WO2013002281A1

WO2013002281A1 - Neutral salt for use in polishing liquid, electronic material polishing liquid, polishing method, and method of manufacturing electronic materials

Info

Publication number: WO2013002281A1
Application number: PCT/JP2012/066424
Authority: WO
Inventors: 山口　俊一郎
Original assignee: 三洋化成工業株式会社
Priority date: 2011-06-29
Filing date: 2012-06-27
Publication date: 2013-01-03
Also published as: TWI513804B; TW201307543A; CN103619982A; CN103619982B; MY163071A

Abstract

This invention comprises: a specific neutral salt (AB) used in a step for polishing an electronic material intermediary using a polishing pad; an electronic material polishing liquid containing said neutral salt (AB); a polishing method for polishing an electronic material intermediary using said electronic material polishing liquid; and a manufacturing method of an electronic material involving a step for polishing an electronic material intermediary with said polishing method. Here, the neutral salt (AB) is a salt of (A) an acidic compound having at least one acid radical (X) in the molecule, and (B) a nitrogen-containing basic compound having a 10-152 kcal/mol heat of formation change (Q2) in protonation reactions, wherein said neutral salt has a 3-200 kcal/mol heat of formation change (Q1) in acid dissociation reactions of the aforementioned acid radical (X). Thus provided is a material which, compared to conventional polishing liquids, results in fewer substrate defects such as scratches, which further, in a subsequent washing step, facilitates removal of polishing debris, and which further makes it possible to sustain polishing speed in the polishing step.

Description

Neutralizing salt for polishing liquid, polishing liquid for electronic material, polishing method and method for producing electronic material

The present invention relates to a neutralized salt used in a polishing step, a polishing liquid for electronic materials containing the neutralized salt, a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic materials, and an electron in this polishing method. The present invention relates to a method for manufacturing an electronic material including a step of polishing a material intermediate.
More specifically, a neutralized salt that is used in a polishing process during the manufacturing process of an electronic material, has a better polishing rate than conventional methods, and improves the surface quality of the electronic material, and an electronic material containing the neutralized salt The present invention relates to a polishing liquid for polishing, a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material, and a method for manufacturing an electronic material including a step of polishing the electronic material intermediate by the polishing method.

Electronic materials, especially magnetic disks, are becoming smaller and higher capacity year by year, and the distance between the magnetic head and the magnetic disk substrate is becoming smaller. Therefore, there is a demand for a substrate in which particles such as abrasive particles used for polishing and generated polishing scraps are not generated as much as possible in a cleaning step immediately after the polishing step in manufacturing a magnetic disk substrate. In recent years, reduction of surface defects such as scratches, pits, surface waviness and sagging has been demanded. Furthermore, in order to meet the recent strong demand, not only the quality of the substrate described above but also the production efficiency is further demanded, and specifically, the sustainability of the polishing rate is strongly demanded.

The magnetic disk manufacturing process includes a lapping process that is a process for chamfering a substrate plate, a substrate manufacturing process that is a process for creating a flattened substrate, and a medium that is a process for forming a magnetic layer on the substrate. Process.
Among these, in the lapping process, the main surface and end face of the substrate are polished using a polishing pad and a polishing liquid in which a grindstone such as diamond is fixed with a resin in order to roughly chamfer the substrate, and then the substrate is cleaned in a subsequent cleaning process. After removing the polishing scraps on the main surface and end face of the substrate, the processed substrate is transported to the substrate manufacturing process through a drying process.
In addition, in the substrate manufacturing process, polishing with a polishing pad and polishing liquid containing polishing particles such as colloidal silica and cerium oxide was performed to flatten the substrate, and polishing particles generated on the substrate surface were generated in the subsequent cleaning process. After removing particles such as polishing debris, the processed substrate is packed in a predetermined container through a drying process and transported to a media process.

Abrasive particles and generated polishing debris in the polishing liquid are very fine and easily aggregate. These aggregates may affect the surface quality of the substrate in the step of polishing the substrate. For example, resistance may be generated between these aggregates and the substrate, and scratches may be generated on the substrate. Scratches generated on the substrate may cause, for example, a poor adhesion between the magnetic film and the substrate in a later media process, and may be a factor that hinders the increase in the capacity of the magnetic disk.
Therefore, in order to suppress the above-described reduction in scratch generation and reduction in the polishing rate, polishing liquids containing azoles such as benzotriazole, maleic acid, and the like have been proposed (for example, Patent Documents 1 and 2).
Moreover, a polishing liquid containing an aromatic sulfonate has been proposed for the purpose of improving the durability of the polishing rate (for example, Patent Document 3).
In order to reduce the adhesion of particles to the substrate surface, a polishing liquid containing hydroxyethyl cellulose has been proposed (for example, Patent Document 4).

