CN101888906A - Cleaning agent and cleaning method for electronic material - Google Patents

Cleaning agent and cleaning method for electronic material Download PDF

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CN101888906A
CN101888906A CN200880119796.5A CN200880119796A CN101888906A CN 101888906 A CN101888906 A CN 101888906A CN 200880119796 A CN200880119796 A CN 200880119796A CN 101888906 A CN101888906 A CN 101888906A
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acid
carbon number
cleaning agent
electronic material
salt
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CN101888906B (en
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胜川吉隆
铃木一充
佐藤祥平
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Sanyo Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/342—Phosphonates; Phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C11D2111/22—
    • C11D2111/46—

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

Disclosed is a cleaning agent for electronic materials, which contains an anionic surfactant (A) having an anionic component represented by the general formula (1) below, and one or more organic solvents (B) selected from the group consisting of alkenes having 6-18 carbon atoms and organic solvents represented by the general formula (2) below. In this cleaning agent for electronic materials, the SP value of the component (B) is within the range of 6-13. R1[-(OA1)a-Q-]b (In the formula (1), R1 represents a hydrocarbon group having 1-10 carbon atoms; A1 represents an alkylene group having 2-4 carbon atoms; Q- represents -COO-, -OCH2COO-, -SO3 -, -OSO3 - or -OPO2(OR2)-; R2 represents a hydrogen or a hydrocarbon group having 1-10 carbon atoms; a represents an average that is a number of 0-20; b represents an integer of 1-6; and when Q- represents -COO- or -SO3 -, a is 0.) R3[-(OA2)c-OH]d (In the formula (2), R3 represents a hydrocarbon group having 1-12 carbon atoms; A2 represents an alkylene group having 2-4 carbon atoms; c represents an average that is a number of 0-20; and d represents an integer of 1-6).

Description

Electronic material cleaning agent and cleaning method
Technical field
The present invention relates to electronic material cleaning agent and cleaning method.More particularly, relate to cleaning agent and the cleaning method that is applicable to flat-panel monitor, photomask (photomask), hard disk or semi-conductive substrate.
Background technology
In the cleaning technique of electronic material and since when making on the substrate residual impurity such as micro-content organism dirt, cullet (glass cullet) and sand grains the performance and the output of electronic material is had big influence, so its processing becomes extremely important.The impurity that particularly the becomes cleaning object particulate (particle) that becomes is more changed, than adhere to whenever all easilier in the past, from the teeth outwards residual, therefore the establishment of height cleaning technique has become the task of top priority.Therefore, for the pollution that prevents that these particulates from causing, proposed to use surfactant to improve the method (with reference to patent documentation 1～4) of particle removal.
Yet, the problem that exists is: make flat-panel monitor with, photomask with, hard disk with and the operation of the glass used of semiconductor or silicon substrate in, dust that disperses in the glass smear metal (being commonly referred to as cullet) that produces when as required glass substrate being cut into suitable dimension from basic pattern glass (mother glass), the toilet or processing wet goods organic matter dirt, the grinding agent that uses during with the operation of substrate surface veining (texturing) or lapping rejects etc. can not fully be removed in matting firmly attached to substrate surface.
Because with these cullet, organic matter dirt, grinding agent and lapping rejects is that the particle of representative is firmly attached to substrate surface, therefore, for they are fully removed, need be with substrate or abrasive surface etching slightly, particle is distributed in the solution, and makes that dispersed particles no longer is attached to substrate surface in the solution.Yet, the cleaning agent that proposes in the patent documentation 1 is the cleaning agent that contains APG, glycerin ether and hydrocarbon, can expect its removal to organic dirt, but the removal to cullet is insufficient, can expect to remove the particle that etching produces by making it contain alkaline agent again, yet have the coarse problem of substrate surface after cleaning.In addition, proposed to contain specific nonionic surface active agent, specific glycol ether and the cleaning agent of hydrocarbon in the patent documentation 2, and the cleaning agent that contains hydrocarbon, specific glycol ether, anionic surfactant and methyl-sulfoxide.The preceding cleaning agent of planting uses nonionic surface active agent in order to improve the particle removal performance, because surfactant component easily residues in the electronic material surface, therefore has the problem that rinsing is poor, productive rate descends.In addition, it is the purpose sulfosuccinic acid type anionic surfactant that contains average carbon atom number 10～20 etc. to improve permeability that cleaning agent is planted in the back, though the removal of particle improves, but because foaming characteristic is very high, and defoaming deficiency, so operability (handling) existing problems.In addition, the cleaning agent that proposes in the patent documentation 3 is the cleaning agent that is dissolved with hydrogen fluoride and ozone, can expect to remove firmly particle attached to substrate surface by etching, yet, owing to contain fluorine ion, the draining processing cost is very high, and owing to can not control strong etching, has the problem of damaged substrate flatness during cleaning.In addition, the cleaning agent that proposes in the patent documentation 4, though by use anionic surfactant to make to prevent particle again adhesion effect get to a certain degree improvement owing to almost there is not etching, so have that particle removal is insufficient, the inadequate problem of cleaning.
Patent documentation 1: the spy opens the 2007-39627 communique
Patent documentation 2: the spy opens the 2004-2691 communique
Patent documentation 3: the spy opens the 2001-276759 communique
Patent documentation 4: the spy opens the 2002-212597 communique
Summary of the invention
The object of the present invention is to provide a kind of flatness that does not damage glass or silicon substrate surface, realize good particle removal, the electronic material of low foaming characteristic and exhibiting excellent stability with time is with cleaning agent and cleaning method.
In order to solve above-mentioned problem, the inventor etc. further investigate, and the result has finished the present invention.Promptly, the present invention is the cleaning method of a kind of electronic material with the electronic material of cleaning agent and this cleaning agent of use, wherein, described cleaning agent contains anion component by the alkene (alkene) of the anionic surfactant (A) of general formula (1) expression, carbon number 6～18 and be selected from the organic solvent more than a kind (B) in the group that the organic solvent by general formula (2) expression constitutes, and the SP value of above-mentioned (B) is 6～13.
R 1[-(OA 1) a-Q -] b (1)
[in the formula, R 1Be the alkyl of carbon number 1～10, A 1Be the alkylidene of carbon number 2～4, Q -For-COO -,-OCH 2COO -,-SO 3 -,-OSO 3 -Or-OPO 2(OR 2) -, R 2Be the alkyl of hydrogen or carbon number 1～10, a is a mean value 0～20, and b is 1～6 integer, Q -For-COO -Or-SO 3 -The time a be 0.]
R 3[-(OA 2) c-OH] d (2)
[in the formula, R 3Be the alkyl of carbon number 1～12, A 2Be the alkylidene of carbon number 2～4, c is a mean value 0～20, and d is 1～6 integer.]
Make flat-panel monitor with, photomask with, hard disk with and the operation of the glass used of semiconductor or silicon substrate in, electronic material of the present invention is with the cleaning agent flatness on damaged substrate surface not, by give can appropriateness control etching, the firm molecule that adheres to is broken away from from substrate surface, particle stabilized being dispersed in the cleaning agent that will break away from again, thereby realize good particle removal, reach low foaming characteristic and exhibiting excellent stability with time, can improve the productive rate when making, and can clean at short notice, this very effective height is cleaned becomes possibility.
The specific embodiment
Anionic surfactant of the present invention (A) is made of anion component and cation constituent, and anion component is represented by above-mentioned general formula (1).
R in the general formula (1) 1Alkyl for carbon number 1～10.As R 1, for example can enumerate the straight chain aliphatic group of carbon number 1～10, the side chain aliphatic group of carbon number 3～10 and the aryl of carbon number 6～10.
Straight chain aliphatic group as carbon number 1～10, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl are for example arranged, and the residue etc. of from aklylene glycol (alkylene glycol), glycerine and the D-sorbite etc. of carbon number 2～10, having removed hydroxyl.
As the side chain aliphatic group of carbon number 3～10, the alkyl of isopropyl, isobutyl group or the tert-butyl group, isopentyl or neopentyl, isohesyl, different heptyl, iso-octyl, different nonyl or Zhong Renji, isodecyl or secondary decyl, 1-ethyl octyl group and general formula (3) expression is for example arranged.
[changing 1]
Figure GPA00001153386100031
[in the formula, R 4And R 5The alkyl of representing carbon number 1～6 respectively independently, and R 4With R 5Carbon number add up to 3～8, e is 0～2 integer, R 4With R 5Carbon number add up at 8 o'clock, e is 0 or 1.]
As the R in the general formula (3) 4And R 5Object lesson, methyl is for example arranged, ethyl, n-pro-pyl or isopropyl, isobutyl group or normal-butyl, sec-butyl, the isobutyl group or the tert-butyl group, n-pentyl, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, 2, the 2-dimethyl propyl, n-hexyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, 1,1-dimethyl-2-methyl-propyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methyl-propyl.
As the aryl of carbon number 6～10, the alkyl of general formula (4) expression is for example arranged.
[changing 2]
Figure GPA00001153386100041
[in the formula, f R 6The alkyl of representing hydrogen atom or carbon number 1～4 respectively independently, and f R 6Carbon number add up to below 4, f is 1～4 integer.]
As the R in the general formula (4) 6, the R in the above-mentioned general formula (3) is for example arranged 4And R 5The alkyl of carbon number 1～4 in the illustrated alkyl.
Wherein, from the viewpoint of particle removal and low foaming characteristic, these R 1In the alkyl of preferred carbon number 4～10, be more preferably the alkyl of general formula (3) or (4) expression.
A in the general formula (1) 1Alkylidene for carbon number 2～4.As A 1, ethylidene, 1 is for example arranged, 2-propylidene or 1,3-propylidene and 1,2-butylidene, 1,3-butylidene, 2,3-butylidene or 1,4-butylidene.Wherein, from the viewpoint of ageing stability and low foaming characteristic, preferred ethylidene and 1,2-propylidene.A 1Can use a kind of alkylidene separately or and with the alkylidene more than 2 kinds.
