CN106660914B - The recycling method of reuse method and anti-corrosion agent composition treatment fluid that separation and recovery method, the anti-corrosion agent composition of alkylene glycol monoalky lether dispose waste liquid - Google Patents
The recycling method of reuse method and anti-corrosion agent composition treatment fluid that separation and recovery method, the anti-corrosion agent composition of alkylene glycol monoalky lether dispose waste liquid Download PDFInfo
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- CN106660914B CN106660914B CN201580033942.2A CN201580033942A CN106660914B CN 106660914 B CN106660914 B CN 106660914B CN 201580033942 A CN201580033942 A CN 201580033942A CN 106660914 B CN106660914 B CN 106660914B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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Abstract
The present invention provide, from contain alkylene glycol monoalky lether and its corresponding carboxylate, and include other solvents solvent mixture in high-purity and in high yield separate and recover alkylene glycol monoalky lether method.By to including alkylene glycol monoalky lether (the first solvent), alkylene glycol monoalky lether carboxylic ester (the second solvent) corresponding with alkylene glycol monoalky lether (the first solvent), and alkali compounds is added in the solvent mixture of the solvent (third solvent) different from alkylene glycol monoalky lether (the first solvent) and alkylene glycol monoalky lether carboxylic ester (the second solvent), to which alkylene glycol monoalky lether carboxylic ester (the second solvent) is saponified, it is changed into alkylene glycol monoalky lether (the first solvent), then alkylene glycol monoalky lether (the first solvent) is recycled by distilling.
Description
Technical field
The present invention relates to the recyclings that the separation and recovery method of alkylene glycol monoalky lether, anti-corrosion agent composition dispose waste liquid
The recycling method of method and anti-corrosion agent composition treatment fluid.Further specifically, it is related to from containing alkylene glycol list
The middle separation and recovery alkylene two that disposes waste liquid of the solvent mixture such as anti-corrosion agent composition of alkyl ether carboxylate corresponding with its
The circulation of reuse method and anti-corrosion agent composition treatment fluid that the method for alcohol monoalky lether, anti-corrosion agent composition dispose waste liquid
Application method.
Background technique
In the manufacturing process of semiconductor element, liquid crystal display element, colour filter etc., all the time using using liquid sense
Photosensitiveness composition is (in the present specification hereinafter also referred to " resist ".) photoetching technique.By the liquid photosensitive composite
It is coated on the substrate of semiconductor (silicon substrate etc.), glass, resin (polyimides, polyester etc.) etc. and when carrying out pattern formation,
Need in order to remove be attached to substrate end or inside liquid photosensitive composite or be attached to photosensitive for being coated with liquid
The device of property composition or the liquid photosensitive composite in component surface and the washing carried out.
The purpose of the uncured resin of constituent for dissolution as above-mentioned liquid photosensitive composite etc., with alkylene
Glycol monoalkyl ether carboxylate corresponding with its is that the various solvent mixtures of principal component are widely used (referring to patent document 1
With 2).They are due to being used repeatedly and washability reduces at leisure, if the deterioration of its performance reaches certain level, conduct
Solvent slop is discharged.
In the solvent slop for stating solvent mixture in use to wash liquid photosensitive composite to generate, in addition to originally
Other than the solvent for including in solvent mixture, be also mixed into the resin of the constituent as liquid photosensitive composite, solvent,
Other additives.However, from viewpoints such as the reductions of the Deal with Environment Problem, manufacturing cost that attract attention in recent years, strongly
It is expected that the recycling of solvent slop, that is, separate and recover effective component from solvent slop and recycled.
As the most representative method for separating and recovering solvent composition from the solvent mixture comprising Multiple components, make
With distillation, but especially in comprising multicomponent situation, separated using distillation procedure and refine in solvent slop it is each at
Point not only process is many and diverse, is economically also difficult.For example, alkylene glycol monoalky lether and alkylene glycol monoalky lether monocarboxylic acid
Relatively, therefore, it is difficult to separate and recover them with high-purity and high-recovery for the boiling point of ester.In addition, from 3 kinds or more
Specific two kinds of ingredients are recycled in solvent mixture (for example, corresponding alkylene glycol monoalky lether and alkylene glycol monoalky lether
Monocarboxylate) in the case where, can with the boiling point of the relatively low ingredient of segregation ratio boiling point (alkylene glycol monoalky lether) it is lower at
Divide the higher ingredient of boiling point of (low boiling fraction) and ingredient more relatively high than boiling point (alkylene glycol monoalky lether monocarboxylate) (high
Boil fraction), but in the case where 3rd ingredient of the boiling point between two kinds of ingredients is mixed in, it is difficult to it is separated only by out the 3 one-tenth
Point.
In patent document 1, it as resist resin alcohol/ester series solvent solvent reuse method, discloses: wrapping
Resist containing pure and mild ester corresponding thereto carries out ester hydrolysis reaction, before making the amount and hydrolysis of alcohol with water is added in solvent
Compared to increase, then resulting reaction mass is distilled and is refined.
It discloses in patent document 2: being made by ester exchange reaction containing alkylene glycol monoalky lether (A ingredient) and A ingredient
Acetic acid esters (B component) solvent mixture in B component be changed into A ingredient, solvent mixture is distilled to separate back
Receive A ingredient.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-335535 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-247816 bulletin
Summary of the invention
Problems to be solved by the invention
Although disclosing the esterification or ester hydrolysis for causing alcohol by addition carboxylic acid in patent document 1, so as to appoint
Ester/alcohol ratio in meaning ground adjustment solvent mixture, but in embodiment, before the esterification as caused by addition carboxylic acid or water
It is containing in waste liquid before solution, as the ingredient other than the ester and alcohol of target be extremely micro 0.3%, be not need substantially
Consider to implement under conditions of the coexisting of other compositions.That is, substantially disclosing only how to control in patent document 1 and including
The mixing ratio of the two in the mixed liquor of two kinds of ingredients of ester/alcohol.In patent document 2, although ester exchange reaction is utilized, by
It is balanced reaction in ester exchange reaction, therefore, it is difficult to convert A ingredient for B component 100%, therefore, it is difficult to obtain in high yield.
The present invention in view of the foregoing, one of its goals is to provide, from contain alkylene glycol monoalky lether and its correspondence
Carboxylate and include other solvents solvent mixture in, with high-purity and in high yield separation and recovery alkylene glycol monoalkyl
The method of ether.In addition, one of the objects of the present invention is to provide, containing alkylene glycol monoalky lether and its corresponding carboxylate
The reuse method of anti-corrosion agent composition to dispose waste liquid and the recycling method of anti-corrosion agent composition treatment fluid.