JP 2007-92064 A JP 2005-138197 A JP-A-08-109389 JP-A-11-116942

However, conventional polishing liquids as typified by Patent Documents 1 to 4 are not sufficient in suppressing the generation of scratches and adhesion of particles during polishing, and the substrate quality allowed to achieve high capacity is achieved. It could not be supported. Further, the polishing liquid of Patent Document 2 is not sufficient, although it has a slight effect on the sustainability of the polishing rate, and the substrate quality after polishing is not satisfactory.
Therefore, there are fewer defects in the substrate such as scratches in the polishing process during the electronic material manufacturing process than in conventional polishing liquids, and polishing debris generated by polishing can be easily removed in the subsequent cleaning process. A material capable of sustaining the polishing rate in the process, a polishing liquid for electronic material containing the material, a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material, and an electronic material intermediate by this polishing method It is an object of the present invention to provide a method for manufacturing an electronic material including a polishing step.

The inventor of the present invention has arrived at the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a specific neutralized salt (AB) used in the step of polishing an electronic material intermediate using a polishing pad, a polishing liquid for electronic material containing the neutralized salt (AB), and the electronic material A polishing method for polishing an electronic material intermediate using a polishing liquid, and an electronic material manufacturing method including a step of polishing an electronic material intermediate by the polishing method.
Here, the neutralized salt (AB) includes an acidic compound (A) having at least one acid group (X) in the molecule, and nitrogen having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol. A salt with the basic compound (B), which is a neutralized salt having a change in heat of formation (Q1) in the acid dissociation reaction of the acid group (X) of 3 to 200 kcal / mol.

The neutralized salt of the present invention used in the polishing step has an effect of significantly reducing surface defects generated on the surface of the object to be polished in the polishing step. Further, it has an effect of reducing adhesion of particles during polishing and facilitating removal of the particles from the substrate in the subsequent cleaning step. Moreover, the polishing liquid for electronic materials containing this neutralized salt is excellent in sustainability of the polishing rate, in addition to the above-described effects, as compared with the conventional polishing liquid. Therefore, an electronic material with few surface defects such as scratches or pits and / or residual particles can be stably produced.

The neutralized salt of the present invention is a specific neutralized salt (AB) used in the step of polishing an electronic material intermediate using a polishing pad. Here, the neutralized salt (AB) includes an acidic compound (A) having at least one acid group (X) in the molecule, and nitrogen having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol. A salt with a basic compound (B), which is a neutralized salt having a change in heat of formation (Q1) in the acid dissociation reaction of the acid group (X) of 3 to 200 kcal / mol.

The electronic material in the present invention is not particularly limited as long as it is an electronic material manufactured by a process including a process of polishing using a polishing pad during the manufacturing process.
For example, (1) a magnetic disk substrate such as a hard disk glass substrate or a hard disk aluminum substrate whose surface is plated with nickel-phosphorus (Ni-P), (2) a semiconductor substrate such as a semiconductor element or a silicon wafer, (3) Examples thereof include compound semiconductor substrates such as SiC substrates, GaAs substrates, GaN substrates, and AlGaAs substrates, and (4) sapphire substrates for LEDs.

Of these, a magnetic disk substrate is preferable from the viewpoint of improving production efficiency, and specifically, a glass substrate for hard disk or an aluminum substrate for hard disk plated with nickel-phosphorus (Ni-P).

The electronic material intermediate refers to an object to be polished before becoming an electronic material. For example, in the case of a glass substrate for hard disk, the glass substrate before lapping, or before rough polishing with cerium oxide or the like. It refers to a glass substrate, a glass substrate before being precisely polished with colloidal silica or the like, and all electronic materials before polishing processing mean an electronic material intermediate.

The polishing step in the present invention refers to a step of processing a material flat using a grindstone or abrasive particles, for example, a lapping step of rough chamfering using a polishing pad to which a grindstone is fixed, or using abrasive particles It includes a polishing process for precise planarization.