As hereinafter described, because (A 1O) be that alkylidene by alkylene oxide (alkylene oxide) (below be abbreviated as AO) is A 1The addition reaction of compound generate, therefore, the addition molal quantity of these addition products has certain scope.Therefore, a represents with mean value, is generally 0～20, from the viewpoint of ageing stability, is preferably 0～10, is more preferably 0～5, is preferably 0 especially.
In addition, form (A 1O) time, when using the AO more than 2 kinds simultaneously, can be block addition (inserting (チ Star プ) type, symmetry (バ ラ Application ス) type, active auxiliary (active セ カ Application ダ リ one) type etc.), it also can be random addition, perhaps both mixed forms [group that inserts after the random addition: have the oxygen ethylene chain (oxyethylene chain) that 0～50% (preferred 5～40%) distribute arbitrarily in the molecule, the oxygen ethylene chain of 0～30% (preferred 5～25%) is inserted into molecular end].
Above and hereinafter, unless otherwise mentioned, % represents weight %.
Q in the general formula (1) -For-COO -,-OCH 2COO -,-SO 3 -,-OSO 3 -Or-OPO 2(OR 2) -, the viewpoint from the cleaning agent rinsing is preferably-OSO 3 -With-OPO 2(OR 2) -
In addition, Q -For-COO -Or-SO 3 -The time, above-mentioned a is 0.
R 2Alkyl for hydrogen atom or carbon number 1～10.As the alkyl of carbon number 1～10, can enumerate with general formula (1) in R 1The group that illustrative group is identical from the viewpoint of the dispersion stabilization of particle, is preferably the alkyl of carbon number 4～10, is more preferably the alkyl of general formula (3) or (4) expression.
B in the general formula (1) is 1～6 integer, and the viewpoint of the surface after clean is preferably 1～3, is more preferably 1.
Object lesson as the anion component that constitutes anionic surfactant (A), can enumerate from following alcohol and carbon number thereof is the anion that removes deprotonation the sulfuric ester of 2～4 AO addition product or the phosphate: methyl alcohol, ethanol, 1-propyl alcohol or 2-propyl alcohol, the 1-butanols, the 2-butanols or the tert-butyl alcohol, the 1-amylalcohol, 2-amylalcohol or 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-2-butanols, the 1-hexanol, 2-hexanol or 3-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 3,3-dimethyl-2-butanols, 3-methyl-2-amylalcohol, the 1-enanthol, the 2-enanthol, 3-enanthol or 4-enanthol, 2,4-dimethyl-3-amylalcohol, 3-methyl isophthalic acid-hexanol, 5-methyl-2-hexanol, the 1-octanol, sec-n-octyl alcohol, 3-octanol or 4-octanol, 6-methyl-2-enanthol, 2,2-dimethyl-3-hexanol, 2,5-dimethyl-3-hexanol, 2-ethyl-1-hexanol, 5-methyl-2-enanthol, 5-methyl-3-enanthol, 6-methyl-3-enanthol, 2,2-dimethyl-3-enanthol, 1 nonyl alcohol, the 2-nonyl alcohol, the 3-nonyl alcohol, 4-nonyl alcohol or 5-nonyl alcohol, 2-methyl-3-octanol, the 1-decyl alcohol, the 2-decyl alcohol, the 3-decyl alcohol, 4-decyl alcohol or 5-decyl alcohol, 3,7-dimethyl-1-octanol, ethylene glycol, 1, the 6-hexylene glycol, 1, the 10-decanediol, alcohol such as glycerine and D-sorbite and carbon number thereof are 2～4 AO (oxirane, 1,2-expoxy propane or 1,3-expoxy propane and 1, the 2-epoxy butane, 1, the 3-epoxy butane, 2,3-epoxy butane or 1,4-epoxy butane etc.) remove the anion of deprotonation in the sulfuric ester of addition product (addition molal quantity 1～20) or the phosphate; From following acid, remove the anion of deprotonation: propionic acid, 2 Methylpropionic acid, 2, the 2-neopentanoic acid, butyric acid, 2-Methyl Butyric Acid or 3 Methylbutanoic acid, 2 Ethylbutanoic acid, 2,3-acid dimethyl or 3, the 3-acid dimethyl, 2-ethyl-3 Methylbutanoic acid, valeric acid, 2 methyl valeric acid, 3 methylvaleric acid or 4-methylvaleric acid, 2-ethyl valeric acid or 3-ethyl valeric acid, 2-n-pro-pyl valeric acid or isopropyl valeric acid, 2,4-dimethyl valeric acid, 2,4,4-trimethyl valeric acid or 3,4,4-trimethyl valeric acid, caproic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, 4-methylhexanoic acid or 5-methylhexanoic acid, 2 ethyl hexanoic acid, the 3-thylhexoic acid, or 4-thylhexoic acid, 2-n-pro-pyl caproic acid or 3-n-pro-pyl caproic acid, 2-isopropyl caproic acid or 3-isopropyl caproic acid, 2,5-dimethyl caproic acid or 3,5-dimethyl caproic acid, 2,5,5-or 3,5, the 5-tri-methyl hexanoic acid, enanthic acid, the 2-methyl enanthic acid, the 3-methyl enanthic acid, the 4-methyl enanthic acid, 5-methyl enanthic acid or 6-methyl enanthic acid, 2-ethyl enanthic acid, 3-ethyl enanthic acid, 4-ethyl enanthic acid or 5-ethyl enanthic acid, 2-n-pro-pyl enanthic acid, 3-n-pro-pyl enanthic acid or 4-n-pro-pyl enanthic acid, 2-isopropyl enanthic acid, 3-isopropyl enanthic acid or 4-isopropyl enanthic acid, 2,6-dimethyl enanthic acid or 3,6-dimethyl enanthic acid, 2,6,6-trimethyl enanthic acid, 2,4,6-trimethyl enanthic acid or 3,6,6-trimethyl enanthic acid, sad, the 2-methyloctanoic acid, the 3-methyloctanoic acid, the 4-methyloctanoic acid, the 5-methyloctanoic acid, 6-Methyloctanoic Acid or 7-methyloctanoic acid, the 2-ethyl is sad, the 3-ethyl is sad, the 4-ethyl is sad, the 5-ethyl is sad or the 6-ethyl is sad, 2, the 7-dimethyl is sad or 3, and the 7-dimethyl is sad, n-nonanoic acid and 2-methyl nonanoic acid, the 3-methyl nonanoic acid, the 4-methyl nonanoic acid, the 5-methyl nonanoic acid, the 6-methyl nonanoic acid, 7-methyl nonanoic acid or 8-methyl nonanoic acid; From 1-methyl propane sulfonic acid, 1-methylpent sulfonic acid and 1-ethyl fourth sulfonic acid, remove the anion of deprotonation; Above-mentioned alcohol or its carbon number alkyl ether carboxy acid salt's that to be 2～4 AO addition product (addition molal quantity 1～20) obtain with 2-chloracetate (sylvite or sodium salt) reaction anion; From benzene sulfonic acid, toluenesulfonic acid, xylene monosulfonic acid, isopropyl sulfonic acid and benzoic acid, remove the anion of deprotonation etc.
Constitute in these anion components of anionic surfactant (A), viewpoint from particle removal and low foaming characteristic, preferably from 1-butanols, 2-ethyl-1-hexanol, 3-methyl isophthalic acid-hexanol, 3,7-dimethyl-1-octanol and carbon number thereof are 2～4 AO (oxirane, 1,2-expoxy propane or 1,3-expoxy propane and 1,2-epoxy butane, 1,3-epoxy butane, 2,3-epoxy butane or 1,4-epoxy butane etc.) remove the anion of deprotonation in the sulfuric ester of addition product (addition molal quantity 1～20) or the phosphate; And from 2-ethyl valeric acid, 2-n-pro-pyl valeric acid, 2-isopropyl valeric acid, 2,4,4-trimethyl valeric acid or 3,4, remove the anion of deprotonation in 4-trimethyl valeric acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, 2-n-pro-pyl caproic acid, 2-isopropyl caproic acid, 2-methyl enanthic acid, 2-ethyl enanthic acid, 2-methyloctanoic acid, benzene sulfonic acid, toluenesulfonic acid and the xylene monosulfonic acid; Be more preferably from 2-ethyl-1-hexanol, 3-methyl isophthalic acid-hexanol and 3, remove the anion of deprotonation in the sulfuric ester of 7-dimethyl-1-octanol or the phosphate; And from 2-n-pro-pyl valeric acid, 2-isopropyl valeric acid, 2,4,4-trimethyl valeric acid or 3,4 removes the anion of deprotonation in 4-trimethyl valeric acid, 2 ethyl hexanoic acid, 2-methyl enanthic acid, p-methyl benzenesulfonic acid, o-toluene sulfonic acid, meta-xylene sulfonic acid and the paraxylene sulfonic acid; Especially preferably from the sulfuric ester of 2-ethyl-1-hexanol or phosphate, remove the anion of deprotonation; And the anion that from sad, p-methyl benzenesulfonic acid and meta-xylene sulfonic acid, removes deprotonation; Most preferably from sulfuric ester, p-methyl benzenesulfonic acid and the meta-xylene sulfonic acid of 2-ethyl-1-hexanol, remove the anion of deprotonation.
As the cation constituent that constitutes anionic surfactant of the present invention (A), can enumerate alkali metal cation, alkaline-earth metal cation, the ammonium cation of carbon number 0～25, proton and add to aromatic series that cation on the alkanolamine that cation, proton on the amidine compound that cation, proton on the aliphatic amine that cation, proton on the azanol add to carbon number 1～36 add to carbon number 4～10 add to carbon number 1～23 and proton add to carbon number 6～20 or the cation on the aromatic-aliphatic amine.These may be used alone, two or more kinds can also be used.