The method used for solving the problem
The present inventors further investigate in order to solve the above problems, as a result, it has been found that, make containing alkylene glycol monoalky lether
(the first solvent), as the alkylene glycol monoalky lether carboxylic ester (the second solvent) and other solvent (thirds of corresponding carboxylate
Solvent) solvent mixture in the second solvent alkylene glycol monoalky lether (the first solvent) is changed by saponification, so
After distilled, so as to expeditiously separate and recover alkylene glycol monoalky lether (the first solvent).
That is, the present invention includes the embodiment of [1] below~[15].
[1] a kind of separation and recovery method of alkylene glycol monoalky lether, which is characterized in that be from comprising the first solvent,
The method that the first solvent is separated and recovered in first solvent mixture of two solvents and third solvent, first solvent is by following logical
Formula (I) indicates that second solvent is indicated by the following general formula (II), the third solvent and first solvent and the second solvent
Difference,
The separation and recovery method of the alkylene glycol monoalky lether includes following first steps and the second step,
First step: by adding alkali compounds into first solvent mixture, to obtain described second
Solvent saponification is simultaneously changed into the second solvent mixture obtained by the first solvent,
The second step: second solvent mixture is distilled and recycles the first solvent.
R(OR’)nOH (I)
R(OR’)nOCOR” (II)
[in logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4
Alkylidene, R " indicates that carbon atom number is 1~2 alkyl, the R in logical formula (I) and logical formula (II) be it is identical, lead to formula (I) and
R ' in logical formula (II) be also it is identical, n is 1 or 2.]
[2] separation and recovery method of the alkylene glycol monoalky lether according to [1], the alkali compounds are selected from hydrogen
At least one of sodium oxide molybdena, potassium hydroxide, calcium hydroxide and ammonium hydroxide hydroxide alkali compounds.
[3] separation and recovery method of the alkylene glycol monoalky lether according to [2], the alkali compounds are hydroxide
Sodium.
[4] separation and recovery method of the alkylene glycol monoalky lether according to any one of [1]~[3], described first
Solvent is propylene glycol monomethyl ether, and second solvent is propylene glycol monomethyl ether, and the third solvent is selected from ring
At least one of pentanone, cyclohexanone and 3- methoxy methyl propionate.
[5] separation and recovery method of the alkylene glycol monoalky lether according to any one of [1]~[4], described first
Solvent mixture is handled obtained by anti-corrosion agent composition using comprising the mixed solvent of first solvent and the second solvent
Manage waste liquid.
[6] a kind of reuse method that anti-corrosion agent composition disposes waste liquid, which is characterized in that including following processes,
First step: use is molten comprising shown in the first solvent shown in the following general formula (I) and the following general formula (II) second
The mixed solvent of agent handles anti-corrosion agent composition,
The second step: recycling is disposed waste liquid by what first step generated,
The third step: Xiang Suoshu disposes waste liquid middle addition alkali compounds, so that second in described dispose waste liquid is molten
Agent is saponified and is changed into the first solvent,
The solvent mixture obtained by the third step: being distilled and is recycled the first solvent by the fourth step, and
5th process: the second new solvent is added into the first solvent recycled by the fourth step, is modulated again
Mixed solvent with defined match ratio.
R(OR’)nOH (I)
R(OR’)nOCOR” (II)
[in logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4
Alkylidene, R " indicates that carbon atom number is 1~2 alkyl, the R in logical formula (I) and logical formula (II) be it is identical, lead to formula (I) and
R ' in logical formula (II) be also it is identical, n is 1 or 2.]
[7] reuse method that the anti-corrosion agent composition according to [6] disposes waste liquid, the alkali compounds are to be selected from
At least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide hydroxide alkali compounds.
[8] reuse method that the anti-corrosion agent composition according to [7] disposes waste liquid, the alkali compounds are hydrogen-oxygen
Change sodium.
[9] reuse method that the anti-corrosion agent composition according to any one of [6]~[8] disposes waste liquid, described
One solvent is propylene glycol monomethyl ether, and second solvent is propylene glycol monomethyl ether.
[10] reuse method that the anti-corrosion agent composition according to any one of [6]~[9] disposes waste liquid, described
After the third step before the fourth step, have following processes: include in disposing waste liquid described in separation is generated by saponification
Solid component.
[11] a kind of recycling method of anti-corrosion agent composition treatment fluid, which is characterized in that there are following first steps
~the seven process implements the second step~the 7th process repeatedly,
First step: user buys in molten comprising shown in the following general formula (I) first with defined match ratio from manufacturer
The mixed solvent of second solvent shown in agent and the following general formula (II),
The second step: user handles anti-corrosion agent composition using the mixed solvent,
The third step: manufacturer or recycling dealer's recycling are disposed waste liquid by what the second step generated,
The fourth step: manufacturer or recycling dealer are by the middle addition alkali compounds that disposes waste liquid, thus will
It is described dispose waste liquid in the second solvent saponification and be changed into the first solvent,
5th process: the solvent mixture obtained by the fourth step is distilled and is recycled by manufacturer or recycling dealer
First solvent,
6th process: manufacturer or recycling dealer add new the into the first solvent recycled by the 5th process
Two solvents, modulation has the mixed solvent of the defined match ratio again,
7th process: user buys in the mixed solvent modulated again from manufacturer or recycling dealer.
R(OR’)nOH (I)
R(OR’)nOCOR” (II)
[in logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4
Alkylidene, R " indicates that carbon atom number is 1~2 alkyl, the R in logical formula (I) and logical formula (II) be it is identical, lead to formula (I) and
R ' in logical formula (II) be also it is identical, n is 1 or 2.]
[12] recycling method of the anti-corrosion agent composition treatment fluid according to [11], the alkali compounds are choosings
From at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide hydroxide alkali compounds.
[13] recycling method of the anti-corrosion agent composition treatment fluid according to [12], the alkali compounds are hydrogen
Sodium oxide molybdena.
[14] recycling method of the anti-corrosion agent composition treatment fluid according to any one of [11]~[13], it is described
First solvent is propylene glycol monomethyl ether, and second solvent is propylene glycol monomethyl ether.
[15] recycling method of the anti-corrosion agent composition treatment fluid according to any one of [11]~[14], in institute
State after the fourth step before the 5th process, with following processes: it is that separation is generated by saponification, described dispose waste liquid in include
Solid component.