The polishing pad in the present invention is a pad made of polyurethane resin or polyester resin, and includes a pad on which a grindstone such as diamond is fixed. Further, it may be a foam type or a suede type, and various hardnesses can be used. These polishing pads are not particularly limited, and commercially available polishing pads can be used.
The polishing pad is used by being affixed to a surface plate of a polishing apparatus in the lapping step for rough chamfering described above or the polishing step for precise flattening using abrasive particles.

The neutralized salt (AB) in the present invention is a neutralized salt (AB1) of an acidic compound (A1) and a compound (B) and / or a neutralized salt of a polymer (A2) which is an acidic compound and a compound (B). (AB2).
The neutralized salt (AB1) comprises at least an acid group (X1) of an acid having a heat of formation (Q1) in an acid dissociation reaction of 3 to 200 kcal / mol and a hydrophobic group (Y) having 1 to 36 carbon atoms, respectively. A neutral salt of one acidic compound (A1) and a compound (B) having a heat of formation (Q2) of 10 to 152 kcal / mol in a proton addition reaction, wherein (X1) is a sulfonic acid group, sulfuric acid A neutralized salt which is at least one selected from the group consisting of a group, a carboxyl group, a carboxymethyloxy group, a carboxyethyloxy group, a (di) carboxymethylamino group and a (di) carboxyethylamino group, (AB2) includes a polymer (A2) that is an acidic compound having at least one acid group (X2) in the molecule, and a change in heat of formation (Q2) in the proton addition reaction. Is 0 ~ 152kcal / mol, compound (B) and neutralization salts.

The acidic compound (A1) includes at least one acid group (X1) of an acid having a heat of formation (Q1) in an acid dissociation reaction of 3 to 200 kcal / mol and a hydrophobic group (Y) having 1 to 36 carbon atoms. The polymer (A2) has at least one acid group (X2) in the molecule. The acid group (X2) also has a heat generation change (Q1) in the acid dissociation reaction of 3 to 200 kcal / mol.
The heat of formation (Q1) in the acid dissociation reaction of the acid groups (X1) and (X2) is the heat of formation of HX and the heat of formation of X ⁻ in the acid dissociation reaction of the acid (HX) represented by the following formula (1). Means the difference.
HX → H ⁺ + X ⁻ (1)
The change in the heat of formation in the acid dissociation reaction of the acid group (X1) is a value assuming that the hydrophobic group (Y) is a hydrogen atom.
In addition, the change in heat of formation in the acid dissociation reaction of the acid group (X2) is a value assuming that the polymer chain to which the acid group (X2) is bonded is a hydrogen atom.
For example, in the case of a sulfonic acid group (—SO ₃ H), a value calculated as H—SO ₃ H; in the case of a sulfate group (—OSO ₃ H), a value calculated as H—OSO ₃ H; a carboxyl group (—COOH ), The value calculated as H—COOH; in the case of carboxymethyloxy group (—OCH ₂ COOH), the value calculated as H—OCH ₂ COOH; in the case of carboxyethyloxy group (—OCH ₂ CH ₂ COOH), Calculated as H—OCH ₂ CH ₂ COOH; (di) In the case of a carboxymethylamino group (—NRCH ₂ COOH or —N (CH ₂ COOH) ₂ ), calculated as H—NHCH ₂ COOH; for carboxyethyl amino group _(-NRCH ₂ CH ₂ COOH or _{_{_{-N (CH 2 CH 2 COOH)}}} 2), H-NHCH Is a calculated value as CH ₂ COOH. R represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms (methyl, ethyl, propyl, butyl, octyl, nonyl, decyl, dodecyl, etc.).

That is, the generated heat change (Q1) is expressed by the following formula (2).
Q1 = Δ _f H ^o _HX −Δ _f H ^o _X− (2)
[In the formula, Δ _f H ^o _HX and Δ _f H ^o _X− represent the heat of formation in vacuum for HX and X ^{− in} order, respectively. ]

Here, the value of the heat of formation (Δ _f H ^o ) Chem. Soc. Perkin Trans. 2, p. 923 (1995), and can be calculated using the semiempirical molecular orbital method (MOPAC PM3 method).
The value of the generated heat can be calculated as generated heat (25 ° C.) in a vacuum using, for example, “CAChe Worksystem 6.01” manufactured by Fujitsu Limited. That is, the value of this heat of formation is calculated by writing the molecular structure to be calculated on “Work Space”, optimizing the structure with the molecular force field method “MM2 geometry”, and then “PM3 geometry” which is a semi-empirical molecular orbital method. Is obtained by calculation.

