular structure of 5 or more, and a nonionic surfactant having no acetylene group. .
The processing liquid contains the component (B) so as to satisfy the content ratio [A / B], so that the processing liquid is excellent in antifoaming property and contamination suppression effect.
When the number of moles of EO added to the component (B) is less than 5, the effect of suppressing contamination of the processing liquid is deteriorated. From such a viewpoint, the EO addition mole number is preferably 6 or more, more preferably 7 or more, still more preferably 10 or more, and still more preferably 20 or more. Further, the upper limit of the EO addition mole number is not particularly limited, but is preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less, from the viewpoint of obtaining a better defoaming property and contamination suppressing effect of the processing liquid. It is.
Moreover, the solubility to the water of a component (B) is inferior that the HLB value of the said component (B) is less than 6. From such a viewpoint, the HLB value is preferably 7 or more, more preferably 8 or more.
The upper limit of the HLB value of the component (B) is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and still more preferably from the viewpoint of further improving the antifoaming property and the contamination suppressing effect of the processing liquid. 10 or less.

 成分(B)としては、例えば、エチレンオキサイドとアルキレンオキサイドとの共重合体、ポリエチレングリコールのエステル誘導体、ポリエチレングリコールのエーテル誘導体が挙げられる。
 成分(B)としては、好ましくはEOとAOとのブロック共重合体(すなわち、ポリオキシエチレンポリオキシアルキレンブロック共重合体)、ポリオキシエチレンアルキルエーテル及びポリオキシエチレンアルキレンアルキルエーテルからなる群より選ばれる1種以上、より好ましくはEOとAOとのブロック共重合体が挙げられる。
Examples of the component (B) include a copolymer of ethylene oxide and alkylene oxide, an ester derivative of polyethylene glycol, and an ether derivative of polyethylene glycol.
Component (B) is preferably selected from the group consisting of block copolymers of EO and AO (ie, polyoxyethylene polyoxyalkylene block copolymers), polyoxyethylene alkyl ethers and polyoxyethylene alkylene alkyl ethers. One or more types, more preferably a block copolymer of EO and AO.

 前記EOとAOとの共重合体としては、EOと後述するAOとの共重合体であり、当該EOとAOとの付加の態様は、ランダム付加又はブロック付加のいずれでもよく、ランダム付加とブロック付加とが混在していてもよいが、好ましくはブロック付加した共重合体であり、より好ましくはプルロニック型の共重合体である。
 当該AOとしては、例えば、炭素数3又は4のアルキレンオキサイドが挙げられ、プロピレンオキサイド(PO)、オキセタン、1,2-ブチレンオキサイド、2,3-ブチレンオキサイド、1,3-ブチレンオキサイド、テトラヒドロフランが挙げられる。
 EOとAOとの共重合体としては、より好ましくはEOとPOとの共重合体であり、更に好ましくはEOとPOとのブロック共重合体であり、より更に好ましくはEOとPOとのトリブロック共重合体であり、より更に好ましくはポリプロピレングリコールにエチレンオキシドを付加したプルロニック型共重合体である。
 また、当該EOとAOとの共重合体中、AOに由来する構造部分の数平均分子量(Mn)は、好ましくは500以上、より好ましくは1,000以上、更に好ましくは1,500以上であり、そして、好ましくは5,000以下、より好ましくは3,000以下、更に好ましくは2,000以下である。
The copolymer of EO and AO is a copolymer of EO and AO, which will be described later. The addition mode of EO and AO may be either random addition or block addition, and random addition and block addition. Addition may be mixed, but a block-added copolymer is preferable, and a pluronic-type copolymer is more preferable.
Examples of the AO include alkylene oxides having 3 or 4 carbon atoms, such as propylene oxide (PO), oxetane, 1,2-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, and tetrahydrofuran. Can be mentioned.
The copolymer of EO and AO is more preferably a copolymer of EO and PO, still more preferably a block copolymer of EO and PO, and still more preferably a triblock of EO and PO. A block copolymer, more preferably a pluronic copolymer obtained by adding ethylene oxide to polypropylene glycol.
Further, in the copolymer of EO and AO, the number average molecular weight (Mn) of the structural portion derived from AO is preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more. And preferably 5,000 or less, more preferably 3,000 or less, and still more preferably 2,000 or less.

 前記ポリオキシエチレンアルキルエーテルとしては、高級アルコールのEO付加物であることが好ましい。当該高級アルコールとしては、例えば、炭素数6以上24以下の脂肪族アルコールが挙げられる。当該高級アルコールの炭素数としては、好ましくは8以上、より好ましくは10以上、更に好ましくは12以上であり、そして、好ましくは20以下、より好ましくは18以下、更に好ましくは16以下である。
 当該脂肪族アルコールとしては、好ましくは1級アルコール又は2級アルコール、より好ましくは1級アルコールである。また、直鎖状でもよく、分岐状でもよく、環状であってもよい。
 当該脂肪族アルコールとしては、例えば、オクタノール、2-エチルヘキサノール、ノナノール、デカノール、ウンデシルアルコール、ラウリルアルコール、トリデシルアルコール、イソトリデシルアルコール、ミリスチルアルコール、ペンタデシルアルコール、パルミチルアルコール、ヘプタデカノール、ステアリルアルコール、イソステアリルアルコール、ノナデシルアルコール、エイコサノール等の飽和脂肪族アルコール;オクテニルアルコール、デセニルアルコール、ドデセニルアルコール、トリデセニルアルコール、テトラデセニルアルコール、パルミトレイルアルコール、オレイルアルコール、ガドレイルアルコール、リノレイルアルコール等の不飽和脂肪族アルコール;エチルシクロヘキシルアルコール、プロピルシクロヘキシルアルコール、オクチルシクロヘキシルアルコール、ノニルシクロヘキシルアルコール、アダマンチルアルコール等の環状脂肪族アルコールが挙げられる。
The polyoxyethylene alkyl ether is preferably an EO adduct of a higher alcohol. Examples of the higher alcohol include aliphatic alcohols having 6 to 24 carbon atoms. The carbon number of the higher alcohol is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less.
The aliphatic alcohol is preferably a primary alcohol or a secondary alcohol, and more preferably a primary alcohol. Further, it may be linear, branched or cyclic.
Examples of the aliphatic alcohol include octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, isotridecyl alcohol, myristyl alcohol, pentadecyl alcohol, palmityl alcohol, heptadecanol. Saturated fatty alcohols such as stearyl alcohol, isostearyl alcohol, nonadecyl alcohol, eicosanol; octenyl alcohol, decenyl alcohol, dodecenyl alcohol, tridecenyl alcohol, tetradecenyl alcohol, palmitoleyl alcohol, Unsaturated aliphatic alcohols such as oleyl alcohol, gadrel alcohol, linoleyl alcohol; ethyl cyclohexyl alcohol, propyl cyclohexyl Alcohol, octylcyclohexyl alcohol, nonylcyclohexyl alcohol, cyclic aliphatic alcohols, such as adamantyl alcohol.

 前記ポリオキシエチレンアルキレンアルキルエーテルとしては、高級アルコールのEO及びAO付加物であることが好ましい。当該高級アルコールとしては、前記ポリオキシエチレンアルキルエーテルで説明したものと同様である。
 また、EO以外のAOとしては、例えば、炭素数3又は4のアルキレンオキサイドが挙げられ、1,2-プロピレンオキサイド、1,3-プロピレンオキサイド、1,2-ブチレンオキサイド、2,3-ブチレンオキサイド、1,3-ブチレンオキサイド、テトラヒドロフランが挙げられる。
 なお、前記ポリオキシエチレンアルキルエーテル及びポリオキシエチレンアルキレンアルキルエーテルは、前記高級アルコールにEO及び/又はAOを付加して合成することができるが、高級アルコールへのEO及びAOの付加は、公知の方法で行うことができ、無触媒又は触媒の存在下、常圧又は加圧下、1段階又は多段階で行ってもよい。
 なお、成分(B)は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
The polyoxyethylene alkylene alkyl ether is preferably an EO and AO adduct of a higher alcohol. The higher alcohol is the same as that described for the polyoxyethylene alkyl ether.
Examples of AO other than EO include alkylene oxides having 3 or 4 carbon atoms, such as 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. 1,3-butylene oxide and tetrahydrofuran.
The polyoxyethylene alkyl ether and the polyoxyethylene alkylene alkyl ether can be synthesized by adding EO and / or AO to the higher alcohol, but the addition of EO and AO to the higher alcohol is known. It can be carried out by a method, and may be carried out in one step or in multiple steps in the presence of no catalyst or in the presence of a catalyst, at normal pressure or under pressure.
In addition, a component (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

 成分(B)の含有量は、前記加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下である。当該含有量が0.020質量%未満であると、加工液の消泡性及び汚染抑制効果が悪化する。また、当該含有量が0.500質量%超えであると、微粉混入前の加工液の消泡性が悪化する。
 このような観点から、成分(B)の含有量は、前記加工液の全量100質量%基準で、好ましくは0.030質量%以上、より好ましくは0.035質量%以上、更に好ましくは0.060質量%以上であり、そして、好ましくは0.200質量%以下、より好ましくは0.175質量%以下、更に好ましくは0.120質量%以下である。
Content of a component (B) is 0.020 mass% or more and 0.500 mass% or less on the basis of 100 mass% of the whole quantity of the said processing liquid. When the content is less than 0.020% by mass, the antifoaming property and the contamination suppressing effect of the processing liquid are deteriorated. Moreover, the defoaming property of the processing liquid before fine powder mixing will deteriorate that the said content is over 0.500 mass%.
From such a viewpoint, the content of the component (B) is preferably 0.030% by mass or more, more preferably 0.035% by mass or more, and still more preferably 0.00% by mass, based on the total amount of the machining fluid of 100% by mass. It is 060% by mass or more, and preferably 0.200% by mass or less, more preferably 0.175% by mass or less, and further preferably 0.120% by mass or less.