As alkali metal cation, can enumerate sodium cation and potassium cationic etc.
As the alkaline-earth metal cation, can enumerate calcium cation and magnesium cation etc.
As the ammonium cation of carbon number 0～25, can enumerate ammonium, tetramethyl-ammonium, trimethyl-ethylene base ammonium, trimethylphenyl ammonium, benzyl triethyl ammonium ammonium, dodecyl trimethyl ammonium, TBuA, trimethyl myristyl ammonium, benzyl tributyl ammonium, four pentyl ammonium, ethylhexadecyl Dimethyl Ammonium and octadecyl trimethyl ammonium etc.
Add to the aliphatic amine of the carbon number 1～36 in the cation on the aliphatic amine of carbon number 1～36 as proton, can enumerate the Alkylenediamine of alkylamine, the carbon number 2～6 of carbon number 1～12, the cyclic amine of carbon number 3～7, poly-(n=3～7) amine of poly-(n=2～6) alkylidene (carbon number 2～6) and carbon number thereof and be 2～4 AO (oxirane, 1,2-expoxy propane or 1,3-expoxy propane and 1,2-epoxy butane, 1,3-epoxy butane, 2,3-epoxy butane or 1,4-epoxy butane etc.) addition product etc.
As the alkylamine of carbon number 1～12, can enumerate the monoalkylamine (methylamine, ethamine, propylamine, isopropylamine, butylamine and hexylamine etc.) of carbon number 1～6 and the dialkylamine (dimethylamine, ethyl dimethylamine, propyl methylamine, butyl methylamine, diethylamine, propyl group ethamine, diisopropylamine and dihexylamine etc.) of carbon number 2～12 etc.
As the Alkylenediamine of carbon number 2～6, can enumerate ethylenediamine, 1,2-propane diamine or 1,3-propane diamine, tetra-methylenedimine, five methylene diamine and hexamethylene diamine etc.
As the cyclic amine of carbon number 3～7, can enumerate cyclopropylamine, cyclohexylamine, piperidines, piperazine, quinuclidine, 2-pyridine amine, cis-3-methyl cyclohexylamine and 1,4-diazabicylo [2.2.2] octane (DABCO) etc.
As poly-(n=3～7) amine of poly-(n=2～6) alkylidene (carbon number 2～6), can enumerate diethylenetriamines, dipropylenetriamine, two (hexa-methylene) triamine (dihexylenetriamine), trien, tetren, penten and six ethylidene, seven amine etc.
Add to the amidine compound of the carbon number 4～10 in the cation on the amidine compound of carbon number 4～10 as proton, can enumerate 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (below be abbreviated as DBU), 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (below be abbreviated as DBN), glyoxal ethyline, 2-butyl benzimidazole and 2-(4-thiazolyl) benzimidazole etc.
Add to the alkanolamine of the carbon number 1～23 in the cation on the alkanolamine of carbon number 1～23 as proton, can enumerate MEA, diethanol amine, triethanolamine, N methyldiethanol amine, N, the N-dimethylethanolamine, N, the N-diethyl ethylene diamine, 2-amino-2-methyl-1-propanol, N-(amino-ethyl) monoethanolamine, 2-(2-amino ethoxy) ethanol and carbon number thereof are 2～4 AO (oxirane, 1,2-expoxy propane or 1,3-expoxy propane and 1, the 2-epoxy butane, 1, the 3-epoxy butane, 2,3-epoxy butane or 1,4-epoxy butane etc.) addition product etc.
Add to the aromatic series of carbon number 6～20 or the aromatic series or the aromatic-aliphatic amine of the carbon number 6～20 in the cation on the aromatic-aliphatic amine as proton, can enumerate aniline, phenylenediamine, toluenediamine, methylene dianiline (MDA), diphenyl ether diamines, naphthylenediamine, anthradiamine, benzylamine, xyxylene diamines and carbon number thereof and be 2～4 AO (oxirane, 1,2-expoxy propane or 1,3-expoxy propane and 1,2-epoxy butane, 1,3-epoxy butane, 2,3-epoxy butane or 1,4-epoxy butane etc.) addition product etc.
Viewpoint from particle removal, in these cation constituents, the preferred as alkali cation, proton adds to the monovalent cation on the aliphatic amine of carbon number 1～15, proton adds to the monovalent cation on the alkanolamine that cation on the amidine compound of carbon number 4～10 and proton add to carbon number 1～15, be more preferably sodium cation, potassium cationic and proton add to trimethylamine, DBU, cation on DBN and the diethanol amine, preferred especially sodium cation, potassium cationic, proton adds to cation on the DBU and proton and adds to cation on the diethanol amine.
In the general formula (1), Q -For-COO -,-SO 3 -,-OSO 3 -Or-OPO 2(OR 2) -The time, anionic surfactant (A) for example can be by following method manufacturing: polynary (two～seven yuan) amine of the acid that is formed by anion component and proton and the amine of alkali compounds or above-mentioned carbon number 1～15 or carbon number 2～36 carries out neutralization reaction to be made, and described alkali compounds is to be formed by the ammonium cation of above-mentioned alkali metal cation, alkaline-earth metal cation or carbon number 0～25 and hydroxyl anion.The temperature of neutralization reaction is generally 10～60 ℃, and the time is generally 30～200 minutes.Degree of neutralization is generally 95～100%, and the pH of corrective (5% aqueous solution of corrective) is generally 7～12.
In the general formula (1), Q -For-OSO 3 -Or-OPO 2(OR 2) -The time, for example can make by the acid that anion component and proton form by the reaction of following (1) and (2).
(1) addition reaction of AO
With usual way the AO of carbon number 2～4 is added to R in the general formula (1) 1On the hydroxyl of the compound that is replaced by hydroxyl.Particularly, above-mentioned hydroxy-containing compounds is added in the compressive reaction container, (the particularly rear half stage of AO addition) feeds AO in the presence of catalyst-free or catalyst, and normal pressure or add is depressed and carried out one and go on foot or multistep reaction.As catalyst, can enumerate base catalyst, for example the hydroxide of alkali metal (lithium, sodium, potassium and caesium etc.); Acid [high hydracid (perchloric acid, hyperbromic acid and periodic acid), sulfuric acid, phosphoric acid and nitric acid etc. (preferred perchloric acid)] and salt [salt of preferred divalence or trivalent metal (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu and Al etc.)] thereof.
Reaction temperature is generally 50～150 ℃, and the reaction time is generally 2～20 hours.
After the AO addition reaction finishes, can be as required with the catalyst neutralization and use sorbent treatment, catalyst is removed is made with extra care.
(2) sulfuric acid esterification or phosphating reaction
With the R in the general formula (1) 1The terminal hydroxyl of gained AO addition product carries out Sulfation or Phosphation in the compound that is replaced by hydroxyl or above-mentioned (1), obtains Sulfation thing or Phosphation thing.
As esterification method, for example can enumerate (i) use the method for chlorosulfonic acid, (ii) use the method for sulfuric anhydride, (iii) use the method for sulfamic acid, (iv) use sulfuric acid method, (v) use the method for phosphoric acid etc.About sulfuric anhydride (ii), use with dilution backs such as drying nitrogens.
About reaction temperature, occasion (i) and (ii) is generally-10～70 ℃, is preferably-5～40 ℃.(iii), (iv) and (occasion v) is generally 50～150 ℃, is preferably 60～130 ℃.
The terminal point of esterification preferably reaches 80～105% point for the acid value of representing with 56100/ (molecular weight of ester compounds) (AV) reaches 70～110% point of theoretical value.
In the general formula (1), Q -For-SO 3 -The time, the acid that is formed by anion component and proton for example can be by following method manufacturing: the method for alkyl halide or alkyl sulfate and alkaline sulfite reaction, use oleum with the method for hydrocarbon Direct Sulfonation and make method that hydrocarbon and sulfur dioxide and chlorine reacts etc. under the ultraviolet ray irradiation.
In the general formula (1), Q -For-COO -The time, the acid that is formed by anion component and proton for example can be by following method manufacturing: adopt high-pressure decomposing method (8～50 atmospheric pressure) or Twitchell decomposition method (add the Twitchell distintegrant and a small amount of sulfuric acid is removed fatty acid pitch) hydrolysis natural oil to make.
In the general formula (1), Q -For-OCH 2COO -The time, anionic surfactant (A) for example can be by following method manufacturing: with the R in the general formula (1) 1Gained AO addition product and chloroacetate salt (sodium salt and sylvite etc.) carry out carboxy methylation and make in the compound that is replaced by hydroxyl or above-mentioned (1) in the presence of alkali (NaOH and potassium hydroxide etc.).
As the organic solvent among the present invention (B), can enumerate the alkene of carbon number 6～18, organic solvent of general formula (2) expression and composition thereof.
Alkene as carbon number 6～18, can enumerate the straight or branched alkene of carbon number 6～18, concrete example is if any 1-hexene, 2-heptene, 3-octene, 4-nonene, 5-decene, 1-endecatylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, butene dimerization body, butylene tripolymer, the butylene tetramer, isobutene tripolymer, propylene dimerization body, Propylene trimers, the propylene tetramer and propylene pentamer etc.
R in the general formula (2) 3Be the alkyl of carbon number 1～12,, be preferably the alkyl of hydrogen or carbon number 1～8 from the viewpoint of organic matter dirt removal performance.
As the alkyl of carbon number 1～12, can enumerate the R in the above-mentioned general formula (1) 1The alkyl of illustrated carbon number 1～10, n-undecane base, secondary undecyl or different undecyl and dodecyl, secondary dodecyl or Permethyl 99A base etc.