Invention effect
In accordance with the invention it is possible to from molten containing alkylene glycol monoalky lether and its corresponding carboxylate and other solvents
With high-purity and high yield separation and recovery alkylene glycol monoalky lether in agent composition.Furthermore it is possible to from alkylene glycol list is contained
With high-purity and high yield in the disposing waste liquid of the anti-corrosion agent composition of alkyl ether and its corresponding carboxylate and other solvents
Separate and recover alkylene glycol monoalky lether.Therefore, according to the present invention, by the recycling of anti-corrosion agent composition to dispose waste liquid,
Semiconductor element, liquid crystal display element, colour filter etc. can be manufactured with low cost.
Detailed description of the invention
Fig. 1 is the outline figure of the distilling apparatus used in embodiment.
Specific embodiment
It disposes waste liquid below for separation and recovery method, the anti-corrosion agent composition of alkylene glycol monoalky lether of the invention
The recycling method of reuse method and anti-corrosion agent composition treatment fluid is described in detail, but the present invention is not said by these
Embodiment used in bright limits.
First embodiment
First embodiment of the invention is from comprising alkylene glycol monoalky lether (the first solvent), alkylene glycol monoalkyl
Ether carboxylate (the second solvent) and with alkylene glycol monoalky lether (the first solvent) and alkylene glycol monoalky lether carboxylic ester
Alkylene glycol is separated and recovered in the solvent mixture (the first solvent mixture) of (the second solvent) different solvent (third solvent)
The method of monoalky lether (the first solvent).It is characterized in that, having following first steps and the second step, the first step
It is: by adding alkali compounds into the first solvent mixture, thus by the alkylene glycol list alkane in the first solvent mixture
The saponification of base ether carboxylate is changed into alkylene glycol monoalky lether and obtains the second solvent mixture, and the second step is: passing through
Second solvent mixture is distilled to separate and recover alkylene glycol monoalky lether.
The first solvent mixture as the process object of separation and recovery includes: the following general formula in the first embodiment
(I) the correspondence carboxylic acid shown in alkylene glycol monoalky lether shown in (the first solvent), the following general formula (II) as the first solvent
The alkylene glycol monoalky lether carboxylic ester (the second solvent) of ester, and at least one kind of solvent (third other than both solvents
Solvent).
R(OR’)nOH (I)
R(OR’)nOCOR” (II)
[in logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4
Alkylidene, R " indicates that carbon atom number is 1~2 alkyl, the R in logical formula (I) and logical formula (II) be it is identical, lead to formula (I) and
R ' in logical formula (II) be also it is identical, n is 1 or 2.]
As described above, as long as the first solvent mixture includes the first solvent respectively by leading to formula (I) and the expression of logical formula (II)
As an essential component with the second solvent, also just not special comprising at least one kind of solvent (third solvent) other than both solvents
It does not limit, but the present invention is special in the case where the boiling point of third solvent is between the boiling point of the first solvent and the boiling point of the second solvent
Not not effectively.For example, in the manufacturing process of semiconductor element, liquid crystal display element, colour filter etc., as anti-corrosion agent composition
The solvent slop for the mixed organic solvents that removing solvent, washer solvent etc. use becomes the object of separation and recovery.
In logical formula (I) and logical formula (II), as the concrete example of R, methyl, ethyl, propyl, isopropyl, positive fourth can be enumerated
The alkyl that the carbon atom numbers such as base, isobutyl group are 1~4, as the concrete example of R ', can enumerate ethylidene, trimethylene, propylidene,
Butylidene etc..R in logical formula (I) and logical formula (II) be it is identical, the R ' led in formula (I) and logical formula (II) is identical.General formula
(II) R " in is methyl or ethyl.N is 1 or 2.
As the concrete example of the first solvent shown in logical formula (I), can enumerate for example, ethylene glycol single methyl ether, ethylene glycol list
Ethylether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol
Monomethyl ether etc..As the second solvent shown in logical formula (II), their acetic acid esters or propionic ester can be enumerated.
First solvent mixture is the mixture comprising the first solvent and the second solvent, can be enumerated comprising ethylene glycol monomethyl
It is the mixed liquor of ether and ethylene glycol single methyl ether acetic acid esters, mixed comprising ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate
It closes liquid, the mixed liquor comprising ethylene glycol monopropyl ether and ethylene glycol monopropyl ether acetic acid esters, include ethylene glycol monobutyl ether and second
The mixed liquor of glycol monobutyl ether acetate, the mixing comprising diethylene glycol monoethyl ether and diethylene glycol monoethyl ether acetic acid esters
Liquid, the mixed liquor comprising propylene glycol monomethyl ether and propylene glycol monomethyl ether include dipropylene glycol monomethyl ether and two
The mixed liquor etc. of propylene glycol monomethyl ether.Wherein, for comprising propylene glycol monomethyl ether as the first solvent and the third two
Solvent mixture of the alcohol monomethyl ether acetate as the second solvent can preferably apply separation and recovery method of the invention.
About the content ratio of the first solvent and the second solvent in the first solvent mixture, as long as their binaries mix
It is just not particularly limited, but the mixing ratio (the first solvent/the second solvent) of the first solvent and the second solvent is excellent in terms of mass conversion
It is selected as 1 or more, more preferably 1.5 or more, further preferably 2 or more.If the content ratio of the second solvent is few, can subtract
The amount of alkali compounds (sodium hydroxide etc.) required for the saponification of few aftermentioned second solvent, can make alkali compounds
It is evenly dispersed into solvent mixture.As preferred first solvent mixture, can enumerate using propylene glycol monomethyl ether/the third
Glycol monomethyl ether acetic acid esters=6.8/3.2~7.2/2.8 (mass ratio), more preferably propylene glycol monomethyl ether/propylene glycol list
Methylether acetate=6.9/3.1~7.1/2.9 (mass ratio) is most preferably propylene glycol monomethyl ether/propylene glycol monomethyl ether
The mixed solvent of acetic acid esters=7/3 (mass ratio) disposes waste liquid come the resist generated when handling resist.
First solvent mixture includes at least one kind of third solvent other than the first solvent and the second solvent.?
In the case that one solvent mixture is the waste liquid for removing or the washing of anti-corrosion agent composition, cooperate in anti-corrosion agent composition
Solvent can become third solvent.As third solvent, it specifically may be exemplified out the ketones such as cyclopentanone, cyclohexanone, ethyl lactate,
The esters such as 3- methoxy methyl propionate.First solvent mixture can contain ingredient in addition to solvents.It is being used for resist
Resin, additive (curing agent, pigment from anti-corrosion agent composition are typically contained in the waste liquid of removing or the washing of composition
Deng) etc..