Further, the heat of formation (Q1) (kcal / mol, 25 ° C.) in the acid dissociation reaction of the acid group (X1) or (X2) is 3 to 200, and is preferably 10 from the viewpoint of lowering the zeta potential. To 150, then preferably 15 to 100, then preferably 20 to 80, particularly preferably 20 to 65.

As the acid group (X2), a sulfonic acid group (—SO ₃ H) (Q1 = 32 kcal / mol), a sulfuric acid group (—OSO ₃ H) (Q1 = 46 kcal / mol), a carboxyl group (—COOH) (Q1 = 21 kcal / mol), carboxymethyloxy group (—OCH ₂ COOH) (Q1 = 19 kcal / mol), carboxyethyloxy group (—OCH ₂ CH ₂ COOH) (Q1 = 20 kcal / mol), (di) carboxymethylamino group (—NRCH ₂ COOH or —N (CH ₂ COOH) ₂ ) (Q1 = 26 kcal / mol), (di) carboxyethylamino group (—NRCH ₂ CH ₂ COOH or —N (CH ₂ CH ₂ COOH) ₂ ) ( Q1 = 20 kcal / mol).
Among these acid groups, sulfonic acid groups, sulfuric acid groups, or carboxyl groups are preferable from the viewpoint of preventing re-adhesion of particles and easy industrial production, and the viewpoint of preventing hydrolysis of the neutralized salt (AB2). More preferably a sulfonic acid group or a carboxyl group.

As the acid group (X1), among the acid groups (X2) exemplified above, a sulfonic acid group, a sulfuric acid group, a carboxyl group, a carboxymethyloxy group, a carboxyethyloxy group, a (di) carboxymethylamino group, ) Carboxyethylamino group and the like.
Of these acid groups, sulfonic acid groups, sulfuric acid groups, carboxymethyloxy groups, or carboxyethyloxy groups are preferable from the viewpoint of preventing re-adhesion of particles and industrially easy production, and the neutral salt (AB1). From the viewpoint of preventing hydrolysis and the like, a sulfonic acid group, a carboxymethyloxy group or a carboxyethyloxy group is more preferable, and a sulfonic acid group is particularly preferable.

Examples of the hydrophobic group (Y) in the acidic compound (A1) include an aliphatic hydrocarbon group and an aromatic ring-containing hydrocarbon group.
Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, a cycloalkyl group having 3 to 36 carbon atoms, and the like (which may be linear or branched) ).
Examples of the alkyl group include methyl, ethyl, n- or i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
Alkenyl groups include n- or i-propenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl and the like.

Examples of the cycloalkyl group having 3 to 36 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the aromatic ring-containing hydrocarbon group include aromatic hydrocarbons having 7 to 36 carbon atoms, such as methylphenyl, ethylphenyl, n- or i-propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, Examples include octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, octylnaphthyl, nonylnaphthyl, dodecylnaphthyl and the like.

Of the hydrophobic group (Y), an aliphatic hydrocarbon group or an aromatic ring-containing hydrocarbon group is preferable, and more preferable is octyl, nonyl, decyl, undecyl, dodecyl, octylphenyl, nonylphenyl, dodecylphenyl, octylnaphthyl, nonyl. Naphthyl and dodecylnaphthyl, particularly preferably octyl, nonyl, dodecyl, octylphenyl, dodecylphenyl and octylnaphthyl.

The number of carbon atoms of the hydrophobic group (Y) is 1 to 36, more preferably 4 to 24, and particularly preferably 8 to 24. In these hydrophobic groups, some or all of the hydrogen atoms are other atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) or functional groups (hydroxyl group, amino group, mercapto group, perfluoroalkyl group, carboxyl group) Or an organic group including an ether bond, an amide bond, or an ester bond), and the functional group may include one or more oxyalkylene groups.