 また、前述のとおり、前記加工液中、成分(A)と成分(B)との含有量比〔A/B〕は、質量比で0.05以上2.00以下である。
 当該含有量比が0.05未満であると、加工液の消泡性及び汚染抑制効果が悪化する。同様に、当該含有量比が2.00を超える場合にも、加工液の消泡性及び汚染抑制効果が悪化する。
 このような観点から、当該含有量比〔A/B〕は、質量比で、好ましくは0.10以上、より好ましくは0.15以上、更に好ましくは0.20以上であり、そして、好ましくは0.90以下、より好ましくは0.80以下、更に好ましくは0.75以下である。
Moreover, as above-mentioned, content ratio [A / B] of a component (A) and a component (B) in the said process liquid is 0.05 or more and 2.00 or less by mass ratio.
When the content ratio is less than 0.05, the antifoaming property and the contamination suppressing effect of the processing liquid are deteriorated. Similarly, when the content ratio exceeds 2.00, the antifoaming property and the contamination suppressing effect of the processing liquid are deteriorated.
From such a viewpoint, the content ratio [A / B] is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more, and preferably by mass ratio. 0.90 or less, more preferably 0.80 or less, and still more preferably 0.75 or less.

<水>
 前記水は、特に限定されず、蒸留水、イオン交換水(脱イオン水)等の精製水;水道水;工業用水;等を用いることができ、好ましくは精製水、より好ましくはイオン交換水(脱イオン水)である。
 前記加工液の難燃性を向上させ安全性を高める観点、及び加工液を低粘度化してハンドリング性を向上させる観点から、当該水の含有量は、前記加工液の全量100質量%基準で、好ましくは50.000質量%以上、より好ましくは75.000質量%以上、更に好ましくは95.000質量%以上、より更に好ましくは96.000質量%以上、より更に好ましくは96.500質量%以上である。そして、前記加工液中の有効成分量を確保する観点から、好ましくは99.970質量%以下、より好ましくは99.930質量%以下、更に好ましくは99.900質量%以下である。
 ここで、本明細書中、「有効成分」とは、前記加工液から水を除いた全成分を指す。
<Water>
The water is not particularly limited, and purified water such as distilled water and ion exchange water (deionized water); tap water; industrial water; and the like can be used, preferably purified water, more preferably ion exchange water ( Deionized water).
From the viewpoint of improving the flame retardancy of the machining fluid and increasing safety, and from the viewpoint of improving the handling property by reducing the viscosity of the machining fluid, the water content is based on the total amount of the machining fluid of 100% by mass, Preferably it is 50.000 mass% or more, More preferably, it is 75.000 mass% or more, More preferably, it is 95.000 mass% or more, More preferably, it is 96.000 mass% or more, More preferably, it is 96.500 mass% or more It is. And from a viewpoint of ensuring the amount of active ingredients in the processing fluid, it is preferably 99.970 mass% or less, more preferably 99.930 mass% or less, and still more preferably 99.900 mass% or less.
Here, in this specification, the “active ingredient” refers to all ingredients excluding water from the processing liquid.

<成分(C)>
 前記加工液は、加工液の保水性が向上する観点から、前述の成分(A)、成分(B)及び水に加えて、更に、成分(C)として多価アルコール及び多価アルコール誘導体からなる群より選ばれる1種以上であるアルコール成分を含有することが好ましい。
<Ingredient (C)>
From the viewpoint of improving the water retention of the working fluid, the working fluid is composed of a polyhydric alcohol and a polyhydric alcohol derivative as the component (C) in addition to the aforementioned component (A), component (B) and water. It is preferable to contain at least one alcohol component selected from the group.

 成分(C)としては、例えば、エチレングリコール、プロピレングリコール、1,4-ブタンジオール、ヘキサメチレングリコール、ネオペンチルグリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、グリセリン、これらのエステル誘導体、これらのエーテル誘導体;ポリエチレングリコール、ポリプロピレングリコール等が挙げられる。
 成分(C)としては、好ましくはエチレングリコール、プロピレングリコール、ジプロピレングリコール、ジエチレングリコール、ポリエチレングリコール、グリセリン、これらのエステル誘導体及びこれらのエーテル誘導体からなる群より選ばれる1種以上、より好ましくはエチレングリコール、ジエチレングリコール、ポリエチレングリコール、グリセリン、これらのエステル誘導体及びこれらのエーテル誘導体からなる群より選ばれる1種以上、更に好ましくはジエチレングリコール、グリセリン、これらのエステル誘導体、及びこれらのエーテル誘導体からなる群より選ばれる1種以上である。
 なお、成分(C)は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
Examples of the component (C) include ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, glycerin, and ester derivatives thereof. , These ether derivatives; polyethylene glycol, polypropylene glycol and the like.
Component (C) is preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, polyethylene glycol, glycerin, their ester derivatives and their ether derivatives, more preferably ethylene glycol , One or more selected from the group consisting of diethylene glycol, polyethylene glycol, glycerin, their ester derivatives and their ether derivatives, more preferably selected from the group consisting of diethylene glycol, glycerin, their ester derivatives, and their ether derivatives One or more.
In addition, a component (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

 前記加工液が成分(C)を含有する場合、成分(C)の含有量は、加工液中の保水性を向上させる観点から、前記加工液の全量100質量%基準で、好ましくは0.010質量%以上、より好ましくは0.030質量%以上、更に好ましくは0.060質量%以上、より更に好ましくは1.000質量%以上であり、また、含有量に見合った効果を得る観点から、好ましくは5.000質量%以下、より好ましくは4.000質量%以下、更に好ましくは3.500質量%以下、より更に好ましくは1.500質量%以下である。 When the processing liquid contains the component (C), the content of the component (C) is preferably 0.010 based on the total amount of the processing liquid of 100% by mass from the viewpoint of improving water retention in the processing liquid. % By mass, more preferably 0.030% by mass or more, more preferably 0.060% by mass or more, still more preferably 1.000% by mass or more, from the viewpoint of obtaining an effect commensurate with the content, Preferably it is 5.000 mass% or less, More preferably, it is 4.000 mass% or less, More preferably, it is 3.500 mass% or less, More preferably, it is 1.500 mass% or less.

 前記加工液が成分(C)を含有する場合、前記加工液中、成分(A)と成分(C)との含有量比〔C/A〕は、質量比で好ましくは1.00以上、より好ましくは1.20以上、更に好ましくは1.40以上、より更に好ましくは5.00以上であり、そして、好ましくは300以下、より好ましくは250以下、更に好ましくは230以下、より更に好ましくは10.0以下である。 When the working fluid contains the component (C), the content ratio [C / A] of the component (A) and the component (C) in the working fluid is preferably 1.00 or more by mass ratio. Preferably it is 1.20 or more, more preferably 1.40 or more, still more preferably 5.00 or more, and preferably 300 or less, more preferably 250 or less, still more preferably 230 or less, and even more preferably 10 0.0 or less.

 前記加工液が成分(C)を含有する場合、前記加工液中、成分(B)と成分(C)との含有量比〔C/B〕は、質量比で好ましくは0.20以上、より好ましくは0.30以上、更に好ましくは0.50以上、より更に好ましくは5.00以上であり、そして、好ましくは100以下、より好ましくは90.0以下、更に好ましくは87.0以下、より更に好ましくは10.0以下である。 When the working fluid contains the component (C), the content ratio [C / B] of the component (B) and the component (C) in the working fluid is preferably 0.20 or more by mass ratio. Preferably it is 0.30 or more, more preferably 0.50 or more, still more preferably 5.00 or more, and preferably 100 or less, more preferably 90.0 or less, still more preferably 87.0 or less, more More preferably, it is 10.0 or less.