A in the general formula (2) 2Alkylidene (ethylidene, 1,2-propylidene or 1,3-propylidene and 1,2-butylidene, 1 for carbon number 2～4,3-butylidene, 2,3-butylidene or 1,4-butylidene etc.), from the viewpoint of ageing stability and low foaming characteristic, be preferably ethylidene and 1,2-propylidene, A 2Can use a kind of alkylidene or the alkylidene more than 2 kinds and usefulness separately.
Because (A 2O) with general formula (1) in (A 1O) form equally, so its addition molal quantity has certain limit.Therefore, c represents with mean value, is generally 0～20, and the viewpoint from ageing stability is preferably 0～10.
D in the general formula (2) is 1～6 integer, and the viewpoint of the rinsing after clean is preferably 1～3, is more preferably 1.
As the object lesson of the organic solvent of general formula (2) expression, can enumerate isopropyl alcohol, n-amyl alcohol, 2-Ethylhexyl Alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, BC, the hexyl carbitol, triethylene glycol monomethyl ether, the TEG monomethyl ether, the triethylene glycol dimethyl ether, Triethylene glycol ethyl ether, TEG list ether, methyl alcohol oxirane (10mol) addition product, isopropyl alcohol oxirane (5mol) addition product, allyl alcohol oxirane (5mol) expoxy propane (15mol) block addition product, random addition product of glycerine oxirane (15mol) expoxy propane (2mol) and D-sorbite oxirane (2mol) addition product etc.
Viewpoint from particle removal, in the organic solvent (B), preferred 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, isobutene tripolymer, the propylene tetramer, propylene pentamer, 2-Ethylhexyl Alcohol, BC, hexyl carbitol and triethylene glycol monomethyl ether are more preferably 1-dodecylene, isobutene tripolymer, the propylene tetramer, propylene pentamer, BC, hexyl carbitol and triethylene glycol monomethyl ether.
(B) can use in the organic solvent of the alkene of carbon number 6～18 and general formula (2) expression a kind separately, also can more than 2 kinds and use.
(B) SP value is generally 6～13, is preferably 7～12, is more preferably 8～11.If the SP value is less than 6 or surpass 13, then organic dirt property removed variation.
In addition, the SP value is the value of calculating according to the Fedors method of record in " Polymer Engineering and Science, Vol.14, No.2, p147～154 (1974) ".
By containing following alkaline components (C), etching and rinsing are further enhanced electronic material of the present invention with cleaning agent.
As alkaline components (C), can enumerate aliphatic amine (C-2), inorganic base (C-3), the alkanolamine (C-4) of carbon number 1～23, the amidine compound (C-5) of carbon number 4～10 of ammonia, azanol, quaternary ammonium base (C-1), carbon number 1～36 and composition thereof.
As (C-1), can enumerate TMAH, ethyl-trimethyl ammonium hydroxide, tetraethyl ammonium hydroxide, triethyl group ammonium hydroxide, TPAOH, TBAH, four pentyl ammonium hydroxide, four hexyl ammonium hydroxide, ethoxy trimethylammonium hydroxide, triethyl group hydroxyethylammoniumhydroxide hydroxide, dihydroxy ethyl dimethyl hydrogen amine-oxides and trihydroxyethyl ammonium hydroxide etc.
As (C-2), can enumerate the identical composition of aliphatic amine of illustrated carbon number 1～36 in the record with the cation constituent that constitutes above-mentioned anionic surfactant (A).
As (C-3), can enumerate lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide and magnesium hydroxide etc.
As (C-4), can enumerate the identical composition of alkanolamine of illustrated carbon number 1～23 in the record with the cation constituent that constitutes above-mentioned anionic surfactant (A).
As (C-5), can enumerate the identical composition of amidine compound of illustrated carbon number 4～10 in the record with the cation constituent that constitutes above-mentioned anionic surfactant (A).
From etching with the viewpoint of the contact angle (rinsing) of the water after cleaning, (C) in preferred (C-2), (C-3), (C-4), (C-5) and composition thereof, be more preferably potassium hydroxide, NaOH, DBU, butylamine, hexylamine, cyclohexylamine, triethanolamine, N methyldiethanol amine, cyclohexylamine oxirane (2mol) addition product, cyclohexylamine expoxy propane (2mol) addition product, N, the N-dimethylethanolamine, triethanolamine oxirane (5mol) addition product, triethanolamine expoxy propane (5mol) addition product, N, N-dimethylethanolamine oxirane (3mol) addition product, N, N-dimethylethanolamine oxirane (3mol) addition product and composition thereof.
Electronic material of the present invention with cleaning agent can further contain be selected from the group that following high-molecular type dispersing agent (D) and chelating agent (E) constitute more than a kind.
Electronic material of the present invention with cleaning agent by containing high-molecular type dispersing agent (D), the dispersiveness of particle and prevent that contaminative is further enhanced again.
As (D), can enumerate and have weight average molecular weight (below be abbreviated as Mw) is 2, the polymer electrolyte anionic surfactant (D-1) of 500～800,000 sulfonic acid (salt) base, have sulfuric ester (salt) base polymer electrolyte anionic surfactant (D-2), have phosphate (salt) base polymer electrolyte anionic surfactant (D-3), have phosphonic acids (salt) base polymer electrolyte anionic surfactant (D-4), have polymer electrolyte anionic surfactant (D-5) and the polysaccharide and the derivative (D-6) thereof etc. of carboxylic acid (salt) base.
Object lesson as (D) is listed below.
Polymer electrolyte anionic surfactant (D-1) with sulfonic acid (salt) base:
Polystyrolsulfon acid, styrene/styrene sulfonic acid copolymer, poly-[2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid], 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid/styrol copolymer, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid/acrylamide copolymer, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid/(methyl) acrylic copolymer, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid/(methyl) acrylic acid copolymer, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid/styrene/acrylamide copolymer, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid/styrene/(methyl) acrylic copolymer, naphthalene sulfonic acid-formaldehyde condensation product, condensation compound of methyl naphthalene sulfonic acid and formaldehyde, the dimethylnaphthalene sulfonic formaldehyde condensation compound, the rylnthracene sulfonin formaldehyde condensation products, the melamine sulfonic formaldehyde condensation compound, aminobenzenesulfonic acid-P-F condensation product etc. and salt thereof;
Polymer electrolyte anionic surfactant (D-2) with sulfuric ester (salt) base:
Poly-[(methyl) acrylic acid-2-hydroxyl ethyl ester sulfuric ester], acrylic acid-2-hydroxyl ethyl ester/acrylic acid-2-hydroxyl ethyl ester sulfuric ester copolymer, 2-hydroxyethyl methacry-late/2-hydroxyethyl methacry-late sulfuric ester copolymer, the Sulfation thing of poly-[(methyl) acrylic acid-2-hydroxyl ethyl ester], poly-[(methyl) acryloxy polyoxyalkylene sulfuric ester], (methyl) acryloxy polyoxyalkylene sulfuric ester/acrylic copolymer and cellulose, Sulfation thing of methylcellulose or ethyl cellulose etc. and salt thereof;
Polymer electrolyte anionic surfactant (D-3) with phosphate (salt) base:
Poly-[(methyl) acrylic acid-2-hydroxyl Acetoxon acid esters], acrylic acid-2-hydroxyl ethyl ester/acrylic acid-2-hydroxyl Acetoxon acid ester copolymer, 2-hydroxyethyl methacry-late/2-hydroxyethyl methacry-late phosphate copolymer, the Phosphation thing of poly-[(methyl) acrylic acid-2-hydroxyl ethyl ester], poly-[(methyl) acryloxy polyoxyalkylene phosphate], (methyl) acryloxy polyoxyalkylene phosphate/acrylic copolymer and cellulose, Phosphation thing of methylcellulose or ethyl cellulose etc. and salt thereof;
Polymer electrolyte anionic surfactant (D-4) with phosphonic acids (salt) base:
Poly-[(methyl) acryloxy ethylphosphonic acid], acrylic acid-2-hydroxyl ethyl ester/acryloxy ethylphosphonic acid copolymer, 2-hydroxyethyl methacry-late/methacryloxyethyl phosphonic acid copolymer, naphthalene phosphonic acids formaldehyde condensation products, methyl naphthalene phosphonic acids formaldehyde condensation products, dimethylnaphthalene phosphonic acids formaldehyde condensation products, anthracene phosphonic acids formaldehyde condensation products, aminophenylphosphoniacid acid-P-F condensation product etc. and salt thereof;
Polymer electrolyte anionic surfactant (D-5) with carboxylic acid (salt) base:
Poly-(methyl) acrylic acid, (methyl) acrylic acid-maleic acid, (methyl) acrylic acid-itaconic acid copolymer, (methyl) acrylic acid-fumaric acid copolymer, (methyl) acrylic acid/vinyl acetate copolymer, 2-hydroxyethyl methacry-late/(methyl) acrylic copolymer, the carboxy methylation thing of poly-[(methyl) acrylic acid-2-hydroxyl ethyl ester], carboxymethyl cellulose, carboxy methyl cellulose, carboxymethylethylcellulose, the benzoic acid formaldehyde condensation products, benzoic acid-P-F condensation product etc. and salt thereof;
Polysaccharide and derivative thereof (D-6):
Hydroxyethylcellulose, cationized cellulose, CMC, hydroxypropyl cellulose, guar gum, JR-125, xanthans, alginates, cationic starch etc., polyvinyl alcohol and phosphate [phytic acid, two (polyoxyethylene) alkyl ether phosphoric acid and three (polyoxyethylene) alkyl ether phosphoric acid etc.] etc.
Counter ion counterionsl gegenions during to (D) salify are not particularly limited, and for example can enumerate alkali metal salt (sodium salt and sylvite etc.), ammonium salt, primary amine salt (alkylamines such as methylamine, ethamine and butylamine, MEA and guanidine etc.), secondary amine salt (dialkylamine such as dimethylamine, diethylamine and dibutyl amine and diethanol amine etc.), tertiary ammonium salt (trialkylamines such as trimethylamine, triethylamine and tri-n-butylamine, triethanolamine, DBU, DBN and DABCO etc.) and quaternary ammonium salt (tetraalkylammonium salt etc.).