For alkylene glycol monoalky lether of the recycling as the first solvent from the first solvent mixture, of the invention the
The second solvent in the first solvent mixture is changed into the first solvent in one process, therefore applies saponification.Saponification
It can be carried out by addition alkali compounds, preferably addition is in sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide
Any hydroxide alkali compounds.Saponification when as an example, using sodium hydroxide is by following reaction formula (III) tables
Show.
R(OR’)nOCOR”+NaOH→
R(OR’)nOH+R”COONa (III)
It reacting in formula (III), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4 alkylidene,
R " indicates that carbon atom number is 1~2 alkyl, and n is 1 or 2.
The amount of the alkali compounds used in saponification is relative to the second solvent for including in the first solvent mixture
For 0.8~1.2 molar equivalent, preferably 0.9~1.1 molar equivalent, further preferably 0.95~1.05 molar equivalent.If
The amount of alkali compounds is fewer than 0.8 molar equivalent, then the residual quantitative change for being not converted into the second solvent of the first solvent is more, receives
Rate decline.If the amount of alkali compounds is more than 1.2 molar equivalents, not only inoperative quantitative change is more in saponification,
It and in terms of being evenly dispersed into the first solvent mixture is unfavorable.Using sodium hydroxide, potassium hydroxide or hydroxide
In the case that calcium is as alkali compounds, due to these solubility of hydroxide alkali compounds in the first solvent mixture
It is small, therefore being preferably stirred keeps its evenly dispersed.Sodium hydroxide, potassium hydroxide or calcium hydroxide sedimentation in order to prevent, and
In order to carry out saponification successfully, as sodium hydroxide, potassium hydroxide or calcium hydroxide, it is preferable to use the object of small particle
Matter, such as granular substance.Sodium hydroxide or potassium hydroxide have hygroscopy, therefore even if not adding water, they also include
The micro moisture itself absorbed.Therefore, even if directly being added in solid form in the case where not adding water, saponification
Also it will do it.Calcium hydroxide is compared with sodium hydroxide and potassium hydroxide, and solubility in water is small, and correspondingly reaction speed is slow.
Comprising ketone series solvents such as cyclopentanone, cyclohexanone as third solvent, if using hydroxide alkali compounds,
The dimerization (aldol condensation) that these ketone series solvents occur, generates the dimerization compound of higher boiling point, and this point is aftermentioned.Therefore, example
It such as, is propylene glycol monomethyl ether in the ingredient for wanting recycling, ketone series solvent is with the boiling point (120 with propylene glycol monomethyl ether
DEG C) in the case where the cyclopentanone (131 DEG C) of boiling point relatively, keep its generation bigger with the boiling-point difference of propylene glycol monomethyl ether
Ketone series solvent dimerization compound (160 DEG C of boiling point >), it can be easily separated out from propylene glycol monomethyl ether.Hydrogen
Although the reactivity of potassium oxide and sodium hydroxide is same degree, more expensive than sodium hydroxide, calcium hydroxide is low cost, but is reacted
Property is poor, therefore it is preferable to use sodium hydroxides.
Also ammonium hydroxide can be used, but if being heated, then can be vaporized as ammonia, therefore become high temperature in reaction
When have undesirable situation.Hydroxide alkali compounds can also use in form of an aqueous solutions.It uses in form of an aqueous solutions,
This is advantageous in terms of being uniformly mixed into the viewpoint in solvent mixture, but separates and recovers in aftermentioned distillation process molten
Azeotropic occurs for agent and water, therefore becomes unfavorable in terms of yield.It is therefore preferable that the addition of water is suppressed to necessary minimum (example
Such as in the case where using sodium hydroxide in form of an aqueous solutions, 48 mass % or more are used).
It is in the case where disposing waste liquid of anti-corrosion agent composition in the first solvent mixture, in anti-corrosion agent composition sometimes
Comprising the carboxylate other than leading to carboxylate shown in formula (II), carboxylate shown in these carboxylates and logical formula (II) is had
The case where being carried out similarly saponification and consuming alkali compounds.Therefore, comprising in addition to general formula in the first solvent mixture
(II) in the case where the carboxylate other than carboxylate shown in, it is preferable to use relative to the whole for including in the first solvent mixture
Carboxylate amount is the alkali compounds of above-mentioned defined range.
Saponification condition (temperature, time, atmosphere etc.) is not particularly limited, the range of preferred room temperature~100 DEG C of temperature,
Time preferably 1~10 hour range.Reaction atmosphere is also not particularly limited, can be under atmosphere, inert atmosphere (nitrogen, argon gas
Deng) under any atmosphere under carry out, but using bibulous sodium hydroxide, gas preferably low in humidity
Atmosphere, such as relative humidity are to carry out in 50% atmosphere below, are more preferably carried out in the atmosphere that relative humidity is 10~40%.
In the second step, in order to be separated back from the solvent mixture (the second solvent mixture) obtained after saponification
It receives the first solvent and distills the second solvent mixture.It include the carboxylate generated in saponification in second solvent mixture.
Carboxylate is almost not dissolved in solvent mixture (the second solvent mixture), so if including in the second solvent mixture
It is distilled in the state of carboxylate, then carboxylate is precipitated in distillation procedure sometimes and pollutes distillation equipment.It is therefore preferable that
The process of setting separation carboxylate before distillation.For separation process, it is not particularly limited as long as it can separate carboxylate, it can be with
Using evaporation separate, be separated by filtration, be centrifugated etc. well known to method, but in order to reduce include in solid content (carboxylate) molten
The ratio of agent, and efficiently stable discharge is carried out, it is preferable to use thin film evaporator.So-called thin-film distillation is by circle
The wall surface of cylinder forms the film of solution and improves the evaporator of evaporation efficiency, can enumerate such as Co., Ltd.'s mind steel loop border ソ リ ユ
エ Network セ バ (registered trademark), the action of forced stirring formula evaporator of Co., Ltd. Kimura chemical industry machine, Co., Ltd. cherry of one シ ヨ Application
Production mono- タ mono- (registered trademark) of Ha イ エ バ オ レ etc..Thin-film distillation can also carry out under normal pressure, but preferably 100
Carried out under the decompression of~300torr or so, this ensure supply heat source in terms of be advantageous.
It is in the case where disposing waste liquid of anti-corrosion agent composition in the first solvent mixture, in separation process, processing is useless
The solid component contained in liquid is also separated simultaneously.The separation of these solid components can also be in the saponification of the first solvent mixture
The process implemented before reaction, but need the carboxylate that will be generated to separate again sometimes after saponification, thus it is anti-in saponification
Ying Houyu carboxylate separates be advantageous together.
The distillating method and distilling apparatus of second solvent mixture are not particularly limited, can be with for example, as distillating method
Using air-distillation, vacuum distillation etc., any one of well known method, distilling apparatus are also that can apply continuously all the time
Any one of various distilling apparatus well known to formula, intermittent etc..