<その他添加剤>
 前記加工液は、本発明の目的を阻害しない範囲で、前述の成分(A)、成分(B)及び水、並びに必要に応じて含有する成分(C)に加えて、更に、その他添加剤を含有していてもよい。
 その他添加剤としては、成分(A)及び(B)以外の界面活性剤、pH調整剤、消泡剤、金属不活性化剤、殺菌剤・防腐剤、防錆剤、酸化防止剤等が挙げられる。これらの添加剤は、単独で用いてもよく、又は2種以上を組み合わせて使用してもよい。また、これらの添加剤の中では、成分(A)及び(B)以外の界面活性剤並びにpH調整剤からなる群より選ばれる1種以上が好ましい。
<Other additives>
In addition to the above-mentioned component (A), component (B) and water, and component (C) contained as necessary, the processing fluid further contains other additives as long as the object of the present invention is not impaired. You may contain.
Other additives include surfactants other than components (A) and (B), pH adjusters, antifoaming agents, metal deactivators, bactericides / preservatives, rust inhibitors, antioxidants, and the like. It is done. These additives may be used alone or in combination of two or more. Moreover, in these additives, 1 or more types chosen from the group which consists of surfactant other than a component (A) and (B) and a pH adjuster are preferable.

 成分(A)及び(B)以外の界面活性剤としては、アニオン界面活性剤、カチオン界面活性剤、成分(A)及び(B)以外の非イオン界面活性剤、及び両性界面活性剤等が挙げられる。
 アニオン界面活性剤としては、アルキルベンゼンスルホン酸塩、アルファオレフィンスルホン酸塩等が挙げられる。カチオン界面活性剤としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩などの四級アンモニウム塩等が挙げられる。
 成分(A)及び(B)以外の非イオン界面活性剤としては、例えば、HLB値が4未満12超えであるアセチレングリコール、HLB値が4未満12超えであるアセチレングリコールのアルキレンオキサイド付加物、分子構造中のエチレンオキサイドの付加モル数が5未満であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、及びHLBが6未満であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤等(例えば、成分(A)及び(B)以外のポリオキシエチレンアルキルエーテル、成分(A)及び(B)以外のポリオキシエチレンアルキルフェニルエーテル等のエーテル、脂肪酸アルカノールアミドのようなアミド等)が挙げられる。
 両性界面活性剤としては、ベタイン系としてアルキルベタインなどが挙げられる。
 界面活性剤の中では、好ましくは成分(A)及び(B)以外のエーテル等の非イオン界面活性剤、より好ましくはHLB値が4未満12超えであるアセチレングリコール、HLB値が4未満12超えであるアセチレングリコールのアルキレンオキサイド付加物、分子構造中のエチレンオキサイドの付加モル数が5未満であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、及びHLBが6未満であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤からなる群より選ばれる1種以上、更に好ましくはHLB値が4未満12超えであるアセチレングリコール及びHLB値が4未満12超えであるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上が挙げられる。
Examples of surfactants other than components (A) and (B) include anionic surfactants, cationic surfactants, nonionic surfactants other than components (A) and (B), and amphoteric surfactants. It is done.
Examples of the anionic surfactant include alkyl benzene sulfonate and alpha olefin sulfonate. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts.
Nonionic surfactants other than components (A) and (B) include, for example, acetylene glycol having an HLB value of less than 4 and greater than 12, an alkylene oxide adduct of acetylene glycol having an HLB value of less than 4 and greater than 12, and molecules An ethylene oxide adduct in which the number of moles of ethylene oxide in the structure is less than 5, and a nonionic surfactant having no acetylene group, and an ethylene oxide adduct having an HLB of less than 6. Nonionic surfactants having no acetylene group (for example, polyoxyethylene alkyl ethers other than components (A) and (B), ethers such as polyoxyethylene alkylphenyl ethers other than components (A) and (B), Amides such as fatty acid alkanolamides).
Examples of amphoteric surfactants include alkyl betaines as betaines.
Among the surfactants, preferably nonionic surfactants such as ethers other than components (A) and (B), more preferably acetylene glycol having an HLB value of less than 4 and more than 12, and an HLB value of less than 4 and more than 12 An alkylene oxide adduct of acetylene glycol, an ethylene oxide adduct in which the number of moles of ethylene oxide in the molecular structure is less than 5, and a nonionic surfactant having no acetylene group, and an HLB of less than 6 One or more selected from the group consisting of non-ionic surfactants having an acetylene group, and more preferably an acetylene glycol having an HLB value of less than 4 and exceeding 12 and an HLB value of 4 Selected from the group consisting of alkylene oxide adducts of acetylene glycol that are less than 12 One or more members, and the like.

 pH調整剤は、主に加工液のpHを調整するために用いられる。当該pH調整剤としては、各種酸成分や塩基成分が挙げられ、これら成分の含有量比を調整することで、適宜、加工液のpHを調整することができる。
 なお、当該酸成分と塩基成分は互いに反応して塩を形成し得る。
 そのため、pH調整剤として酸成分及び塩基成分を用いる場合、前記加工液中に当該酸成分と塩基成分との反応物が存在する場合、前述のとおり、当該酸成分及び塩基成分の反応物の含有量から算出される当該反応に寄与した当該酸成分及び塩基成分の各含有量を算出することもできる。また、その場合、当該反応物に代えて、反応前の当該酸成分及び塩基成分を含有しているものとみなすことができる。
The pH adjuster is mainly used to adjust the pH of the processing liquid. Examples of the pH adjuster include various acid components and base components, and the pH of the processing liquid can be appropriately adjusted by adjusting the content ratio of these components.
The acid component and the base component can react with each other to form a salt.
Therefore, when an acid component and a base component are used as a pH adjuster, when a reaction product of the acid component and the base component exists in the processing liquid, as described above, the reaction product of the acid component and the base component is contained. Each content of the acid component and the base component contributing to the reaction calculated from the amount can also be calculated. Moreover, it can replace with the said reaction material in that case, and can be considered that the said acid component and base component before reaction are contained.

 pH調整剤として用いられる酸成分としては、例えば、ラウリン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、ネオデカン酸、イソノナン酸、カプリン酸、イソステアリン酸等の各種脂肪酸;酢酸、リンゴ酸、クエン酸等のカルボン酸;ポリアクリル酸等の高分子酸及びその塩;リン酸等の無機酸;が挙げられる。これらの中では、脂肪酸が好ましく、ネオデカン酸、イソノナン酸、カプリン酸、ドデカン二酸等の炭素数12以下の脂肪酸がより好ましく、ネオデカン酸、イソノナン酸、カプリン酸、及びドデカン二酸からなる群より選ばれる1種以上が更に好ましい。 Examples of the acid component used as a pH adjuster include various fatty acids such as lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, neodecanoic acid, isononanoic acid, capric acid, and isostearic acid; acetic acid, malic acid, and citric acid. Examples thereof include carboxylic acids such as acids; polymer acids such as polyacrylic acid and salts thereof; and inorganic acids such as phosphoric acid. Among these, fatty acids are preferable, fatty acids having 12 or less carbon atoms such as neodecanoic acid, isononanoic acid, capric acid, and dodecanedioic acid are more preferable, and a group consisting of neodecanoic acid, isononanoic acid, capric acid, and dodecanedioic acid. One or more selected are more preferable.

 pH調整剤として用いられる塩基成分としては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、トリ-n-プロパノールアミン、トリ-n-ブタノールアミン、トリイソブタノールアミン、トリ-tert-ブタノールアミン、N-メチルエタノールアミン、N-エチルエタノールアミン、N-ブチルエタノールアミン、N-シクロヘキシルエタノールアミン、N-メチルジエタノールアミン、N-エチルジエタノールアミン、N-シクロヘキシルジエタノールアミン、N,N-ジメチルエタノールアミン、N,N-ジエチルエタノールアミン等のアルカノールアミン;メチルアミン、ジメチルアミン、エチルアミン、ジエチルアミン、プロピルアミン、ジプロピルアミン等のアルキルアミン;アンモニアが挙げられる。これらの中では、3級アミンが好ましく、トリエタノールアミン、トリイソプロパノールアミン、N-メチルジエタノールアミン、及びN-シクロヘキシルジエタノールアミンからなる群より選ばれる少なくとも1種がより好ましい。 Examples of the base component used as a pH adjuster include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tri-n-propanolamine, tri-n-butanolamine, Isobutanolamine, tri-tert-butanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-cyclohexylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-cyclohexyldiethanolamine, Alkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine; methylamine, dimethylamine, ethylamine , Diethylamine, propylamine, alkyl amines such as dipropylamine; and the ammonia. Among these, tertiary amines are preferable, and at least one selected from the group consisting of triethanolamine, triisopropanolamine, N-methyldiethanolamine, and N-cyclohexyldiethanolamine is more preferable.