Viewpoint from the particle dispersiveness, (D) in preferred (D-1) and (D-5), be more preferably polystyrolsulfon acid, styrene/styrene sulfonic acid copolymer, poly-(methyl) acrylic acid, (methyl) acrylic acid-maleic acid and salt thereof, especially preferably poly-(methyl) acrylic acid and (methyl) acrylic acid-maleic acid and salt thereof.
Reach the viewpoint of low foaming characteristic etc. from the tack that prevents again of particle, Mw (D) is preferably 3,000～400,000, is more preferably 4,000～80,000, is preferably 5,000～40,000 especially.
Mw among the present invention adopt gel permeation chromatography, with polyoxyethylene as standard substance in 40 ℃ measure [for example, apparatus main body: HLC-8120 ((East ソ one Co., Ltd. of TOSOH Co., Ltd) manufacturing); Post: TSKgel α 6000, G3000PWXL that TOSOH Co., Ltd makes; Detector: the built-in differential refractometer of apparatus main body detector; Eluent: 0.5% sodium acetate water/methyl alcohol (volume ratio 70/30), eluent flow rate: 1.0ml/ minute; Column temperature: 40 ℃; Sample: 0.25% eluate solution; Injection volume: 200 μ l; Standard substance: the TSK standard polyoxyethylene (STANDARD POLYETHYLENE OXIDE) that TOSOH Co., Ltd makes; Data processing software: GPC-8020modelII (TOSOH Co., Ltd's manufacturing)].
By containing chelating agent (E), the etching of substrate becomes and is easier to control electronic material of the present invention with cleaning agent, and the dispersion stabilization of particle also is further enhanced.
As (E), (E-1) [for example, ethylenediamine tetra-acetic acid (salt) (EDTA) can to enumerate aminopolycarboxylic (salt), diethylene triamine pentacetic acid (DTPA) (salt) (DTPA), triethylenetetramine hexaacetic acid (salt) (TTHA), hydroxyethylethylene diamine tri-acetic acid (salt) (HEDTA), dihydroxy ethyl ethylenediamine tetra-acetic acid (salt) (DHEDDA), aminotriacetic acid (salt) (NTA), hydroxyethyliminodiacetic acid (salt) (HIDA), Beta-alanine oxalic acid (salt), aspartic acid oxalic acid (salt), methylglycine oxalic acid (salt), imino-diacetic butanedioic acid (salt), serine oxalic acid (salt), oxyimino disuccinic acid (salt), dihydroxyethylglycin (salt), aspartic acid (salt) and glutamic acid (salt)];
Hydroxycarboxylic acid (salt) is [for example, glycolic acid (salt), tartaric acid (salt), citric acid (salt) and gluconic acid (salt)] (E-2);
Ether carboxylic acid (salt) is [for example, carboxymethyl mesoxalate (carboxymethyltartronate), carboxymethyl hydroxyl succinate (carboxymethyl oxysuccinate), hydroxyl disuccinate (oxydisuccinate), tartaric acid monosuccinic acid salt and tartaric acid disuccinate] (E-3);
Other carboxylic acids (salt) are [for example, maleic acid derivatives and oxalic acid (salt)] (E-4);
Phosphonic acids (salt) (E-5) [for example, methylenediphosphonate (salt), amino three (methylene phosphonic acid) (salt), 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (salt), ethylenediamine tetraacetic (methylene phosphonic acid) (salt), hexamethylene diamine four (methylene phosphonic acid) (salt), propane diamine four (methylene phosphonic acid) (salt), diethylenetriamine five (methylene phosphonic acid) (salt), triethylene tetramine six (methylene phosphonic acid) (salt), triamido triethylamine six (methylene phosphonic acid) (salt), anti-form-1,2-cyclohexanediamine four (methylene phosphonic acid) (salt), glycol ether diamines four (methylene phosphonic acid) (salt) and TEPA seven (methylene phosphonic acid) (salt)];
Condensed phosphoric acid (salt) is [for example, metaphosphoric acid (salt), tripolyphosphate (salt) and hexa metaphosphoric acid (salt)] etc. (E-6).
In addition, the counter ion counterionsl gegenions during as (E) salify can be enumerated illustrated material in the above-mentioned high-molecular type dispersing agent (D).In addition, these may be used alone, two or more kinds can also be used.
From the etching control of substrate and the viewpoint of cleaning performance, (E) in preferred (E-1), (E-2), (E-4), (E-5) reach (E-6), be more preferably (E-1), (E-2), (E-5) reach (E-6), preferred especially ethylenediamine tetra-acetic acid (salt) (EDTA), diethylene triamine pentacetic acid (DTPA) (salt) (DTPA), dihydroxy ethyl ethylenediamine tetra-acetic acid (salt) (DHEDDA), aspartic acid oxalic acid (salt), aspartic acid (salt), glutamic acid (salt), citric acid (salt), amino three (methylene phosphonic acid) (salt), 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (salt), ethylenediamine tetraacetic (methylene phosphonic acid) (salt), metaphosphoric acid (salt) and hexa metaphosphoric acid (salt), more special optimization citric acid (salt), amino three (methylene phosphonic acid) (salt), 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (salt), ethylenediamine tetraacetic (methylene phosphonic acid) (salt) and hexa metaphosphoric acid (salt).
In addition, the ring carboxylic acid (salt) in the anionic surfactant of the present invention (A) [for example, Pyromellitic Acid (salt), benzo polycarboxylic acids (salt) and pentamethylene tetrabasic carboxylic acid (salt)] also has the effect as chelating agent.
In the scope of the effect of not damaging cleaning agent, electronic material of the present invention also can further contain other additives (F) with cleaning agent.As (F), can enumerate reducing agent, antioxidant, antirust agent, pH conditioning agent, buffer, defoamer, anticorrisive agent and hydrotropic agent etc.
As reducing agent, the reductones that can enumerate carbon number 6～70 [for example, L-ascorbic acid (salt), arabo-ascorbic acid (salt), 5,6-alkylidene-L-ascorbic acid { 5,6-isopropylidene-L-ascorbic acid, 5,6-(butane-2-subunit)-L-ascorbic acid and 5,6-(pentane-3-subunit)-L-ascorbic acid etc. } (salt), L-ascorbic acid-6-carboxylate (L-ascorbic acid-6-acetic acid esters and L-ascorbic acid-6-propionic ester etc.) (salt), ascorbic acid sulfuric ester (salt), ascorbic acid phosphoric acid esters (salt), ascorbic acid glucoside (salt), the different palmitate of ascorbic acid (salt), erythorbic acid (salt), erythorbic acid phosphate (salt), erythorbic acid palmitate (salt) and four different palmitic acid erythorbic acids (salt)]; The aromatic amine of carbon number 6～9 (p-phenylenediamine (PPD) and para-aminophenol etc.); The oxybenzene compound of carbon number 6～30 [monohydric phenol compound { 3-flavonol and tocopherol (alpha-tocopherol, betatocopherol, Gamma-Tocopherol, Delta-Tocopherol, ε-tocopherol or η-tocopherol) etc. } and polyphenol (3,4,5-trihydroxybenzoic acid, catechol, resorcinol, hydroquinones, naphthoresorcinol, pyrogallol and phloroglucin etc.) etc.]; Phosphorus reducing agent (three-2-carboxyethyl phosphine etc.); Aldehyde (formaldehyde, acetaldehyde, propionic aldehyde and hexenal etc.); Boranes complex compound (borine-tert-butylamine complex compound, borine-N, N-diethylbenzene amine complex and borine-trimethylamine complex compound etc.); Thio-alcohol reducing agent (L-cysteine and aminoothyl mercaptan etc.); Azanol class reducing agent (azanol and diethyl hydroxylamine etc.); Inorganic reducing agent [sulfurous acid (salt), two sulfurous acid (salt), hydrosulfurous acid (salt), thiosulfuric acid (salt), dithionic acid (salt), polythionic acid (salt), phosphorous acid (salt), phosphorous acid hydracid (salt), hypophosphorous acid (salt), ferrous sulfate, stannic chloride, sodium cyanoborohydride and sodium borohydride etc.] etc.
Counter ion counterionsl gegenions during as the reducing agent salify can use illustrated identical material in the above-mentioned high-molecular type dispersing agent (D).Reducing agent may be used alone, two or more kinds can also be used.In addition, above-mentioned alkaline components (C) illustrated (C-2), (C-4) reach the effect that (C-5) also has as reducing agent.
As antioxidant, can enumerate phenol antioxidant (2,6-two-tert-butyl phenol, the 2-tert-butyl group-4-metoxyphenol and 2,4-dimethyl-6-tert-butyl phenol etc.), amine antioxidants (monoalkyl diphenylamines such as single octyl diphenylamine, single nonyl diphenylamine; 4,4 '-dibutyl diphenylamines, 4, dialkyl diphenylamine such as 4 '-diamyl diphenylamines; Poly-alkyl diphenylamines such as tetrabutyl diphenylamines, four hexyl diphenylamines; Naphthylamines such as alpha-naphthylamine and PA etc.), sulphur compounds [phenthazine, pentaerythrite-four-(3-lauryl thiopropionate) and two (3,5-tertiary butyl-4-hydroxy benzyl) sulfide etc.] and Phosphorus antioxidant [two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphites, phosphorous acid phenyl two isodecyl esters, phosphorous acid diphenyl di-isooctyl and triphenyl phosphite etc.] etc.