Examples of the acidic compound (A1) include the following compounds.
Compound having sulfonic acid group (A1-1)
Alkylsulfonic acid (octylsulfonic acid, decylsulfonic acid, dodecylsulfonic acid, myristylsulfonic acid, cetylsulfonic acid, stearylsulfonic acid, etc.), benzenesulfonic acid, alkylbenzenesulfonic acid (toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid) , Eicosylbenzenesulfonic acid, etc.), naphthalenesulfonic acid, sulfosuccinic acid, alkylnaphthalenesulfonic acid (methylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, eicosylnaphthalenesulfonic acid, etc.), polyoxyalkylene alkyl ether sulfonic acid (polyoxyethylene) Octyl ether sulfonic acid, polyoxyethylene lauryl ether sulfonic acid, etc.), α-olefin sulfonic acid, alkyloylaminoethyl sulfone Etc. The.

Compound having a sulfate group (A1-2)
Alkyl sulfate (octyl sulfate, decyl sulfate, dodecyl sulfate, myristyl sulfate, cetyl sulfate, stearyl sulfate, etc.), polyoxyalkylene alkyl ether sulfate (polyoxyethylene octyl ether sulfate, polyoxyethylene lauryl) Ether sulfates, etc.), polyoxyalkylene alkyl aryl ether sulfates (polyoxyethylene octyl phenyl ether sulfates, polyoxyethylene nonyl phenyl ether sulfates, etc.), acylamide alkyl sulfates, and the like.

Among these, alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, sulfosuccinic acid, polyoxyalkylene alkyl ether sulfonic acid, polyoxyalkylene alkylaryl ether sulfonic acid, α-olefin sulfonic acid, alkyloylaminoethyl sulfonic acid, Alkyl sulfate ester, polyoxyalkylene alkyl ether sulfate ester, polyoxyalkylene alkyl aryl ether sulfate ester, and acylamide alkyl sulfate ester are preferable, and alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, sulfosuccinic acid, polyoxy are more preferable. Alkylene alkyl ether sulfonic acid, polyoxyalkylene alkyl aryl ether sulfonic acid, α-o Refin sulfonic acid, alkyloylaminoethyl sulfonic acid.

The HLB value of the acidic compound (A1) is preferably 5 to 30, more preferably 7 to 17, more preferably 9 to 16, particularly preferably 10 to 15, and most preferably 10.5 to 14.5.
In the present invention, the HLB value is a value calculated using the following formula (3) by the Oda method (Takehiko Fujimoto, Introduction to Surfactant (Sanyo Chemical Industry Co., Ltd.), p212 (2007)). .

HLB = 10 × (inorganic / organic) (3)
In addition, the organic property and inorganic property in a formula are the total value of the numerical value defined for every atom and functional group which comprise a molecule | numerator, and can use the value described in the said literature.

The pKa of the acidic compound (A1) is preferably 8.0 or less, more preferably 7.0 or less, particularly preferably 5.5 or less, and most preferably 3.0 or less from the viewpoint of lowering the zeta potential. . Moreover, Preferably it is 0.5 or more. Here, pKa means the acid dissociation constant at the first stage. In addition, pKa is a known method {for example, J.P. Am. Chem. Soc. , 1673 (1967)} and the like.

Examples of the polymer (A2) having at least one acid group (X2) include a polymer having a sulfonic acid group (A2-1) and a polymer having a sulfate group (A2-2) from the viewpoint of preventing reattachment of particles. Alternatively, a polymer (A2-3) having a carboxyl group is preferable, and a polymer (A2-1) having a sulfonic acid group or a polymer (A2-3) having a carboxyl group is more preferable.

Examples of the polymer (A2-1) having a sulfonic acid group include a polymer (A2-1-1) obtained by radical polymerization using an unsaturated monomer (aX-1) having a sulfonic acid group, and a sulfonic acid group in the molecule. And a polymer (A2-1-2) obtained by a polycondensation reaction with formaldehyde using an aromatic compound (aY-1) having

Examples of the polymer (A2-2) having a sulfate group include a polymer (A2-2-1) obtained by radical polymerization using an unsaturated monomer (aX-2) having a sulfate group.

Examples of the polymer (A2-3) having a carboxyl group include a polymer (A2-3-1) obtained by radical polymerization using an unsaturated monomer (aX-3) having a carboxyl group.

Among the polymers (A2), from the viewpoint of preventing particle reattachment, a polymer (A2-3) having a carboxyl group and a polymer (A2-1) having a sulfonic acid group are preferable, and (A2-3) is more preferable. -1), (A2-1-1) or (A2-1-2).
Although the polymer (A2) used for this invention may be used independently, it can also be used as a 2 or more types of mixture.