 消泡剤としては、例えば、シリコーン油、フルオロシリコーン油及びフルオロアルキルエーテルが挙げられる。
 金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、チアジアゾール及びベンゾトリアゾールが挙げられる。
 殺菌剤・防腐剤としては、例えば、パラオキシ安息香酸エステル類(パラベン類)の他、安息香酸、サリチル酸、ソルビン酸、デヒドロ酢酸、p-トルエンスルホン酸及びそれらの塩類、並びにフェノキシエタノールが挙げられる。
 防錆剤としては、例えば、アルキルベンゼンスルフォネート、ジノニルナフタレンスルフォネート、アルケニルコハク酸エステル、及び成分(C)以外の多価アルコールエステルが挙げられる。
 酸化防止剤としては、例えば、フェノール系酸化防止剤及びアミン系酸化防止剤が挙げられる。
Examples of the antifoaming agent include silicone oil, fluorosilicone oil, and fluoroalkyl ether.
Examples of the metal deactivator include imidazoline, pyrimidine derivatives, thiadiazole, and benzotriazole.
Examples of the disinfectant / preservative include p-oxybenzoates (parabens), benzoic acid, salicylic acid, sorbic acid, dehydroacetic acid, p-toluenesulfonic acid and salts thereof, and phenoxyethanol.
Examples of the rust inhibitor include alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, and polyhydric alcohol esters other than component (C).
Examples of the antioxidant include phenolic antioxidants and amine antioxidants.

 前記加工液がその他添加材を含有する場合、前記加工液中、その他添加剤の合計含有量は、前記加工液の全量100質量%基準で、好ましくは0.001質量%以上、より好ましくは0.002質量%以上、更に好ましくは0.010質量%以上であり、そして、好ましくは0.200質量%以下、より好ましくは0.150質量%以下、更に好ましくは0.130質量%以下、より更に好ましくは0.100質量%以下、より更に好ましくは0.050質量%以下である。 When the processing liquid contains other additives, the total content of other additives in the processing liquid is preferably 0.001% by mass or more, more preferably 0, based on the total amount of the processing liquid of 100% by mass. 0.002% by mass or more, more preferably 0.010% by mass or more, and preferably 0.200% by mass or less, more preferably 0.150% by mass or less, still more preferably 0.130% by mass or less, more More preferably, it is 0.100 mass% or less, More preferably, it is 0.050 mass% or less.

 前記加工液がその他添加材を含有する場合、前記加工液中、その他添加剤の配合量と成分(A)の含有量との比〔(その他添加剤)/A〕は、質量比で好ましくは0.01以上、より好ましくは0.05以上、更に好ましくは0.10以上、より更に好ましくは0.20以上であり、そして、好ましくは10.0以下、より好ましくは9.00以下、更に好ましくは5.00以下、より更に好ましくは1.00以下、より更に好ましくは0.50以下である。 When the processing liquid contains other additives, the ratio ((other additives) / A) between the amount of the other additives and the content of the component (A) in the processing liquid is preferably a mass ratio. 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.20 or more, and preferably 10.0 or less, more preferably 9.00 or less, further Preferably it is 5.00 or less, More preferably, it is 1.00 or less, More preferably, it is 0.50 or less.

 また、消泡性及び汚染抑制効果を向上させる観点から、前記加工液がその他添加材を含有する場合、前記加工液中、水、成分(A)及び成分(B)、並びに必要に応じて含有する成分(C)の合計含有量は、前記加工液の全量100質量%基準で、好ましくは98.000質量%以上、より好ましくは99.000質量%以上、更に好ましくは99.800質量%以上、より更に好ましくは99.900質量%以上であり、そして、好ましくは100質量%以下、より好ましくは99.999量%以下、更に好ましくは99.998質量%以下、より更に好ましくは99.950質量%以下である。 Moreover, from the viewpoint of improving the defoaming property and the contamination suppressing effect, when the processing liquid contains other additives, water, component (A) and component (B), and if necessary, contained in the processing liquid The total content of the component (C) is preferably 98.000% by mass or more, more preferably 99.000% by mass or more, and still more preferably 99.800% by mass or more, based on the total amount of the processing fluid of 100% by mass. , More preferably 99.900% by mass or more, and preferably 100% by mass or less, more preferably 99.999% by mass or less, still more preferably 99.998% by mass or less, and still more preferably 99.950. It is below mass%.

 また、消泡性及び汚染抑制効果を向上させる観点から、前記加工液がその他添加材を含有する場合、前記加工液中、成分(A)及び成分(B)、並びに必要に応じて含有する成分(C)及びその他添加剤の合計含有量(有効成分量)は、前記加工液の全量100質量%基準で、好ましくは0.030質量%以上、より好ましくは0.080質量%以上、更に好ましくは0.100質量%以上であり、そして、好ましくは5.500質量%以下、より好ましくは3.500量%以下、更に好ましくは2.000質量%以下、より更に好ましくは1.000質量%以下、より更に好ましくは0.500質量%以下である。 Moreover, from the viewpoint of improving the defoaming property and the contamination suppressing effect, when the processing liquid contains other additives, the component (A) and the component (B), and the component included as necessary in the processing liquid The total content (active ingredient amount) of (C) and other additives is preferably 0.030% by mass or more, more preferably 0.080% by mass or more, and still more preferably, based on the total amount of the processing liquid of 100% by mass. Is 0.100% by mass or more, and preferably 5.500% by mass or less, more preferably 3.500% by mass or less, further preferably 2.000% by mass or less, and still more preferably 1.000% by mass. Hereinafter, it is more preferably 0.500% by mass or less.

 また、前記加工液のpHは、好ましくは4以上9以下である。
 前記加工液のpHが4以上であると、前記ワイヤや加工装置等の腐食を抑制できるため好ましい。また、前記加工液のpHが9以下であると、例えば、シリコン等を加工する際に切粉から水素が大量に発生することを抑制できるため好ましい。
 このような観点から、前記加工液のpHは、より好ましくは4以上8以下、更に好ましくは5以上8以下である。
The pH of the working fluid is preferably 4 or more and 9 or less.
It is preferable that the pH of the processing liquid is 4 or more because corrosion of the wire, processing apparatus, and the like can be suppressed. Moreover, it is preferable that the pH of the processing liquid is 9 or less because, for example, a large amount of hydrogen can be suppressed from chips when processing silicon or the like.
From such a viewpoint, the pH of the processing liquid is more preferably 4 or more and 8 or less, and further preferably 5 or more and 8 or less.

[脆性材料加工液の製造方法]
 前記脆性材料加工液の製造方法は、
 少なくとも水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを配合する、脆性材料加工液の製造方法であって、
 成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下となるように配合して脆性材料加工液を得る、脆性材料加工液の製造方法である。
[Manufacturing method of brittle material processing fluid]
The manufacturing method of the brittle material processing liquid is:
At least with water,
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
A method for producing a brittle material processing liquid,
The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) It is a manufacturing method of the brittle material processing liquid which mixes so that ratio [A / B] may be 0.05 or more and 2.00 or less by mass ratio, and obtains a brittle material processing liquid.

 水、成分(A)及び成分(B)を配合する順序は特に制限はなく、水に対して、成分(A)及び成分(B)を逐次又は同時に配合してもよく、予め成分(A)に対し成分(B)を配合して、その混合物を水に配合してもよい。
 また、当該製造方法では、水、成分(A)及び成分(B)を配合し、更に必要に応じて成分(C)及びその他添加剤からなる群より選ばれる1種以上を配合してもよく、その場合、配合する各成分の配合順、配合方法等は特に限定されない。
 なお、水、成分(A)、成分(B)、成分(C)、及びその他添加剤は、それぞれ、脆性材料加工液の欄で前述したものと同様であり、その好適な態様も同様であるため、その詳細な説明は省略する。また、水、成分(A)、成分(B)、成分(C)、及びその他添加剤の好適な配合量及び各成分間の好適な配合量比についても、それぞれ、脆性材料加工液の欄で前述した前記加工液中の各含有量及び各含有量比と同様であるため、その詳細な説明は省略する。
The order in which water, component (A) and component (B) are blended is not particularly limited, and component (A) and component (B) may be blended sequentially or simultaneously with water. Alternatively, the component (B) may be blended and the mixture may be blended in water.
Moreover, in the said manufacturing method, water, a component (A), and a component (B) may be mix | blended, and also 1 or more types chosen from the group which consists of a component (C) and another additive may be mix | blended as needed. In that case, the blending order, blending method and the like of each component to be blended are not particularly limited.
In addition, water, a component (A), a component (B), a component (C), and other additives are respectively the same as what was mentioned above in the column of a brittle material processing liquid, The suitable aspect is also the same. Therefore, the detailed description is abbreviate | omitted. In addition, the preferred blending amount of water, component (A), component (B), component (C), and other additives and the preferred blending ratio between the components are also listed in the column of brittle material processing liquid, respectively. Since it is the same as each content and each content ratio in the said process liquid mentioned above, the detailed description is abbreviate | omitted.