As antirust agent, can enumerate BTA, azimido-toluene, have nitrogenous organic corrosion inhibitors such as BTA, the benzimidazole of the alkyl of carbon number 2～10, imidazoles, the thiazole of alkyl and 2-mercaptobenzothiazole with carbon number 2～20 with alkyl of carbon number 2～20; Alkyl or alkenyl succinic such as dodecenyl succinic succinic acid half-ester, vaccenic acid base succinyl oxide and dodecenyl succinic succinamide; Polyol partial esters such as single oleic acid sorbitan ester, glycerin mono-fatty acid ester and pentaerythritol monooleate etc.These may be used alone, two or more kinds can also be used.
As the pH conditioning agent, can enumerate inorganic acid (hydrochloric acid, sulfuric acid, nitric acid and sulfamic acid etc.), organic acid (citric acid, oxalic acid and lactic acid etc.) and above illustrative alkaline components (C) etc.These may be used alone, two or more kinds can also be used.
As buffer, can enumerate organic acid (acetate, formic acid, gluconic acid, glycolic acid, tartaric acid, fumaric acid, levulic acid, valeric acid, maleic acid and mandelic acid etc.), inorganic acid (phosphoric acid and boric acid etc.) and the salt thereof of carbon number 1～10 with cushioning effect.In addition, the counter ion counterionsl gegenions during as the buffer salify can use illustrated identical material in the above-mentioned high-molecular type dispersing agent (D).These may be used alone, two or more kinds can also be used.
As defoamer, can enumerate silicone defoamer (with dimethyl silscone, fluorosilicone and polyethers silicone etc. as defoamer of constituent etc.) etc.These may be used alone, two or more kinds can also be used.
As anticorrisive agent, can enumerate pyrrolotriazine derivatives [six hydrogen-1,3,5-three (2-ethoxy)-S-triazine etc.], isothiazoline derivative (1, the 2-benzisothiazole-3-ketone, 2-methyl-4-isothiazoline-3-ketone and 5-chloro-2-methyl-4-isothiazoline-3-ketone etc.), pyridine derivate [pyridine 2-mercaptopyridine-1-oxide (salt) etc.], morpholine derivative [4-(2-nitro butyl) morpholine and 4,4-(2-ethyl-2-nitrotrimethylolmethane methylene)-dimorpholine etc.], benzimidizole derivatives [2-(4-thiazolyl) benzimidazole etc.], poly-[oxygen ethylidene (two auxotox radicals) ethylidene (two auxotox radicals) ethylidene] dichloride, parachlorometaxylenol, Phenoxyethanol, benzene oxygen propyl alcohol, the acetoxyl group dimethyl dioxane, isopropyl methyl phenol, daconil M, two (acetyl bromide oxygen base) ethane, 3-iodo-2-propynyl butyl carbamate and 2-bromo-2-nitropropane-1,3-glycol etc.These may be used alone, two or more kinds can also be used.
As hydrotropic agent, can enumerate resorcinol and salicylic acid (salt) etc.In addition, the counter ion counterionsl gegenions during as the hydrotropic agent salify can use illustrated identical material in above-mentioned (D).These may be used alone, two or more kinds can also be used.In addition, also have as the illustrated toluenesulfonic acid of anionic surfactant (A) (salt), xylene monosulfonic acid (salt), isopropyl sulfonic acid (salt) and benzoic acid (salt) as efficiency of hydrotrope.
As mentioned above, electronic material of the present invention contains anionic surfactant (A), organic solvent (B) and contains alkaline components (C), high-molecular type dispersing agent (D), chelating agent (E) and other additives (F) as required with cleaning agent, also can further contain water, particularly ion exchange water (electrical conductivity 0.2 μ S/cm is following) or ultra-pure water (more than the resistivity 18M Ω cm).
Among the present invention, so-called active ingredient is meant the composition beyond the water.
From the viewpoint of particle removal and low foaming characteristic, based on the weight of electronic material with the active ingredient of cleaning agent, content (A) is preferably 0.5～99%, is more preferably 1～95%, is preferably 2～90% especially, most preferably is 5～80%.
From the viewpoint of particle removal, based on the weight of electronic material with the active ingredient of cleaning agent, content (B) is preferably 1～99.5%, is more preferably 2～95%, is preferably 5～90% especially, most preferably is 10～85%.
From the viewpoint of etching and rinsing, based on the weight of electronic material with the active ingredient of cleaning agent, content (C) is preferably 0～55%, is more preferably 1～55%, is preferably 3～50% especially, most preferably is 5～45%.
From particle dispersiveness and the viewpoint that prevents again contaminative, based on the weight of electronic material with the active ingredient of cleaning agent, content (D) is preferably 0～25%, is more preferably 0.1～20%, is preferably 0.5～15% especially, most preferably is 1～10%.
From the etching control of substrate and the viewpoint of dispersion stabilization, based on the weight of electronic material with the active ingredient of cleaning agent, content (E) is preferably 0～10%, is more preferably 0.01～7%, be preferably 0.05～5% especially, most preferably be 0.1～3%.
Based on the weight of electronic material with the active ingredient of cleaning agent, (F) each additive reducing agent, antioxidant, antirust agent, buffer and hydrotropic content in are preferably 0～20%, be more preferably 0.1～15%, be preferably 0.5～10% especially, most preferably be 1～5%.In addition, the content of defoamer is preferably 0～2%, is more preferably 0.01～1.5%, is preferably 0.02～1% especially, most preferably is 0.05～0.5%.
Based on the weight of electronic material with the active ingredient of cleaning agent, total content (F) is preferably 0～25%, is more preferably 0.5～20%, is preferably 1～15% especially, most preferably is 2～10%.
In addition, in the above-mentioned optional member (C)～(F), the content when forming identical duplicating is not simply with the content addition of each optional member, also will consider to play simultaneously separately the situation as the effect of other optional members, adjusts according to application target.
From the viewpoint of conevying efficiency, electronic material of the present invention is preferably 1～100% with the active ingredient concentration of cleaning agent, is more preferably 2～90%, is preferably 5～70% especially, most preferably is 10～50%.
In addition, the operability during from use and the viewpoint of cost, when using electronic material of the present invention to use cleaning agent, as required, preferably using dilution water, particularly ion exchange water (electrical conductivity 0.2 μ S/cm is following) or ultra-pure water (more than the resistivity 18M Ω cm) is 0.1～15% with the active ingredient concentration dilution, is preferably 0.5～10% especially.
When the occasion of above-mentioned dilute with water, organic solvent (B) were used the alkene of carbon number 6～18, from the viewpoint to the removal of organic matter dirt, above-mentioned alkene preferably existed with dispersity in the cleaning agent.
From the viewpoint of etching and rinsing, when diluting electronic material of the present invention and use cleaning agent with dilution water, under 25 ℃, active ingredient concentration is that the pH of 0.1～15% cleaning agent is preferably 10～14, is more preferably 11～13.
In addition, pH of the present invention measures for 25 ℃ in measuring temperature with pH meter (Horiba Ltd's (the Ku Games System of Co., Ltd. does institute) manufacturing, M-12).
In addition, from the viewpoint to the wetting autgmentability of substrate, to be 0.1～15% cleaning agent be preferably below 10 ° the contact angle of glass active ingredient concentration, is more preferably below 8 °, is preferably especially below 5 °, most preferably is below 1 °.
Contact angle adopt the contact angle meter to glass measure [apparatus main body: PD-W (consonance surface chemistry (Association of company and surface chemistry society) makes); Glass plate: glass plate #1737 (Corning company (コ one ニ Application グ society) manufacturing); Testing conditions: detect automatically; Condition determination: measure the contact angle of drippage after 10 seconds].
Electronic material of the present invention for example can be by with anionic surfactant (A), organic solvent (B) and as required optional member (C)～(F) and water were made in 10～40 ℃ of mixed dissolutions in 30～300 minutes with cleaning agent.
The device that mixed dissolution is used is not particularly limited, and for example can use paddle blade mixing stirring device or spiral vane mixing stirring device.
To the method for electronic material with the cleaning agent dilute with water is not particularly limited, for example can enumerate and use paddle blade mixing stirring device or spiral vane mixing stirring device etc., use cleaning agent and water in 30～300 minutes method of 10～40 ℃ of mixed dissolutions electronic material.
The cleaning method of electronic material of the present invention has and uses above-mentioned cleaning agent, by be selected from by ultrasonic wave cleaning, spray Cleaning for High Capacity, spraying cleanings, brush cleaning, dipping clean, dipping swing and one chip clean (Mei Leaf formula and clean) at least a kind of cleaning method in the group of formation method of cleaning.
From the viewpoint of cleaning, cleaning temperature is preferably 10～80 ℃, is more preferably 15～60 ℃, is preferably 20～50 ℃ especially.
Surface roughness (Ra) with the glass surface after the cleaning method cleaning of the present invention is preferably below the 1.0nm, is more preferably 0.75nm, is preferably below the 0.5nm especially.If Ra is below the 1.0nm, then in subsequent handling, can forms uniform film during by film forming such as sputters, thereby improve productive rate.
In addition, Ra uses the E-sweep of SII NanoTechnology company (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ one society) manufacturing to measure by following condition.
Mode determination: DFM (rapping pattern (tapping mode))
Scanning area: 10 μ m * 10 μ m
Number of scanning lines: 256 lines (Y scanning direction)
Proofread and correct: the flat field correction of X, Y direction
With respect to the glass that uses electronic material of the present invention to clean with cleaning agent, the contact angle of water is below 20 °, is preferably below 15 °.
Embodiment
Below by embodiment the present invention is described in more detail, yet the present invention is not limited to this.Short of special qualification, part is hereinafter all represented weight portion.In addition, hereinafter ultra-pure water uses than resistance value and is the water more than the 18M Ω cm.
Production Example 1
In having the glass system reaction unit of agitating device and temperature control equipment, add 256 parts of 2-Ethylhexyl Alcohols, stir down and be cooled to 0 ℃, temperature in the system is kept 0 ℃ under, with 229 parts of 3 hours dropping chlorosulfonic acids, obtain sulfuric ester.Slowly add 583 parts of 252 parts of 48% potassium hydroxide aqueous solutions and ion exchange waters again, mix neutralizing in 60 minutes in 20 ℃, obtain active ingredient concentration and be 1248 parts of 40% anionic surfactant (A-1).