The ingredient lower than the first solvent boiling point (low boiling fraction) is distilled off by distillation procedure, it is molten then to recycle first
Agent.In the case where first solvent mixture of the distillation comprising the first solvent and the second solvent, it is difficult to by boiling point in the first solvent
Separated with the third solvent of the centre of the second solvent, but in the present invention, by saponification by the second solvent switch be first
Solvent, so as to be separated and recovered from third solvent.Condition when being separated by distillation the first solvent of recycling is not limited especially
It is fixed, but preferably the boiling point of the first solvent or so at a temperature of flow back 10 minutes~2 hours or so, then the first solvent is distilled
And it separates.Operation in this way can recycle the first solvent of purity is high.As previously mentioned, being boiling point and the in third solvent
In the case where the close ketone series solvent of the boiling point of one solvent, in the saponification of the first solvent mixture, ketone series solvent passes through
Aldol condensation and dimerization occurs, generate with the bigger dimerization compound of the first solvent boiling point difference, therefore can be easy and high-purity
Separate and recover the first solvent.
First embodiment according to the present invention, can from containing alkylene glycol monoalky lether and its corresponding carboxylate,
And the alkylene glycol monoalky lether of purity is high is efficiently separated and recovered in the solvent mixture of other at least one solvents.
Second embodiment
Second embodiment of the present invention be using containing alkylene glycol monoalky lether (the first solvent) and as first it is molten
The mixed solvent of the alkylene glycol monoalky lether carboxylic ester (the second solvent) of the correspondence carboxylate of agent handles anti-corrosion agent composition
Obtained by waste liquid reuse method.The waste liquid used in this second embodiment be illustrated in the first embodiment
Anti-corrosion agent composition dispose waste liquid it is same.Therefore, the third step in second embodiment and the fourth step respectively correspond
First step and the second step in first embodiment, and the description is omitted.
First step in second embodiment is molten using the mixing comprising leading to solvent shown in formula (I) and logical formula (II)
The removing solvent of agent such as anti-corrosion agent composition, washer solvent etc. come handle anti-corrosion agent composition, for example carry out washing or
The process of flushing.It more specifically, will be adhered in the manufacturing process of semiconductor element, liquid crystal display element, colour filter etc.
Unwanted anti-corrosion agent composition in semiconductor substrate or glass substrate or described anti-corrosion agent composition to be applied to
The process that the upper anti-corrosion agent composition adhered to such as nozzle, piping of the apparatus for coating used when on substrate removes.Resist combination
The removing solvent and washer solvent of object do not include generally substantially other than leading to solvent shown in formula (I) and logical formula (II)
Third solvent." not including substantially " mentioned here means and does not add third solvent specially, but it is anti-not to be included in satisfaction
Lose the case where removing with including impurity in the range of the product specification of solvent and washer solvent of agent composition.
The second step in second embodiment is to recycle the processing comprising anti-corrosion agent composition generated by first step
The process of waste liquid.Include the ingredient other than leading to solvent shown in formula (I) and logical formula (II) in the waste liquid of recycling, that is, against corrosion
The solid components such as the solvent, resin, the pigment that include in agent composition, other additive components.
The 5th process in second embodiment is by recycling in the first obtained solvent to by the fourth step is separated
The second solvent of new addition, so that modulation has the process of the mixed solvent of the desired defined match ratio of intended applications again.
As an example, the second solvent that can enumerate addition specified amount makes anti-corrosion agent composition used in mixed solvent and first step
Removing solvent or washer solvent be the process formed on an equal basis, but also it is adjustable for used in other purposes, match
The different composition of composition and division in a proportion.
Second embodiment according to the present invention, by from after processing anti-corrosion agent composition in obtained waste liquid efficiently
Recycle the first solvent of purity is high, new the second solvent for adding specified amount, so as to modulate the stripping of anti-corrosion agent composition again
From with solvent, washer solvent etc., that is, can effectively recycle and dispose waste liquid.By this way, and by that will dispose waste liquid
(solvent mixture) directly distillation is to be separated off the fraction lower than the first solvent boiling point and higher than the second solvent boiling point evaporate
The previous method divided is compared, and the mixed solvent of high-purity can be obtained with low cost.
Third embodiment
Third embodiment is the recycling method of anti-corrosion agent composition treatment fluid.It is handled about from anti-corrosion agent composition
The first solvent and the second solvent of new addition are recycled in waste liquid to modulate the mixed solvent example with defined match ratio again
It is identical as second embodiment such as the removing solvent or washer solvent of anti-corrosion agent composition, therefore the repetitive description thereof will be omitted.
Anti-corrosion agent composition is disposed waste liquid recycled as anti-corrosion agent composition treatment fluid when, as described above,
Recovery processing (the third step) that user can also dispose waste liquid, reaction treatment (the fourth step), distillation handle (the 5th work
Sequence) etc., but the manufacturer of preferred solvent or recycling dealer recycle from multiple users, uniformly handle.Especially exist
In the case that the manufacturer of solvent is handled, waste liquid can be handled, into the first solvent that separation and recovery obtains
Cooperate the second solvent of coming of new, so that modulation mixing is molten again in a manner of the specification for meeting anti-corrosion agent composition treatment fluid
Liquid.In the third embodiment, user buys in anti-corrosion agent composition treatment fluid (first step) from manufacturer, and user resists
The processing (the second step) of agent composition is lost, then manufacturer or recycling dealer implement third~the 6th process, and user is from system
It makes dealer or recycling dealer buys in mixed solvent (the 7th process) made of modulation again, implement the second~the 7th work repeatedly later
Sequence.
Third embodiment according to the present invention, is repeated manufacturer or recycling dealer is used against corrosion by user
Agent compositions-treated waste liquid carries out recycling and regeneration treatment, and user uses as the obtained anti-corrosion agent composition treatment fluid of regeneration
Circulation, therefore carrying capacity of environment is small, efficiently can recycle anti-corrosion agent composition treatment fluid with low cost.
Embodiment
The present invention is further specifically described by the following examples.In addition, the present invention is not by the contents of embodiment
It limits.In addition, in the present invention, for embodiment below, above-mentioned specific description and the rest of the content, as long as
Purport of the invention is not departed from, various changes, amendment, improvement etc. can be added based on the knowledge of those skilled in the art.
Embodiment 1
As comprising alkylene glycol monoalky lether (the first solvent) and its corresponding carboxylate (the second solvent) and other are molten
The solvent mixture of agent (third solvent), prepare following table 1 shown in composition, include propylene glycol monomethyl ether (PGME), third
The solvent mixture (the first solvent mixture) of glycol monomethyl ether acetic acid esters (PGMEA) and other solvents.