[脆性材料加工液の用途]
 前記脆性材料加工液は、前述したワイヤソー、好ましくは固定砥粒ワイヤソーを用いてシリコンインゴット等の脆性材料からなる被加工材をワイヤソー加工する際に好適に用いることができる。すなわち、前記加工液は、ワイヤを用いて脆性材料からなる被加工材を加工する時に好適に用いることができる。
 当該脆性材料としては、例えば、結晶シリコン、サファイア、窒化ガリウム、炭化ケイ素、ネオジム磁石、ジルコニア、グラファイト、ニオブ酸、タンタル酸、水晶及びガラスが挙げられる。前記加工液は、汚染抑制効果の観点から、結晶シリコン、サファイア、炭化ケイ素、ネオジム磁石、水晶、又はガラスを加工する際により好適に用いることができ、結晶シリコン、サファイア、又は炭化ケイ素を加工する際に更に好適に用いることができる。
[Use of brittle material processing fluid]
The brittle material processing liquid can be suitably used when wire sawing a workpiece made of a brittle material such as a silicon ingot using the wire saw described above, preferably a fixed abrasive wire saw. That is, the processing liquid can be suitably used when processing a workpiece made of a brittle material using a wire.
Examples of the brittle material include crystalline silicon, sapphire, gallium nitride, silicon carbide, neodymium magnet, zirconia, graphite, niobic acid, tantalate, quartz and glass. The processing liquid can be more suitably used when processing crystalline silicon, sapphire, silicon carbide, neodymium magnet, crystal, or glass from the viewpoint of the contamination suppression effect, and processes crystalline silicon, sapphire, or silicon carbide. In this case, it can be used more suitably.

[脆性材料加工液の濃縮液]
 前記脆性材料加工液は、例えば、加工液中の水を減量して2倍以上700倍以下に濃縮した濃縮液を、水で希釈することによって得られるものであってもよい。
 すなわち、前述の加工を行う際、前記加工液の濃縮液又は当該濃縮液と同一の組成である加工液用の組成物若しくは原液(以下、単に「濃縮液」ともいう。)を水で2倍以上700倍以下に希釈して、前記脆性材料加工液として使用することができる。
 また、前記加工液を下記に示す濃縮液となるように濃縮して、保管・輸送等に適した態様として用いることもできる。
 ここで、本明細書中、当該「濃縮液」とは、前述のとおり、加工液から水を減量して濃縮したものに限らず、水で希釈して加工液とされることを前提として調製された組成物若しくは原液も含む。
[Concentrate of brittle material processing fluid]
The brittle material processing liquid may be obtained, for example, by diluting a concentrated liquid obtained by reducing the amount of water in the processing liquid and concentrating it two to 700 times with water.
That is, when the above-described processing is performed, the concentrated liquid of the processing liquid or the composition or stock solution for the processing liquid having the same composition as the concentrated liquid (hereinafter also simply referred to as “concentrated liquid”) is doubled with water. It can be diluted to 700 times or less and used as the brittle material processing liquid.
Moreover, the said processing liquid can be concentrated so that it may become the concentrate shown below, and it can also be used as an aspect suitable for storage, transportation, etc.
Here, in the present specification, the “concentrated liquid” is not limited to a concentrated liquid obtained by reducing the amount of water from the processing liquid as described above, but is prepared on the assumption that the processing liquid is diluted with water. Of the prepared composition or stock solution.

 当該濃縮液としては、例えば、
 水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを含み、
 成分(A)の含有量が、脆性材料加工液の濃縮液全量100質量%基準で、好ましくは0.200質量%以上、そして、好ましくは30.000質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の濃縮液全量100質量%基準で、好ましくは0.300質量%以上、そして、好ましくは90.000質量%以下、より好ましくは75.000質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下である、脆性材料加工液の濃縮液が挙げられる。
As the concentrate, for example,
water and,
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
Including
The content of the component (A) is preferably 0.200% by mass or more, and preferably 30.000% by mass or less, based on 100% by mass of the total concentrated liquid of the brittle material processing liquid.
The content of the component (B) is preferably 0.300% by mass or more, and preferably 90.000% by mass or less, more preferably 75.000% by mass, based on 100% by mass of the total concentrated liquid of the brittle material processing liquid. %, And the content ratio [A / B] of the component (A) and the component (B) is 0.05 to 2.00 in terms of mass ratio. It is done.

 前記濃縮液は、更に、成分(C)を、前記濃縮液全量100質量%基準で、好ましくは5.000質量%以上、より好ましくは10.000質量%以上、そして、好ましくは95.000質量%以下で含有してもよい。
 また、前記濃縮液は、本発明の目的を阻害しない範囲で、水、成分(A)、成分(B)及び必要に応じて含有する成分(C)以外に、更に、その他添加剤を含有していてもよい。
 前記濃縮液中の水の含有量は、濃縮液全量100質量%基準で、好ましくは0.100質量%以上50.000質量%未満である。
The concentrate further contains component (C), preferably 5.000% by mass or more, more preferably 10.000% by mass or more, and preferably 95.000% by mass based on the total amount of the concentrate 100% by mass. % Or less.
Further, the concentrated solution contains other additives in addition to water, component (A), component (B), and component (C) contained as necessary, as long as the object of the present invention is not impaired. It may be.
The content of water in the concentrated solution is preferably 0.100% by mass or more and less than 50000% by mass based on the total amount of the concentrated solution of 100% by mass.

 なお、当該濃縮液中、水、成分(A)、成分(B)、成分(C)、及びその他添加剤は、それぞれ、脆性材料加工液の欄で前述したものと同様であり、その好適な態様も同様であるため、その詳細な説明は省略する。
 また、当該濃縮液中の水、成分(A)、成分(B)、成分(C)、及びその他添加剤の好適な含有量の範囲は、特に制限はないが、当該濃縮液を水で2倍以上700倍に濃縮して用いる際、それぞれ、脆性材料加工液の欄で前述した各成分の好適な含有量の範囲を満たすように含有していることが好ましい。
 したがって、水、成分(A)、成分(B)、成分(C)、及びその他添加剤の各成分間の好適な含有量比についても、それぞれ、脆性材料加工液の欄で前述した前記加工液中の各成分間の含有量比と同様であり、その詳細な説明は省略する。
In addition, in the said concentrate, water, a component (A), a component (B), a component (C), and other additives are respectively the same as what was mentioned above in the column of a brittle material processing liquid, The suitable Since the aspect is also the same, detailed description thereof is omitted.
Moreover, although there is no restriction | limiting in particular in the range of suitable content of the water in the said concentrate, a component (A), a component (B), a component (C), and another additive, The said concentrate is 2 with water. When concentrated and used in a range of 700 times to 700 times, it is preferable that each of the components is contained so as to satisfy the range of suitable contents of each component described above in the column of brittle material processing liquid.
Accordingly, the above-mentioned working fluids described above in the column of brittle material working fluid are also respectively used for suitable content ratios among water, component (A), component (B), component (C), and other additives. It is the same as the content ratio between each component in the inside, and the detailed description thereof is omitted.

[脆性材料加工液の濃縮液の使用方法]
 前記濃縮液は、前述のとおり、主に水で希釈して前記加工液を調製するための組成物若しくは原液として用いることができる。
 すなわち、本発明の一実施形態に係る脆性材料加工液の濃縮液の使用方法としては、例えば、
 水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを含み、
 成分(A)の含有量が、濃縮液全量100質量%基準で、好ましくは0.200質量%以上、そして、好ましくは30.000質量%以下であり、
 成分(B)の含有量が、濃縮液全量100質量%基準で、好ましくは0.300質量%以上、そして、好ましくは90.000質量%以下、より好ましくは75.000質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下である、脆性材料加工液の濃縮液を、
 成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下となるように水で希釈して、脆性材料加工液を調製し、
 当該脆性加工液を脆性材料の加工に使用する、脆性材料加工液の濃縮液の使用方法である。
[How to use concentrated liquid of brittle material processing liquid]
As described above, the concentrated liquid can be used as a composition or a stock solution for preparing the processing liquid by mainly diluting with water.
That is, as a method of using a concentrated liquid of brittle material processing liquid according to an embodiment of the present invention, for example,
water and,
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
Including
The content of the component (A) is preferably 0.200% by mass or more, and preferably 30.000% by mass or less based on 100% by mass of the total amount of the concentrate.
The content of component (B) is preferably 0.300% by mass or more, and preferably 90.000% by mass or less, more preferably 75.000% by mass or less, based on 100% by mass of the total concentrate. And the content ratio [A / B] of a component (A) and a component (B) is 0.05 or more and 2.00 or less by mass ratio, The concentrated liquid of a brittle material processing liquid,
The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) The brittle material working fluid is prepared by diluting with water so that the ratio [A / B] is 0.05 or more and 2.00 or less by mass ratio,
This is a method for using a concentrated liquid of brittle material processing liquid, in which the brittle processing liquid is used for processing a brittle material.