Production Example 2
In having the glass system reaction unit of agitating device and temperature control equipment, add 148 parts of n-butanols, stir down adjustment to 70 ℃, under 70 ℃ of temperature maintenances in the system, after dripping 8 parts of phosphatase 79s in 2 hours, continue to stir 4 hours in 70 ℃ again, obtain phosphate.To be cooled to 30 ℃ in the system again, slowly add 201 parts of 133 parts of 30% sodium hydrate aqueous solutions and ion exchange waters, mix neutralizing in 60 minutes in 20 ℃, obtain active ingredient concentration and be 580 parts of 40% anionic surfactant (A-2).
Production Example 3
Except 2-Ethylhexyl Alcohol is replaced to 3, the umber of 7-dimethyl-1-octanol, chlorosulfonic acid replaces to 189 parts, 253 parts of umbers that replace to 271 parts of DBU, ion exchange water of 48% potassium hydroxide aqueous solution and replaces to 912 parts, other are identical with Production Example 1, obtain active ingredient concentration and be 1568 parts of 40% anionic surfactant (A-3).
Production Example 4
In beaker, add 395 parts of 144 parts of 2 ethyl hexanoic acids and ion exchange waters, stirred 15 minutes in 20 ℃, after evenly mixing, slowly add 119 parts of N methyldiethanol amines, mix to neutralize in 60 minutes in 20 ℃, obtain active ingredient concentration and be 658 parts of 40% anionic surfactant (A-4).
Production Example 5
In having the stainless steel autoclave of agitating device and temperature control equipment, add 8 parts of 130 parts of 1-octanols and 28% methanol solution of sodium methylate, stir down and intrasystem gas phase is partly used nitrogen replacement in room temperature (20 ℃), then decompression down (gauge pressure :-0.0025MPa) in 120 ℃ carried out separating methanol with 2 hours after, under then reducing pressure (gauge pressure :-0.05MPa) begin 88 parts in logical oxirane in 120 ℃ of reaction temperatures, gauge pressure is controlled under 0.1～0.3Mpa reacts, in system, do not have pressure to change, obtain 218 parts of the oxirane 2mol addition products of 1-octanol.In the glass system reaction unit that has stirring and temperature control equipment, add 200 parts of 96 parts in 164 parts of oxirane 2mol addition products, the chloroacetic acid sodium of above-mentioned 1-octanol and toluene, slowly raise under temperature kept 50 ℃ behind decompression Du Da-0.01Mpa, decompression dehydration added 38 parts in graininess NaOH with 2 hours down, and maturation added 300 parts of ion exchange waters after 6 hours again, with hydrochloric acid furnishing acidity, by leaving standstill, after the separatory desalination, carrying out piptonychia benzene, obtain structural formula C 8H 17O (CH 2CH 2O) 2CH 2The ether carboxylic acid that COOH represents.In the glass system reaction unit that has stirring and temperature control equipment, add 323 parts of entry, slowly add 30 parts in graininess NaOH, dissolving, add 208 parts of above-mentioned ether carboxylic acids in 60 ℃, obtain active ingredient concentration and be 561 parts of 40% anionic surfactant (A-5).
Production Example 6
In having the stainless steel autoclave of agitating device and temperature control equipment, add 3 parts in 113 parts of 2-Ethylhexyl Alcohols and potassium hydroxide, stir down and intrasystem gas phase is partly used nitrogen replacement in room temperature (20 ℃), under the decompression (gauge pressure :-0.05MPa) begin 384 parts in logical oxirane in 120 ℃ of reaction temperatures, gauge pressure is controlled under 0.1～0.3Mpa reacts, in system, do not have pressure to change, obtain 497 parts of the oxirane 10mol addition products of 2-Ethylhexyl Alcohol.
Replace to 112 parts, the umber of ion exchange water and replace to 833 parts except the umber of 497 parts of oxirane 10mol addition products 256 parts of 2-Ethylhexyl Alcohols being replaced to above-mentioned 2-Ethylhexyl Alcohol, chlorosulfonic acid replaces to 102 parts, the umber of 48% potassium hydroxide aqueous solution, other are identical with Production Example 1, obtain active ingredient concentration and be 1512 parts of 40% anionic surfactant (A-6).
Production Example 7
In having the stainless steel autoclave of agitating device and temperature control equipment, add 297 parts of cyclohexylamine, stir down and intrasystem gas phase is partly used nitrogen replacement in room temperature (20 ℃), under the decompression (gauge pressure :-0.05MPa) begin 264 parts in logical oxirane in 100 ℃ of reaction temperatures, gauge pressure is controlled under 0.1～0.3Mpa reacts, in system, do not have pressure to change, obtain 561 parts of cyclohexylamine oxirane (2mol) addition products.
Embodiment 1～29 and comparative example 1～7
Press in table 1 and the table 2 the cooperation umber of record, use beaker in 20 ℃ with table 1 and table 2 in each composition of record evenly mix, make the cleaning agent of embodiment 1～29 and comparative example 1～7.In addition, the umber of (A)～(F) of record is the umber of active ingredient in table 1 and the table 2, and the umber of ultra-pure water comprises the water among the PANa of (A-1)～(A-6) and aftermentioned (D).
In addition, the contracted notation of the composition in table 1 and the table 2 is as described below.
MeXSNa: meta-xylene sulfonate sodium (the (Bei Xing Xing of the industrial Co., Ltd. of northern star industry Co., Ltd.) is made)
SDS: lauryl sulfate sodium salt (Nacalai Tesque Co., Ltd. (Na カ ラ イ テ ス Network Co., Ltd.) make: relatively the anion surfactant of usefulness)
PELSNa: polyoxyethylene lauryl ether sodium sulfate salt (Sundet EN, Sanyo Chemical Industries, Ltd. (Sanyo Chemical Industries, Ltd.) make: relatively the anion surfactant of usefulness)
D2ehNa: two-2-ethylhexyl sulfosuccinic acid sodium salt (Tokyo HuaCheng Industry Co., Ltd make: relatively the anion surfactant of usefulness)
HC: hexyl carbitol (SP value 10.2)
PP-15: propylene pentamer (SP value 7.6)
TEG-M: triethylene glycol monomethyl ether (SP value 10.8)
FA: formamide (SP value 19.2: relatively the solvent of usefulness)
KOH: potassium hydroxide
DBU:1,8-diazabicylo [5.4.0] 11 carbon-7-alkene [San-Apro Co., Ltd. (サ Application ア プ ロ Co., Ltd.) manufacturing]
The MDEA:N-methyl diethanolamine
CHNEG: cyclohexylamine oxirane (2mol) addition product that obtains in the above-mentioned Production Example 7
PANa: polyacrylic acid sodium salt [Caribon L-400,43% aqueous solution, Sanyo Chemical Industries, Ltd. make]
EDTA: ethylenediamine tetra-acetic acid
The Cys:L-cysteine
Use the cleaning agent of embodiment 1～29 and comparative example 1～7, the contact angle of the water after pH, cleaning-1, cleaning-2, cleaning-3, cleaning-4, cleaning-5, etching, the cleaning, contact angle, surface roughness, foaming characteristic and the ageing stability of cleaning fluid are measured or estimated, and the result is shown in table 3 and table 4.
In addition, as follows the contact angle of the water after pH, cleaning-1, cleaning-2, cleaning-3, cleaning-4, cleaning-5, etching, the cleaning, contact angle, surface roughness, foaming characteristic and the ageing stability of cleaning fluid are measured or estimated.
The mensuration of＜pH 〉
Use pH meter (Horiba Ltd's (the Ku Games System of Co., Ltd. does institute) manufacturing, M-12) to measure for 25 ℃ in measuring temperature.
＜cleaning-1 〉
On commercially available glass substrate (manufacturing of Corning company, glass plate #1737, long 10cm * wide 10cm), to go up fusion 1 minute at 70 ℃ of heating plates (manufacturing of PMC Industries company, numeric type heating plate series 730) as positive melissane (Tokyo HuaCheng Industry Co., Ltd's manufacturing) 10mg of model pollutant matter, and make and pollute substrate.Get cleaning agent 1000g and put into 2L glass system beaker, the pollution substrate that dipping is made cleaned 5 minutes in 30 ℃ in supersonic wave cleaning machine (200kHz).After the cleaning, take out substrate, after the abundant rinsing of ultra-pure water, dry up, press commentary valency grade, adopt differential interference microscope (400 times of the manufacturings of Nikon company, OPTIPHOT-2, multiplying power) to estimate the cleaning of substrate surface with nitrogen.In addition, in order to prevent the pollution from atmosphere, this evaluation is carried out in 1,000 grade of (FED-STD-209D, u.s. federal standard, 1988) toilet.
◎: can roughly remove fully.
Zero: most of can cleaning
△: more residual particles
*: major part can not be cleaned
＜cleaning-2 〉
Coating is as dioctyl phthalate (Tokyo HuaCheng Industry Co., Ltd's manufacturing) 10mg of model pollutant matter, and in addition, other same cleanings-1 are estimated.
＜cleaning evaluation-3 〉
Glass dust 5mg when commercially available glass substrate (manufacturing of Corning company, glass plate #1737, long 10cm * wide 10cm) is gone up distribution cutting (cutting off) glass plate, go up heating 1 hour at 105 ℃ of heating plates (manufacturing of PMCIndustries company, numeric type heating plate series 730), make and pollute substrate, in addition, other same cleanings-1 are estimated.