Table 1
| Substance name | Solvent mixture | Simple distillation recovered liquid | It is distilled to recover liquid |
| MeOH (quality %) | 0.9 | ||
| EtOH (quality %) | 1.0 | ||
| PGME (quality %) | 62.9 | 95.4 | 99.8 |
| PGMEA (quality %) | 27.1 | ≤0.1 | ≤0.1 |
| MMP (quality %) | 2.7 | ≤0.1 | ≤0.1 |
| EL (quality %) | 2.7 | ≤0.1 | ≤0.1 |
| CYP (quality %) | 4.5 | 0.2 | 0.2 |
| Water (quality %) | 0.2 | 2.0 | 0.1 |
| Other (quality %) | 0.6 | ||
| The rate of recovery (%) when distillation | 81 | 71 | |
| The PGME rate of recovery (%) | 86 | 79 |
MeOH: methanol
EtOH: ethyl alcohol
PGME: propylene glycol monomethyl ether
PGMEA: propylene glycol monomethyl ether
MMP:3- methoxy methyl propionate
EL: ethyl lactate
CYP: cyclopentanone
The rate of recovery (%)=(distilling resulting recycling liquid measure)/(amount of solvent mixture) × 100 when distillation
The PGME rate of recovery (%)=(the PGME amount that recycling obtains)/(the PGME amount+PGMEA amount in solvent mixture) ×
100
Implement the saponification of the solvent mixture (the first solvent mixture) for the composition that there is table 1 to record.Specifically,
The solvent that the composition recorded with table 1 is put into 1 liter of capacity of three-neck flask for having reflux cooler and agitating device is mixed
Object (the first solvent mixture) 793g, sodium hydroxide 94g are closed, nitrogen is passed through to flask interior on one side, heats under normal pressure on one side
To 80 DEG C and is kept for 3 hours and carry out saponification.Solvent mixture (the second solvent mixture) after reaction is let cool to room
Then temperature carries out simple distillation using evaporator in order to separate with solid component (sodium acetate), then in order to obtain object
(PGME) it is distilled again.
As distilling apparatus, Oldershaw distilling apparatus 10 shown in FIG. 1 is used.In Fig. 1, A is that have thermometer 15
1L flask, B is that theoretical cam curve is 20 layers of rectifying column.Condense in reflux head 11 as the steam for rising to tower top,
It can use and the structure that switching funnel 12 adjusts reflux ratio is distillated by the reflux that solenoid valve operates.In addition, being configured distillating side
Cock 13 is distillated, prepares receiver 14 in the front.It is small that above-mentioned resulting simple distillation recovered liquid is fitted into progress 2 in flask A
When be heated to reflux, then divide and take distillate.
Using the solvent mixture of the above-mentioned record of table 1 of gas chromatography (GC) analysis, simple distillation recovered liquid and distill back
Liquid is received, table 1 is shown the result in.In table 1, the rate of recovery of the so-called simple distillation recovered liquid in distillation is simple distillation recycling
Ratio of the quality of liquid relative to the quality of used original solvent mixture (the first solvent mixture), so-called simple steaming
The PGME rate of recovery for evaporating recovered liquid is the PGME mass in simple distillation recovered liquid relative to used original solvent mixing
The ratio of PGME mass and PGMEA quality sum in object (the first solvent mixture).It is so-called be distilled to recover liquid distillation when
The rate of recovery is the quality of final distillation recovery liquid relative to used original solvent mixture (the first solvent mixture)
Quality ratio, the so-called PGME rate of recovery being distilled to recover in liquid is the final PGME mass being distilled to recover in liquid relative to
The ratio of PGME mass and PGMEA quality sum in used original solvent mixture (the first solvent mixture).
The determination condition of gas chromatography (GC) is as follows.
Device: GC-14B (Shimadzu Seisakusho Ltd.'s system)
Column: capillary column (CBP1-M50-025)
Stationary phase liquid: methyl polysiloxane
Stationary phase liquid is thick: 0.25 μm
Column material: ultra-high purity silica
Column internal diameter: 0.22mm
Column length: 50m
Carrier gas: helium
Flow velocity: 2mL/ minutes
Pressure: 150kPa
Detector: hydrogen flame ionization detector (FID)
Hydrogen pressure: 50kPa
Air pressure: 50kPa
Column temperature: 50 DEG C (being kept for 1 minute) → 5 DEG C/min heat up → 145 DEG C (being kept for 5 minutes)
Inlet temperature: 200 DEG C
Detector temperature: 200 DEG C
Sample size: 0.2 μ L (split ratio 1/50)
Specified sensitivity: 10-2
Quantitative approach: corrected area percentage method
Comparative example 1
Water 65g is added into the solvent mixture 714g of embodiment 1 and obtains solvent mixture, similarly to Example 1
Using distilling apparatus, then progress 21 hours be heated to reflux divides and takes distillate, calculates its rate of recovery, and utilize gas phase color
The purity of spectrometry confirmation distillate.The determination condition of gas chromatography is identical with the situation of embodiment 1.By the resulting rate of recovery and
Purity is shown in table 2.The PGME rate of recovery is calculated by following formula.The additive amount 65g of above-mentioned water is that consider can will be in solvent mixture
Third ingredient (MMP and CYP) with minimum boiling point azeotrope, (boiling point of azeotropic mixture, i.e., azeotropic temperature is on liquidus
Mixture when minimalization) form remove and the loss of PGME is suppressed to irreducible minimum to determine.In this comparative example
In, different from embodiment 1, not sodium acetate by-product, therefore the process for the simple distillation not being equivalent in embodiment 1.
The PGME rate of recovery (%)=(the PGME amount that recycling obtains)/(the PGME amount+PGMEA amount in solvent mixture) ×
100
Comparative example 2
Methanol 138g is added into the solvent mixture 700g of embodiment 1 and obtains solvent mixture, is mixed to the solvent
Sodium methoxide about 0.8g (0.01 times mole of PGMEA in solvent mixture) of the addition as catalyst in object, in normal pressure, 70 DEG C
Then lower progress heating in 190 minutes reaction is used in the same manner distilling apparatus with comparative example 1, carries out 2 hours up to reaching balance
It is heated to reflux, then divides and take distillate, calculate its rate of recovery, and confirm the purity of distillate with gas chromatography.By gained
The rate of recovery and purity be shown in table 2.The additive amount 138g of methanol is to consider the conversion ratio of ester exchange reaction and based on point later
Separating process calculate cost of energy and determine, be equivalent to 3 times of moles of the PGMEA in solvent mixture.In above-mentioned condition
Under reach balance be pass through through when sampling, become constant using gas chromatography confirmation composition and confirm.In this comparative example,
It is not equivalent to the process of the simple distillation in embodiment 1.