 また、当該使用方法で用いる濃縮液及び加工液は、それぞれ独立に、更に必要に応じて成分(C)及びその他添加剤からなる群より選ばれる1種以上を含有してもよい。
 なお、水、成分(A)、成分(B)、成分(C)、及びその他添加剤は、それぞれ、脆性材料加工液の欄で前述したものと同様であり、その好適な態様も同様であるため、その詳細な説明は省略する。
 また、当該使用方法で用いる濃縮液中、水、成分(A)、成分(B)、成分(C)、及びその他添加剤の含有量及び各成分間の含有量比、並びにそれらの好適範囲についても、それぞれ、前述した前記濃縮液中の各含有量及び各含有量比と同様であるため、その詳細な説明は省略する。
 同様に、当該使用方法で用いる加工液中、水、成分(A)、成分(B)、成分(C)、及びその他添加剤の含有量及び各成分間の含有量比、並びにそれらの好適範囲についても、それぞれ、脆性材料加工液の欄で前述した各含有量及び各含有量比と同様であるため、その詳細な説明は省略する。
Moreover, the concentrated liquid and the processing liquid used in the method of use may each independently contain one or more selected from the group consisting of the component (C) and other additives as necessary.
In addition, water, a component (A), a component (B), a component (C), and other additives are respectively the same as what was mentioned above in the column of a brittle material processing liquid, The suitable aspect is also the same. Therefore, the detailed description is abbreviate | omitted.
Moreover, about the content of water, a component (A), a component (B), a component (C), and other additives in the concentrate used by the said usage method, the content ratio between each component, and those suitable ranges Since each is the same as each content and each content ratio in the concentrated liquid described above, detailed description thereof is omitted.
Similarly, the content of water, the component (A), the component (B), the component (C), and other additives in the working fluid used in the method of use, the content ratio between the components, and their preferred ranges Are the same as the respective contents and ratios described above in the column of brittle material processing liquid, and detailed description thereof will be omitted.

 ここで、当該濃縮液及び加工液は、それぞれ、前述の濃縮液及び加工液と同様であり、それらが含有する各成分も含めて、その好適な態様も同様であるため、その詳細な説明は省略する。
 同様に、当該濃縮液及び加工液が含有する、水、成分(A)、成分(B)、成分(C)、及びその他添加剤も、それぞれ、脆性材料加工液の欄で前述したものと同様であり、その好適な態様も同様であるため、その詳細な説明は省略する。また、水、成分(A)、成分(B)、成分(C)、及びその他添加剤の各成分の好適な含有量及び各成分間の含有量比も、それぞれ、脆性材料加工液の欄で前述した前記加工液中の各成分間の含有量比と同様であり、その詳細な説明は省略する。
Here, the concentrated liquid and the processing liquid are the same as the above-described concentrated liquid and the processing liquid, respectively, and the preferred embodiments including the respective components contained therein are also the same. Omitted.
Similarly, water, the component (A), the component (B), the component (C), and other additives contained in the concentrated liquid and the processing liquid are the same as those described above in the column of the brittle material processing liquid. Since the preferred embodiment is the same, detailed description thereof is omitted. Moreover, the suitable content of each component of water, a component (A), a component (B), a component (C), and other additives and the content ratio between each component are also each in the column of a brittle material processing liquid. This is the same as the content ratio between the components in the processing liquid described above, and a detailed description thereof will be omitted.

[脆性材料の加工方法]
 本発明の一実施形態に係る脆性材料の加工方法は、前記加工液を用いてシリコンインゴット等の前記脆性材料からなる被加工材を加工する方法である。
 ここで、前記加工液は、当該加工液を被加工材に供給して、被加工材に接触させて使用するものである。加工液は、前記被加工材と前記ワイヤソー等の加工具との間を潤滑する。更には、切り屑(切粉)の除去、被加工材の錆止め、工具及び被加工材の冷却等のためにも使用される。
 前記加工液を使用して行う脆性材料の加工は、具体的には、切削加工、研削加工、打抜き加工、研摩、絞り加工、抽伸加工、圧延加工などの各種の加工が挙げられるが、これらの中では、切削加工、研削加工が好ましく、切削加工がより好ましい。
 被加工材としての脆性材料は、前述した材料が挙げられる。
 なお、前述のとおり、前記加工液は、シリコンインゴットの切断加工に用いるものとして好適に使用されるものである。
[Processing of brittle materials]
The brittle material processing method according to an embodiment of the present invention is a method of processing a workpiece made of the brittle material such as a silicon ingot using the processing liquid.
Here, the machining fluid is used by supplying the machining fluid to the workpiece and bringing it into contact with the workpiece. The machining fluid lubricates between the workpiece and a processing tool such as the wire saw. Furthermore, it is used for removal of chips (chips), rust prevention of workpieces, cooling of tools and workpieces, and the like.
Specific examples of the processing of the brittle material performed using the processing liquid include various processing such as cutting, grinding, punching, polishing, drawing, drawing, rolling, and the like. Among them, cutting and grinding are preferable, and cutting is more preferable.
Examples of the brittle material as the workpiece include the materials described above.
Note that, as described above, the processing liquid is preferably used as one used for cutting a silicon ingot.

 ここで、より具体的には、前述したように遊離砥粒方式と固定砥粒方式という両方式のワイヤソー加工方法は、前述のシリコンインゴットから、複数のシリコンウェハを一度に切り出すため、マルチワイヤソー装置が用いられている。マルチワイヤソー装置では、一定間隔で複数の溝が彫られた2以上のガイドローラー上の各溝に1本ずつワイヤを巻きつけ、各ワイヤが一定の張力で平行に保持されている。そして、切断加工時には、各ガイドローラーを回転させ、ノズル等から吐出した加工液をワイヤに付着させながら、該ワイヤを一方向又は双方向に走行させ、加工液が付着したワイヤにシリコンインゴットを押し当てて切断を行っている。また、必要に応じてシリコンインゴット等の被加工物自体に加工液をかけながら加工を行うこともある。
 加工に使用される加工液は、タンク等に貯蔵され、そこから配管等で前述の加工室ノズルまで運ばれる。また、切断時に使用された加工液は、切断装置下部の使用済み加工液受けタンク等で回収される。また、場合によっては、装置内を循環させて再利用されることもある。
 したがって、前記加工液は、このような脆性材料の加工方法で用いる加工液としてより好適に使用され、このうち、固定砥粒ワイヤにより、シリコンインゴットからシリコンウェハを切り出す加工方法に用いる加工液として更に好適に使用され、固定砥粒ワイヤソーを用いたマルチワイヤー装置を用いて、シリコンインゴットからシリコンウェハを切り出す加工方法により更に好適に使用される。
More specifically, as described above, the wire saw processing method of both the free abrasive grain method and the fixed abrasive grain method cuts a plurality of silicon wafers from the silicon ingot at a time. Is used. In the multi-wire saw device, one wire is wound around each groove on two or more guide rollers having a plurality of grooves carved at a constant interval, and each wire is held in parallel with a constant tension. During the cutting process, each guide roller is rotated and the wire is run in one or both directions while the machining liquid discharged from the nozzle or the like is adhered to the wire, and the silicon ingot is pushed onto the wire to which the machining liquid is adhered. Cutting is applied. In addition, processing may be performed while applying a processing liquid to a workpiece itself such as a silicon ingot as necessary.
The processing liquid used for processing is stored in a tank or the like, and is transported from there to the aforementioned processing chamber nozzle by piping or the like. Further, the machining fluid used at the time of cutting is collected in a used machining fluid receiving tank or the like below the cutting device. Moreover, depending on the case, it may be reused by circulating in the apparatus.
Therefore, the processing liquid is more preferably used as a processing liquid used in such a brittle material processing method. Among these, the processing liquid is further used as a processing liquid used in a processing method of cutting a silicon wafer from a silicon ingot with a fixed abrasive wire. It is preferably used and more preferably used by a processing method of cutting a silicon wafer from a silicon ingot using a multi-wire apparatus using a fixed abrasive wire saw.

[加工装置]
 本発明の一実施形態に係る脆性材料の加工装置は、前記本発明の一実施形態である脆性材料加工液を用いる加工装置であり、好ましくはマルチワイヤー切断加工装置であり、より好ましくは固定砥粒ワイヤソーを備えたマルチワイヤー切断加工装置であり、更に好ましくはシリコンインゴット切断用の固定砥粒ワイヤソーを備えたマルチワイヤー切断加工装置である。
 ここで「本発明の一実施形態である脆性材料加工液を用いる加工装置」とは、「本発明の一実施形態である脆性材料加工液を充填した加工装置」ということもできる。
[Processing equipment]
The brittle material processing apparatus according to an embodiment of the present invention is a processing apparatus that uses the brittle material processing liquid according to an embodiment of the present invention, preferably a multi-wire cutting apparatus, and more preferably a fixed abrasive. A multi-wire cutting apparatus provided with a grain wire saw, and more preferably a multi-wire cutting apparatus provided with a fixed abrasive wire saw for cutting a silicon ingot.
Here, the “processing apparatus using a brittle material processing liquid according to an embodiment of the present invention” can also be referred to as “a processing apparatus filled with a brittle material processing liquid according to an embodiment of the present invention”.