Examples of the unsaturated monomer (aX-1) having a sulfonic acid group include aliphatic unsaturated sulfonic acids having 2 to 20 carbon atoms (such as vinyl sulfonic acid and (meth) allyl sulfonic acid), and aromatics having 6 to 24 carbon atoms. Unsaturated sulfonic acid (styrene sulfonic acid, p-nonyl styrene sulfonic acid, etc.), sulfonic acid group-containing (meth) acrylate {2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3 -(Meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p -(Meth) acryloyloxymethylbenzenesulfonic acid, etc.}, including sulfonic acid group (Meth) acrylamide {2- (meth) acryloyl-aminoethanesulfonic acid, 2- (meth) acryloyl-2,2-dimethyl-ethanesulfonic acid, etc.} and the like.
Among these, from the viewpoints of polymerizability and hydrolysis resistance in water, etc., it contains an aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms, an aromatic unsaturated sulfonic acid having 6 to 24 carbon atoms or a sulfonic acid group (meta ) Acrylamide is preferred, and vinyl sulfonic acid, styrene sulfonic acid or 2- (meth) acryloylamino-2,2-dimethylethane sulfonic acid is more preferred.

Examples of the unsaturated monomer (aX-2) having a sulfate group include sulfate ester of a hydroxyl group-containing monomer.
Of these, from the viewpoint of polymerizability and the like, a hydroxyl group-containing (meth) acrylic acid ester sulfate is preferable, and a 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate sulfate is more preferable. .

As unsaturated monomer (aX-3) having a carboxyl group, unsaturated monocarboxylic acid {(meth) acrylic acid, vinylbenzoic acid, allyl acetic acid, (iso) crotonic acid, cinnamic acid, 2-carboxyethyl acrylate, etc. }, Unsaturated dicarboxylic acid or anhydride of unsaturated dicarboxylic acid {(anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc.}.
Of these, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or anhydride of unsaturated dicarboxylic acid is preferable from the viewpoint of polymerizability and hydrolysis resistance in water, and more preferably (meth) acrylic acid, (anhydrous) ) Maleic acid, fumaric acid or (anhydrous) itaconic acid.

Polymers (A2-1-1) to (A2-3-1) obtained by radical polymerization using unsaturated monomers include unsaturated monomers having sulfonic acid groups (aX-1) and unsaturated monomers having sulfuric acid groups. A radically polymerizable unsaturated monomer other than the monomer (aX-2) and the unsaturated monomer having a carboxyl group (aX-3) can be copolymerized.

Monomers (aX-1) to (aX-3) may be used alone or as a mixture of two or more. In the case of a copolymer, the structure may be either a random copolymer or a block copolymer.

Specific examples of the polymer (A2-1-1) include polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, poly {2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid}, 2- ( (Meth) acryloylamino-2,2-dimethylethanesulfonic acid / styrene copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / acrylamide copolymer, or 2- (meth) acryloylamino -2,2-dimethylethanesulfonic acid / styrene / acrylamide copolymer.

Specific examples of the polymer (A2-2-1) include poly {2-hydroxyethyl (meth) acrylate sulfate}, 2-hydroxyethyl acrylate / 2-hydroxyethyl acrylate sulfate copolymer, 2-hydroxyethyl methacrylate. / 2-hydroxyethyl methacrylate sulfate copolymer and the like.

Specific examples of the polymer (A2-3-1) include poly (meth) acrylic acid, (meth) acrylic acid / vinyl acetate copolymer, 2-hydroxyethyl methacrylate / (meth) acrylic acid copolymer, and the like. It is done.

As a synthesis method of the polymers (A2-1-1) to (A2-3-1) obtained by radical polymerization using an unsaturated monomer, a known radical polymerization method can be used. For example, a monomer comprising monomers (aX-1) to (aX-3) and other radical polymerizable unsaturated monomers as required, and a radical initiator (persulfate, azobisamidinopropane salt, azobisisobutylnitrile, etc.) Is polymerized at a temperature of 30 to 150 ° C. in a solvent such as water or an alcohol solvent using 0.1 to 30% by weight based on the monomer. If necessary, a chain transfer agent such as mercaptan may be used.