Comparative example 3
Using distilling apparatus, carried out in the case where making the solvent mixture of embodiment 1 not implement saponification 2 hours
It is heated to reflux, then divides and take distillate, calculate its rate of recovery, and utilize the purity of gas chromatography confirmation distillate.By institute
The rate of recovery and purity obtained is shown in Table 2.In this comparative example, it is not equivalent to the process of the simple distillation in embodiment 1.
Comparative example 4
The mixture 700g that will only contain propylene glycol monomethyl ether and propylene glycol monomethyl ether is mixed as solvent
Object is closed, adds sodium hydroxide 33g and water 14g thereto, under normal pressure then 120 DEG C of progress, 4 hours hydrolysis use steaming
Distillation unit, progress 21 hours be heated to reflux, then divides and takes distillate, calculate its rate of recovery.In this comparative example, without suitable
The process of simple distillation in embodiment 1.
Above result is summarized and is shown in Table 2.As table 2 the result shows that as, added into solvent mixture
Water and the propylene glycol monomethyl ether (PGME) in the comparative example 1 that is distilled, as the high-purity product that purity is 99.5% or more
The rate of recovery be 58%；In contrast, in embodiment 1, the PGME's for the high-purity product for being 99.5% or more as purity returns
Yield is higher than comparative example 1.
In the comparative example 2 that the addition methanol into solvent mixture carries out ester exchange reaction, due to impurity such as cyclopentanone
Boiling point and PGME boiling point it is close, the propylene glycol monomethyl ether (PGME) as the high-purity product that purity is 99.5% or more
The rate of recovery is 73%；In contrast, in embodiment 1, the recycling of the PGME for the high-purity product for being 99.5% or more as purity
Rate is higher than comparative example 2.
In the comparative example 3 that no progress saponification is only distilled, the height for being 99.5% or more as purity
The rate of recovery of the propylene glycol monomethyl ether (PGME) of purity product is 44%, it is known that its significance difference compared with Example 1.
Comparative example 4 is shown to obtain high-purity product in high yield, but this is not include in solvent mixture in addition to third
It is in the case where other impurities other than glycol monomethyl ether (PGME) and propylene glycol monomethyl ether (PGMEA) as a result,
About the separation easiness for the PGME for separating PGME from other impurities, any opinion is not brought.
Table 2
MeOH: methanol
EtOH: ethyl alcohol
PGME: propylene glycol monomethyl ether
PGMEA: propylene glycol monomethyl ether
MMP:3- methoxy methyl propionate
EL: ethyl lactate
CYP: cyclopentanone
ML: methyl lactate
MA: methyl acetate
1) obtained by the composition of solvent mixture is based on being formed shown in " embodiment: table 1 ".On its basis,
Water additive amount is added in comparative example 1 and calculates, methanol additive amount is added in comparative example 2 and calculates.
Industrial availability
In accordance with the invention it is possible to from molten containing alkylene glycol monoalky lether and its corresponding carboxylate and other solvents
In agent composition, with high-purity and high yield separation and recovery alkylene glycol monoalky lether.The present invention is as anti-corrosion agent composition
The reuse method to dispose waste liquid is effectively, can be manufactured with low cost semiconductor element, liquid crystal display element, colour filter
Deng.
Symbol description
10 Oldershaw distilling apparatus
11 reflux heads
12 reflux distillate switching funnel
13 distillate cock
14 receivers
15 thermometers
A 1L flask
B rectifying column
Claims (15)
1. a kind of separation and recovery method of alkylene glycol monoalky lether, which is characterized in that be from comprising the first solvent, the second solvent
With the method for separating and recovering the first solvent in the first solvent mixture of third solvent, first solvent is by the following general formula (I)
It indicating, second solvent indicates that the third solvent is different from first solvent and the second solvent by the following general formula (II),
R(OR')nOH (I)
R(OR')nOCOR” (II)
In logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4 Asia
Alkyl, R " indicate that carbon atom number is 1~2 alkyl, and the R in logical formula (I) and logical formula (II) is identical, logical formula (I) and general formula
(II) R ' in be also it is identical, n is 1 or 2,
The separation and recovery method includes following first steps and the second step,
First step: by adding alkali compounds into first solvent mixture, by second solvent saponification, transformation
For the first solvent, so that the second solvent mixture is obtained,
The second step: second solvent mixture is distilled, and recycles the first solvent.
2. the separation and recovery method of alkylene glycol monoalky lether according to claim 1, the alkali compounds are to be selected from
At least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide hydroxide alkali compounds.
3. the separation and recovery method of alkylene glycol monoalky lether according to claim 2, the alkali compounds is hydrogen-oxygen
Change sodium.
4. the separation and recovery method of alkylene glycol monoalky lether described in any one of claim 1 to 3, described first is molten
Agent is propylene glycol monomethyl ether, and second solvent is propylene glycol monomethyl ether, and the third solvent is selected from ring penta
At least one of ketone, cyclohexanone, ethyl lactate and 3- methoxy methyl propionate.
5. the separation and recovery method of alkylene glycol monoalky lether described in any one of claim 1 to 3, described first is molten
Agent composition is to handle processing obtained by anti-corrosion agent composition using comprising the mixed solvent of first solvent and the second solvent
Waste liquid.
6. a kind of reuse method that anti-corrosion agent composition disposes waste liquid, which is characterized in that including following processes,
First step: it uses and includes the second solvent shown in the first solvent shown in the following general formula (I) and the following general formula (II)
Mixed solvent handles anti-corrosion agent composition,
The second step: recycling is disposed waste liquid by what first step generated,
The third step: Xiang Suoshu disposes waste liquid middle addition alkali compounds, thus by the second solvent soap in described dispose waste liquid
Change, be changed into the first solvent,
The fourth step: the solvent mixture obtained by the third step is distilled, and recycles the first solvent, and
5th process: adding the second new solvent into the first solvent recycled through the fourth step, again modulation tool
There is the mixed solvent of defined match ratio,
R(OR')nOH (I)
R(OR')nOCOR” (II)
In logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4 Asia
Alkyl, R " indicate that carbon atom number is 1~2 alkyl, and the R in logical formula (I) and logical formula (II) is identical, logical formula (I) and general formula
(II) R ' in be also it is identical, n is 1 or 2.