 以下に、本発明を、実施例により、更に具体的に説明するが、本発明は、これらの例によってなんら限定されるものではない。
 なお、各成分及び脆性材料加工液に関する各物性は、以下に示す要領に従って評価した。
Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
In addition, each physical property regarding each component and a brittle material processing liquid was evaluated in accordance with the following procedure.

[HLB値]
 グリフィン法により算出される値を用いた。
[HLB value]
The value calculated by the Griffin method was used.

[pH値]
 実施例及び比較例で得られた各脆性材料加工液のpHを、東亜ディーケーケー株式会社製のガラス電極式水素イオン濃度指示計、型式:HM-25Rを用いて評価した。
 得られた結果を下記表1及び2に示す。
[PH value]
The pH of each brittle material processing solution obtained in the examples and comparative examples was evaluated using a glass electrode type hydrogen ion concentration indicator, model: HM-25R, manufactured by Toa DKK Corporation.
The obtained results are shown in Tables 1 and 2 below.

[消泡性評価]
 実施例及び比較例で得られた各脆性材料加工液を用いて、次の手順に従って評価した。
(液面高さ:微粉なし)
 液循環装置を備えた容量2Lのメスシリンダー(全高:460mm、内径φ85mm)中に、加工液200mLを注入し、メスシリンダー底部から循環装置で加工液を抜き出して循環させ、該2Lメスシリンダーの底面からの高さが400mmとなる位置から、抜き出した加工液を内径φ5mmのノズルを用いて該2Lメスシリンダー内に吐出させた。この時の加工液の流量が1.3L/分となるように循環量を調整した。
 循環開始から5分経過後の液面高さを計測した。
 なお、液面高さは、メスシリンダーの目盛りを利用して、単位「mL」で対比している。
 この時、泡立ちが発生すると当該液面高さが高くなる、すなわち、「mL」の値が大きくなることから、当該液面高さの値「mL」が小さいほど、消泡性に優れる。
 得られた結果を下記表1及び2に示す。
(液面高さ:微粉あり)
 前記加工液に対して、微粉(「グラファイト粉末」、和光純薬工業株式会社製、特級)を評価液中の濃度13質量%となるように配合したものを評価液として準備した。
 当該評価液を用いること以外は、「微粉なし」での液面高さの計測方法と同様の方法で液面高さを計測し、微粉混入時の加工液の消泡性を評価した。
 得られた結果を下記表1及び2に示す。
[Defoaming evaluation]
Evaluation was performed according to the following procedure using each brittle material working fluid obtained in the examples and comparative examples.
(Liquid level: no fine powder)
200 mL of the processing liquid is poured into a 2 L measuring cylinder (total height: 460 mm, inner diameter φ85 mm) equipped with a liquid circulating device, and the processing liquid is extracted from the bottom of the measuring cylinder with a circulating device and circulated, and the bottom of the 2 L measuring cylinder From the position where the height from the nozzle becomes 400 mm, the extracted working fluid was discharged into the 2 L graduated cylinder using a nozzle having an inner diameter of φ5 mm. The circulation rate was adjusted so that the flow rate of the working fluid at this time was 1.3 L / min.
The liquid level after 5 minutes from the start of circulation was measured.
The liquid level is compared with the unit “mL” using the scale of the graduated cylinder.
At this time, when bubbling occurs, the liquid level height increases, that is, the value of “mL” increases. Therefore, the smaller the liquid level height value “mL”, the better the defoaming property.
The obtained results are shown in Tables 1 and 2 below.
(Liquid level: fine powder)
A blend of fine powder (“graphite powder”, manufactured by Wako Pure Chemical Industries, Ltd., special grade) so as to have a concentration of 13 mass% in the evaluation liquid was prepared as an evaluation liquid.
Except using the said evaluation liquid, liquid level height was measured by the method similar to the measuring method of the liquid level height "without fine powder", and the defoaming property of the processing liquid at the time of fine powder mixing was evaluated.
The obtained results are shown in Tables 1 and 2 below.

[汚染抑制効果の評価]
(シリンダー壁面の汚れ評価)
 前記消泡性評価の「液面高さ:微粉あり」評価を行った後の、2Lメスシリンダーの内壁面の汚れを目視にて観察し、以下の基準により評価した。
・A:微粉によるシリンダー壁面の汚れが軽度であり、液面付近の背景が透けて見える。
・B:微粉によるシリンダー壁面の汚れが重度であり、液面付近の背景が透けて見えない。
 得られた結果を下記表1及び2に示す。
[Evaluation of pollution control effect]
(Evaluation of cylinder wall contamination)
After the evaluation of “liquid level height: fine powder” in the defoaming evaluation, the stain on the inner wall surface of the 2 L graduated cylinder was visually observed and evaluated according to the following criteria.
-A: The cylinder wall surface is slightly soiled by fine powder, and the background near the liquid level can be seen through.
-B: The dirt on the cylinder wall surface due to fine powder is severe, and the background near the liquid level cannot be seen through.
The obtained results are shown in Tables 1 and 2 below.

[実施例1~9、比較例1~9]
 下記の表1及び2に示す組成となるように各成分を配合し、脆性材料加工液を調製した。前記評価方法に従って、各実施例及び比較例の脆性材料加工液を評価した。得られた結果を下記表1及び2に示す。
[Examples 1 to 9, Comparative Examples 1 to 9]
Each component was blended so as to have the composition shown in Tables 1 and 2 below to prepare a brittle material processing liquid. According to the said evaluation method, the brittle material processing liquid of each Example and a comparative example was evaluated. The obtained results are shown in Tables 1 and 2 below.

 なお、下記表1及び2に示す各成分は、それぞれ以下の化合物を表す。
・界面活性剤1:2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのEO付加物(アセチレングリコールのEO付加物)、HLB=4
・界面活性剤2:2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのEO付加物(アセチレングリコールのEO付加物)、HLB=8
・界面活性剤3:2,5,8,11-テトラメチル-6-ドデシン-5,8-ジオールのEO付加物(アセチレングリコールのEO付加物)、HLB=8
・界面活性剤4:2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのEO付加物(アセチレングリコールのEO付加物)、HLB=13
・界面活性剤5:エチレンオキサイド(EO)とプロピレンオキサイド(PO)とのブロック共重合体(プルロニック型界面活性剤)、ポリオキシプロピレン鎖部分の数平均分子量=1,750、EO付加モル数=27、HLB=8
・界面活性剤6:炭素数12以上14以下である高級アルコールのEO付加物(主成分:ポリオキシアルキレンアルキルエーテル)、EO付加モル数=14、HLB=15
・界面活性剤7:炭素数12以上14以下である高級アルコールのEO付加物(主成分:ポリオキシアルキレンアルキルエーテル)、EO付加モル数=7、HLB=12
・界面活性剤8:炭素数12以上14以下である高級アルコールのEO付加物(主成分:ポリオキシエチレンアルキルエーテル)、EO付加モル数=4、HLB=9
・ジエチレングリコール
・イソノナン酸
・トリイソプロパノールアミン
・イオン交換水
In addition, each component shown in following Table 1 and 2 represents the following compounds, respectively.
Surfactant 1: EO adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO adduct of acetylene glycol), HLB = 4
Surfactant 2: EO adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO adduct of acetylene glycol), HLB = 8
Surfactant 3: EO adduct of 2,5,8,11-tetramethyl-6-dodecin-5,8-diol (EO adduct of acetylene glycol), HLB = 8
Surfactant 4: EO adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (EO adduct of acetylene glycol), HLB = 13
Surfactant 5: block copolymer of ethylene oxide (EO) and propylene oxide (PO) (pluronic surfactant), number average molecular weight of polyoxypropylene chain portion = 1,750, EO addition mole number = 27, HLB = 8
Surfactant 6: EO adduct of higher alcohol having 12 to 14 carbon atoms (main component: polyoxyalkylene alkyl ether), EO addition mole number = 14, HLB = 15
Surfactant 7: EO adduct of higher alcohol having 12 to 14 carbon atoms (main component: polyoxyalkylene alkyl ether), EO addition mole number = 7, HLB = 12.
Surfactant 8: EO adduct of higher alcohol having 12 to 14 carbon atoms (main component: polyoxyethylene alkyl ether), EO addition mole number = 4, HLB = 9
・ Diethylene glycol ・ Isononanoic acid ・ Triisopropanolamine ・ Ion-exchanged water