＜cleaning-4 〉
Use is as the commercially available cataloid slurry (KEMIRA company (KEMIRA society) manufacturing, VI-80) and the abrasive cloth of grinding agent, after grinding commercially available glass substrate (manufacturing of Corning company, glass plate #1737, long 10cm * wide 10cm), with ultra-pure water rinsing surface, blow with nitrogen, make and pollute substrate, in addition, other same cleanings-1 are estimated.
＜cleaning evaluation-5 〉
Use is as the commercially available ceria slurry (Fujimi Incorporated company (Off ジ ミ イ Application コ one Port レ one テ イ De) manufacturing, CEPOL-120) and the abrasive cloth of grinding agent, after grinding commercially available glass substrate (manufacturing of Corning company, glass plate #1737, long 10cm * wide 10cm), with ultra-pure water rinsing surface, blow with nitrogen, make and pollute substrate, in addition, other same cleanings-1 are estimated.
＜etching evaluation 〉
Getting cleaning agent 10g adds in the 50ml polypropylene container made, after the adjustment to 50 ℃, put into the substrate that commercially available glass substrate (manufacturing of Corning company, glass plate #1737) is cut growth 2cm * wide 2cm size, in 50 ℃ of dippings, leave standstill 24 hours after, take cleaning agent, (manufacturing of VARIAN company, Varian730-ES) measures the Si content in the cleaning agent with the ICP apparatus for analyzing luminosity.In addition, in advance the cleaning agent before testing is measured Si content too, poor by obtaining it, thus obtain the Si content (ppb) of stripping in the test.The Si content of this stripping is many more, and etching is high more.
The contact angle of the water the after＜cleaning 〉
Use full-automatic contact angle meter [consonance the interface science (Association of Co., Ltd. and interface science Co., Ltd.) make, PD-W], soon substrate is to the contact angle (after 25 ℃, 10 seconds) of water behind the evaluation of measuring above-mentioned cleaning-1.
The contact angle of＜cleaning agent 〉
With commercially available glass substrate (manufacturing of Corning company, glass plate #1737, long 10cm * wide 10cm) with after the abundant rinsing of ultra-pure water, use full-automatic contact angle meter [consonance interface science Co., Ltd. makes, PD-W] after 25 ℃ of mensuration dry up with nitrogen soon substrate to the contact angle (after 25 ℃, 10 seconds) of cleaning agent.
＜surface roughness 〉
Getting cleaning agent 10g adds in the 20ml glass container made, after the adjustment to 50 ℃, put into the substrate that commercially available glass substrate (manufacturing of Corning company, glass plate #1737) is cut growth 2cm * wide 2cm size, in 50 ℃ of dippings, leave standstill 5 hours after, take out substrate with tweezers, after removing cleaning agent with the abundant rinsing of ultra-pure water, use AFM (SII NanoTechnology company makes, E-Sweep), the surface roughness (Ra) of the substrate surface that dries up with nitrogen in 25 ℃ of mensuration.Ra is more little, and surface is good more.
＜foaming characteristic 〉
In 100ml glass system band plug graduated cylinder (as the graduated cylinder of the band plug graduated cylinder given size of JIS R3504 " chemistry with stereometer glass material (chemical Yong Ti Plot Meter ガ ラ ス material) "), add the 20ml cleaning agent, in Water Tank with Temp.-controlled with after the adjustment to 25 ℃, cover the lid of band plug graduated cylinder, with thermal agitation 60 times up and down in 30 seconds, measure after the vibration soon with 1 minute after the amount (ml) of bubble.Soon the amount of bubble is few more after the vibration, and foaming characteristic is low more, and the amount of the bubble after 1 minute is few more, and defoaming is high more.
＜ageing stability 〉
Get cleaning agent 45ml and add in the 50ml glass container, under 5 ℃ and 50 ℃ of conditions, leave standstill and preserved 6 months, press commentary valency grade, the evaluation ageing stability.
◎: 5 ℃, 50 ℃ all do not have appearance change.
Zero: 5 ℃ or 50 ℃ is all slightly separated, becomes evenly but shake gently promptly.
△: 5 ℃ or 50 ℃ all have very big separation, become evenly but shake gently promptly.
*: 5 ℃, 50 ℃ are all separated, and shake gently also not become evenly.
Figure GPA00001153386100281
Figure GPA00001153386100291
Figure GPA00001153386100301
According to the result of record in table 3 and the table 4 as can be known, electronic material of the present invention has the etching of appropriateness control with the cleaning agent flatness on damaged substrate surface not, the removal of particles such as organic matter dirt, cullet and grinding agent and prevent that contaminative is good again.
Industrial applicibility
Cleaning agent for electronic materials of the present invention is applicable to the cleaning as cleaning object such as oil content, the organic matter such as dirt (fingerprint etc.), resin, plasticizer (dioctyl phthalate etc.), organic particle from human body and inorganic particle (glass dust, sand grains, ceramic powder and metal powder etc.).
Therefore, [for example flat-panel monitor is with substrate (liquid crystal board glass substrate applicable to various electronic materials for cleaning agent for electronic materials of the present invention, the coloured filter substrate, array (array) substrate, plasma scope with substrate and organic EL with substrate etc.), base board for optical mask, hard disk substrate (aluminium base, the NiP substrate, glass substrate, disk and magnetic head etc.), semiconductor substrate (semiconductor element and silicon wafer etc.), optical lens, the printed wire substrate, the optic communication cable, LED, solar cell is with substrate and crystal oscillator] manufacturing process in matting.
In addition, to be particularly suitable for electronic material be flat-panel monitor to the cleaning method of electronic material of the present invention with substrate, base board for optical mask, the hard disk situation with substrate or semiconductor substrate.

Claims (13)

1. electronic material cleaning agent, wherein, described cleaning agent contains anion component by the alkene of the anionic surfactant (A) of general formula (1) expression, carbon number 6～18 and be selected from the organic solvent more than a kind (B) in the group that the organic solvent by general formula (2) expression constitutes, and the SP value of above-mentioned (B) is 6～13;
R 1[-(OA 1) a-Q -] b (1)
In the formula (1), R 1Be the alkyl of carbon number 1～10, A 1Be the alkylidene of carbon number 2～4, Q -For-COO -,-OCH 2COO -,-SO 3 -,-OSO 3 -Or-OPO 2(OR 2) -, R 2Be the alkyl of hydrogen or carbon number 1～10, a is a mean value 0～20, and b is 1～6 integer, Q -For-COO -Or-SO 3 -The time a be 0;
R 3[-(OA 2) c-OH] d (2)
In the formula (2), R 3Be the alkyl of carbon number 1～12, A 2Be the alkylidene of carbon number 2～4, c is a mean value 0～20, and d is 1～6 integer.
2. electronic material cleaning agent as claimed in claim 1, wherein, the cation constituent of described anionic surfactant (A) is the cation more than a kind that is selected from the group that the monovalent cation on the alkanolamine that cation on the amidine compound that monovalent cation, proton on the aliphatic amine that alkali metal cation, proton add to carbon number 1～15 add to carbon number 4～10 and proton add to carbon number 1～15 constitutes.
3. electronic material cleaning agent as claimed in claim 1, wherein, in the general formula (1), R 1Be the alkyl of general formula (3) or general formula (4) expression,
[changing 1]
Figure FPA00001153386000011
In the formula (3), R 4And R 5The alkyl of representing carbon number 1～6 respectively independently, and R 4With R 5Carbon number add up to 3～8, e is 0～2 integer, R 4With R 5Carbon number add up at 8 o'clock, e is 0 or 1.
[changing 2]
Figure FPA00001153386000021
In the formula (4), f R 6The alkyl of representing hydrogen atom or carbon number 1～4 respectively independently, and f R 6Carbon number add up to below 4, f is 1～4 integer.
4. electronic material cleaning agent as claimed in claim 1, wherein, described cleaning agent further contains alkaline components (C), and in the time of 25 ℃, active ingredient concentration is that the pH of 0.1～15% cleaning agent is 10～14.
5. electronic material cleaning agent as claimed in claim 4, wherein, a in the general formula (1) be 0 and b be 1, the alkaline components more than a kind in the group that above-mentioned alkaline components (C) constitutes for the amidine compound (C-5) of the alkanolamine (C-4) of the aliphatic amine (C-2), the inorganic base (C-3) that are selected from carbon number 1～36, carbon number 1～23 and carbon number 4～10.
6. electronic material cleaning agent as claimed in claim 4, wherein, based on the weight of the active ingredient of cleaning agent, the content of above-mentioned (A) is that the content of 1～95 weight %, above-mentioned (B) is that the content of 2～95 weight % and above-mentioned (C) is 1～55 weight %.
7. electronic material cleaning agent as claimed in claim 4, wherein, described cleaning agent further contain be selected from the group that high-molecular type dispersing agent (D) and chelating agent (E) constitute more than a kind.
8. as each described electronic material cleaning agent in the claim 1～7, wherein, active ingredient concentration is that the cleaning agent of 0.1～15 weight % is below 10 ° to the contact angle of glass.
9. as each described electronic material cleaning agent in the claim 1～7, wherein, water is below 20 ° to the contact angle of the glass that the use cleaning agent cleaned.
10. as each described electronic material cleaning agent in the claim 1～7, wherein, described electronic material is the substrate of flat-panel monitor, the substrate of photomask, the substrate or the semi-conductive substrate of hard disk.
11. the cleaning method of an electronic material, wherein, described cleaning method uses each described cleaning agent in the claim 1～7.
12. the cleaning method of electronic material as claimed in claim 11, wherein, described cleaning method uses and is selected from that ultrasonic wave cleaning, spray Cleaning for High Capacity, spraying cleanings, brush cleaning, dipping are cleaned, the dipping swing is cleaned and the cleaning method more than a kind that one chip cleans in the group of formation cleans.
13. cleaning method as claimed in claim 11, wherein, described electronic material is the substrate of flat-panel monitor, the substrate of photomask, the substrate or the semi-conductive substrate of hard disk.
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