7. the reuse method that anti-corrosion agent composition according to claim 6 disposes waste liquid, the alkali compounds is choosing
From at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide hydroxide alkali compounds.
8. the reuse method that anti-corrosion agent composition according to claim 7 disposes waste liquid, the alkali compounds is hydrogen
Sodium oxide molybdena.
9. the reuse method that the anti-corrosion agent composition according to any one of claim 6~8 disposes waste liquid, described first
Solvent is propylene glycol monomethyl ether, and second solvent is propylene glycol monomethyl ether.
10. the reuse method that the anti-corrosion agent composition according to any one of claim 6~8 disposes waste liquid, described
After the third step before the fourth step, have following processes: include in disposing waste liquid described in separation is generated by saponification
Solid component.
11. a kind of recycling method of anti-corrosion agent composition treatment fluid, which is characterized in that have following first steps~7th
Process implements the second step~the 7th process repeatedly,
First step: user from manufacturer buy in defined match ratio include the following general formula (I) shown in the first solvent and
The mixed solvent of second solvent shown in the following general formula (II),
The second step: user handles anti-corrosion agent composition using the mixed solvent,
The third step: manufacturer or recycling dealer's recycling are disposed waste liquid by what the second step generated,
The fourth step: manufacturer or recycling dealer are by the middle addition alkali compounds that disposes waste liquid, thus will be described
The second solvent saponification in disposing waste liquid, is changed into the first solvent,
5th process: manufacturer or recycling dealer distill the solvent mixture obtained by the fourth step, recycling first
Solvent,
6th process: manufacturer or recycling dealer add new the into the first solvent recycled by the 5th process
Two solvents, modulation has the mixed solvent of the defined match ratio again,
7th process: user buys in the mixed solvent modulated again from manufacturer or recycling dealer,
R(OR')nOH (I)
R(OR')nOCOR” (II)
In logical formula (I) and logical formula (II), R indicates that carbon atom number is 1~4 alkyl, and R ' indicates that carbon atom number is 2~4 Asia
Alkyl, R " indicate that carbon atom number is 1~2 alkyl, and the R in logical formula (I) and logical formula (II) is identical, logical formula (I) and general formula
(II) R ' in be also it is identical, n is 1 or 2.
12. the recycling method of anti-corrosion agent composition treatment fluid according to claim 11, the alkali compounds are
Selected from least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide hydroxide alkali compounds.
13. the recycling method of anti-corrosion agent composition treatment fluid according to claim 12, the alkali compounds are
Sodium hydroxide.
14. the recycling method of anti-corrosion agent composition treatment fluid described in any one of 1~13 according to claim 1, described
First solvent is propylene glycol monomethyl ether, and second solvent is propylene glycol monomethyl ether.
15. the recycling method of anti-corrosion agent composition treatment fluid described in any one of 1~13 according to claim 1, in institute
State after the fourth step before the 5th process with following processes: it is that separation is generated by saponification, described dispose waste liquid in include
Solid component.
Applications Claiming Priority (3)
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| JP2014155104 | 2014-07-30 | ||
| JP2014-155104 | 2014-07-30 | ||
| PCT/JP2015/069667 WO2016017387A1 (en) | 2014-07-30 | 2015-07-08 | Method for separating and recovering alkylene glycol monoalkyl ether, method for recycling liquid waste from processing of resist composition, and method for recycling resist composition processing liquid |
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| CN106660914B true CN106660914B (en) | 2019-06-04 |
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| JPS5589236A (en) * | 1978-12-28 | 1980-07-05 | Yotsukaichi Gosei Kk | Purification of crude glycol ether |
| JP2005247816A (en) * | 2004-03-08 | 2005-09-15 | Sanwa Yuka Kogyo Kk | Method for separating and recovering alkylene glycol monoalkyl ether |
| KR20100000495A (en) * | 2008-06-25 | 2010-01-06 | 덕산약품공업주식회사 | Recovery method of organic solvent from photoresist removal waste |
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| JPS5195008A (en) * | 1975-02-14 | 1976-08-20 | ECHIRENGURIKOORUARUKIRUEETERUNO SEISEIHOHO | |
| JPH01180844A (en) * | 1988-01-12 | 1989-07-18 | Daicel Chem Ind Ltd | Method for purifying diglycerol |
| JP2553146B2 (en) * | 1988-04-27 | 1996-11-13 | 協和油化株式会社 | Purification method of glycol ether |
| DE4309741A1 (en) * | 1993-03-25 | 1994-09-29 | Henkel Kgaa | Process for the preparation of diglycerin |
| JPH08231991A (en) * | 1994-12-27 | 1996-09-10 | Hitachi Ltd | Composition for cleaning, cleaning method and production of cleaning liquid |
| JP2001064221A (en) * | 1999-08-30 | 2001-03-13 | Lion Corp | (poly)ethylene glycol monoalkyl ether-based solvent having improved smell and its production |
| JP4089141B2 (en) * | 2000-08-07 | 2008-05-28 | 三菱化学株式会社 | Stepped column reactor and method for producing polyalkylene ether glycol using the same |
| KR100944400B1 (en) * | 2005-07-19 | 2010-02-25 | 쇼와 덴코 가부시키가이샤 | Removing solution for photosensitive composition |
| JP4475664B2 (en) * | 2005-12-27 | 2010-06-09 | 東京応化工業株式会社 | Cleaning liquid for photolithography and method for circulating the same |
| US9187392B2 (en) * | 2008-01-17 | 2015-11-17 | Lyondell Chemical Technology, L.P. | Production of propylene glycol monoalkyl ether |
| US8614053B2 (en) * | 2009-03-27 | 2013-12-24 | Eastman Chemical Company | Processess and compositions for removing substances from substrates |
| JP5433279B2 (en) * | 2009-03-31 | 2014-03-05 | 東京応化工業株式会社 | Method for producing recycled resist |
| KR101102574B1 (en) * | 2009-09-30 | 2012-01-03 | 조양래 | A preparative method for 1,4-disubstituted cyclohexane derivatives |
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- 2015-07-08 JP JP2016538245A patent/JP6602301B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5589236A (en) * | 1978-12-28 | 1980-07-05 | Yotsukaichi Gosei Kk | Purification of crude glycol ether |
| JP2005247816A (en) * | 2004-03-08 | 2005-09-15 | Sanwa Yuka Kogyo Kk | Method for separating and recovering alkylene glycol monoalkyl ether |
| KR20100000495A (en) * | 2008-06-25 | 2010-01-06 | 덕산약품공업주식회사 | Recovery method of organic solvent from photoresist removal waste |
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| TWI588123B (en) | 2017-06-21 |
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