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

 表1に示すとおり、実施例1~9の脆性材料加工液は、成分(A)及び成分(B)を含み、かつ、所定の含有量比〔A/B〕を満たしているため、いずれも消泡性に優れ、また、微粉の付着による汚れが少なく汚染抑制効果に優れることが確認された。
 一方で、表2に示すとおり、比較例1、4、8及び9の脆性材料加工液は、所定の含有量比〔A/B〕を満たしていないため、いずれも消泡性に劣り、また、微粉の付着による汚れが多いことが確認された。
 また、比較例2、3及び5の脆性材料加工液は、成分(B)を含有しておらず、そして、比較例6及び7の脆性材料加工液は、成分(A)を含有していないため、いずれも消泡性に劣り、また、微粉の付着による汚れが多いことが確認された。
 なお、比較例5の脆性材料加工液は、EO付加モル数5未満である高級アルコールのEO付加物を用いている。また、比較例6の脆性材料加工液は、HLB値が12を超えるアセチレングリコールのEO付加物を用いている。
 なお、実施例1に記載の加工液を用い、固定砥粒方式のマルチワイヤソー装置を用いて、シリコンインゴットを切断加工した結果、加工時に加工液の泡立ちが少なく、消泡性に優れていることが確認された。また、当該装置及び切断されたシリコンウェハ上の汚れも軽度であり、洗浄が容易であることも確認された。
As shown in Table 1, each of the brittle material working fluids of Examples 1 to 9 contains the component (A) and the component (B) and satisfies the predetermined content ratio [A / B]. It was confirmed that the foam was excellent in defoaming property, and there was little contamination due to the adhesion of fine powder, and the anti-contamination effect was excellent.
On the other hand, as shown in Table 2, since the brittle material processing liquids of Comparative Examples 1, 4, 8 and 9 do not satisfy the predetermined content ratio [A / B], all of them are inferior in antifoaming properties. It was confirmed that there were many stains due to adhesion of fine powder.
Further, the brittle material processing liquids of Comparative Examples 2, 3 and 5 do not contain the component (B), and the brittle material processing liquids of Comparative Examples 6 and 7 do not contain the component (A). For this reason, it was confirmed that all of them were inferior in antifoaming properties and that there were many stains due to adhesion of fine powder.
Note that the brittle material processing liquid of Comparative Example 5 uses an EO adduct of a higher alcohol having an EO addition mole number of less than 5. Further, the brittle material working fluid of Comparative Example 6 uses an EO adduct of acetylene glycol having an HLB value exceeding 12.
In addition, as a result of cutting the silicon ingot using the fixed abrasive type multi-wire saw apparatus using the processing liquid described in Example 1, the processing liquid is less foamed during processing and has excellent defoaming properties. Was confirmed. Further, it was confirmed that the contamination on the apparatus and the cut silicon wafer was slight and easy to clean.

 前記本発明の一実施形態である脆性材料加工液は消泡性に優れる。そのため、例えば、シリコンインゴット等の脆性材料からなる被加工材を切断加工する際に、当該加工液の泡立ちを抑制することができ、泡立ちが原因で当該加工液を受けるタンクから当該加工液が溢れだす(オーバーフローの発生)不具合、又は泡立ちが原因で発生する加工精度の低下等の悪影響を防止することができる。
 また、前記本発明の一実施形態である脆性材料加工液は汚染抑制効果に優れる。そのため、例えば、シリコンインゴット等の脆性材料の加工時に、当該加工に用いる切断機等の加工機や被切削材等の被加工材の切粉等の微粉による汚染を抑制できる。結果、加工機や加工物の洗浄が容易となる。
 したがって、前記本発明の一実施形態である脆性材料加工液を用いることで、作業性の効率化及び生産性の向上を図ることができる。
 そして、前述のとおり、前記本発明の一実施形態である脆性材料加工液は、シリコンインゴット等の脆性材料の切断加工に用いるものとして好適に使用されるものであり、より好適には、固定砥粒ワイヤを用いて、シリコンインゴットからシリコンウェハを切り出す加工のクーラントとして使用されるものである。
The brittle material processing liquid according to one embodiment of the present invention is excellent in antifoaming properties. Therefore, for example, when cutting a workpiece made of a brittle material such as a silicon ingot, foaming of the processing liquid can be suppressed, and the processing liquid overflows from the tank that receives the processing liquid due to foaming. It is possible to prevent adverse effects such as a soaking (occurrence of overflow) failure or a reduction in processing accuracy caused by foaming.
In addition, the brittle material processing liquid according to one embodiment of the present invention is excellent in the contamination suppressing effect. Therefore, for example, during processing of a brittle material such as a silicon ingot, contamination by fine powder such as a processing machine such as a cutting machine used for the processing or a cutting material of a workpiece such as a cutting material can be suppressed. As a result, the processing machine and the workpiece can be easily cleaned.
Therefore, by using the brittle material processing liquid according to one embodiment of the present invention, it is possible to improve work efficiency and productivity.
As described above, the brittle material working fluid according to an embodiment of the present invention is preferably used as a material for cutting brittle materials such as silicon ingots, and more preferably, fixed abrasive. A grain wire is used as a coolant for cutting a silicon wafer from a silicon ingot.

Claims (9)

 水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを含み、
 成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下である、脆性材料加工液。
water and,
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
Including
The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) A brittle material processing liquid in which the ratio [A / B] is 0.05 to 2.00 in terms of mass ratio.
 更に、下記成分(C)を含む、請求項1に記載の脆性材料加工液。
(C):多価アルコール及び多価アルコール誘導体からなる群より選ばれる1種以上であるアルコール成分
Furthermore, the brittle material processing liquid of Claim 1 containing the following component (C).
(C): one or more alcohol components selected from the group consisting of polyhydric alcohols and polyhydric alcohol derivatives
 成分(C)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上5.000質量%以下である、請求項2に記載の脆性材料加工液。 The brittle material processing liquid according to claim 2, wherein the content of the component (C) is 0.010% by mass or more and 5.000% by mass or less based on a total amount of 100% by mass of the brittle material processing liquid.  前記水の含有量が、脆性材料加工液の全量100質量%基準で、50.000質量%以上99.970質量%以下である、請求項1~3のいずれか1項に記載の脆性材料加工液。 The brittle material processing according to any one of claims 1 to 3, wherein the water content is 50.000% by mass or more and 99.970% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid. liquid.  ワイヤを用いて脆性材料からなる被加工材を加工する時に用いる、請求項1~4のいずれか1項に記載の脆性材料加工液。 5. The brittle material processing liquid according to claim 1, which is used when a workpiece made of a brittle material is processed using a wire.  前記ワイヤが、固定砥粒ワイヤである、請求項5に記載の脆性材料加工液。 The brittle material processing liquid according to claim 5, wherein the wire is a fixed abrasive wire.  前記脆性材料が、結晶シリコン、サファイア、炭化ケイ素、ネオジム磁石、水晶、又はガラスである、請求項5又は6に記載の脆性材料加工液。 The brittle material processing liquid according to claim 5 or 6, wherein the brittle material is crystalline silicon, sapphire, silicon carbide, neodymium magnet, crystal, or glass.  pHが4以上9以下である、請求項1~7のいずれか1項に記載の脆性材料加工液。 The brittle material processing liquid according to any one of claims 1 to 7, wherein the pH is 4 or more and 9 or less.  少なくとも水と、
(A):HLB値が4以上12以下であるアセチレングリコール、及びHLB値が4以上12以下であるアセチレングリコールのアルキレンオキサイド付加物からなる群より選ばれる1種以上と、
(B):HLB値が6以上であり、分子構造中のエチレンオキサイドの付加モル数が5以上であるエチレンオキサイド付加物であって、かつアセチレン基を有しない非イオン界面活性剤、
とを配合する、脆性材料加工液の製造方法であって、
 成分(A)の含有量が、脆性材料加工液の全量100質量%基準で、0.010質量%以上0.200質量%以下であり、
 成分(B)の含有量が、脆性材料加工液の全量100質量%基準で、0.020質量%以上0.500質量%以下であり、かつ
 成分(A)と成分(B)との含有量比〔A/B〕が、質量比で0.05以上2.00以下となるように配合して脆性材料加工液を得る、請求項1~8のいずれか1項に記載の脆性材料加工液の製造方法。
At least with water,
(A): one or more selected from the group consisting of an acetylene glycol having an HLB value of 4 to 12 and an alkylene oxide adduct of acetylene glycol having an HLB value of 4 to 12, and
(B): nonionic surfactant having an HLB value of 6 or more, an ethylene oxide adduct having an addition mole number of ethylene oxide in the molecular structure of 5 or more, and having no acetylene group,
A method for producing a brittle material processing liquid,
The content of the component (A) is 0.010% by mass or more and 0.200% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid,
The content of the component (B) is 0.020% by mass or more and 0.500% by mass or less based on 100% by mass of the total amount of the brittle material processing liquid, and the content of the component (A) and the component (B) The brittle material processing liquid according to any one of claims 1 to 8, wherein a brittle material processing liquid is obtained by blending such that the ratio [A / B] is 0.05 to 2.00 in terms of mass ratio. Manufacturing method.
PCT/JP2018/010249 2017-03-17 2018-03-15 Brittle material processing liquid Ceased WO2018169008A1 (en)

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