Examples of the aromatic compound (aY-1) having a sulfonic acid group used for the synthesis of the polymer (A2-1-2) include aryl sulfonic acid (benzenesulfonic acid, etc.), alkyl (carbon number 1 to 24) aryl sulfone. Acids (toluenesulfonic acid, dodecylbenzenesulfonic acid, monobutylbiphenylsulfonic acid, etc.), polycyclic aromatic sulfonic acids (naphthalenesulfonic acid, anthracenesulfonic acid, hydroxynaphthalenesulfonic acid, hydroxyanthracenesulfonic acid, etc.), alkyl (carbon number) 1-24) substituted polycyclic aromatic sulfonic acid {alkyl (carbon number 1-24) naphthalenesulfonic acid (methylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, Urylnaphthalenesulfonic acid, eicosylnaphthalenesulfonic acid, etc.), methylanthracenesulfonic acid, laurylanthracenesulfonic acid, eicosylanthracenesulfonic acid, etc.}, phenolsulfonic acid (phenolsulfonic acid, monobutylphenylphenol monosulfonic acid, dibutylphenylphenol) Disulfonic acid, etc.), alkyl (C1-C24) phenolsulfonic acid (cresolsulfonic acid, nonylphenolsulfonic acid, eicosylphenolsulfonic acid, etc.), aromatic aminosulfonic acid (anilinesulfonic acid, etc.), ligninsulfonic acid (lignin) Sulfonates, modified lignin sulfonic acids, etc.), sulfonic acid group-containing compounds having a triazine ring (such as melamine sulfonic acid), and the like.
Of these, alkyl (C1-24) arylsulfonic acid, polycyclic aromatic sulfonic acid, and alkyl (C1-24) substituted polycyclic aromatic sulfonic acid are preferable from the viewpoint of preventing redeposition. More preferred are dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and dimethylnaphthalenesulfonic acid.

In addition to the aromatic compound (aY-1) having a sulfonic acid group, the polymer (A2-1-2) can contain other aromatic compound (aO), urea, or the like as necessary, if necessary.
Other aromatic compounds (aO) include benzene, alkylbenzene (alkyl group having 1 to 20 carbon atoms), naphthalene, alkylnaphthalene (alkyl group having 1 to 20 carbon atoms), phenol, cresol, hydroxynaphthalene, aniline, and the like. Can be mentioned.

Specific examples of the polymer (A2-1-2) include naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, dimethyl naphthalene sulfonic acid formaldehyde condensate, octyl naphthalene sulfonic acid formaldehyde condensate, naphthalene sulfonic acid-methyl. Naphthalene-formaldehyde condensate, naphthalene sulfonic acid-octyl naphthalene-formaldehyde condensate, hydroxy naphthalene sulfonic acid formaldehyde condensate, hydroxy naphthalene sulfonic acid-cresol sulfonic acid-formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate And aniline sulfonic acid-phenol-formaldehyde condensate.

As a synthesis method of the polymer (A2-1-2), a known method can be used. For example, the reaction vessel is charged with the aromatic compound (aY-1) having the sulfonic acid group and, if necessary, other compounds (aO), urea, an acid (such as sulfuric acid) or an alkali (such as sodium hydroxide) used as a catalyst. A predetermined amount of an aqueous formaldehyde solution (for example, 37% by weight aqueous solution) is dropped over 1 to 4 hours with stirring at 70 to 90 ° C., and after the dropwise addition, the mixture is stirred for 3 to 30 hours under reflux and cooled. .
Further, as the compound (aY-1), a polymer (A2-1-2) was synthesized at the same time using a compound in which a part or all of the sulfonic acid groups had been neutralized with the compound (B) in advance, and at the same time a directly neutralized salt ( AB2) may be obtained.
When other compound (aO) is used, the molar ratio ((aY-1) / (aO)} of (aY-1) to (aO) is preferably 1 to 99/99 to 1, more preferably 10 ˜90 / 90˜10, particularly preferably 30˜85 / 70˜15, most preferably 50˜80 / 50˜20.

When urea is used, the molar ratio of (aY-1) to urea {(aY-1) / urea} is preferably 1 to 99/99 to 1, more preferably 10 to 90/90 to 10, particularly preferably. Is from 30 to 85/70 to 15, most preferably from 50 to 80/50 to 20.

Further, (aY-1) or (aO) may be used as a mixture of two or more.
The pKa of the polymer (A2) is preferably 8.0 or less, more preferably 7.0 or less, particularly preferably 5.5 or less, and most preferably 3.0 or less from the viewpoint of lowering the zeta potential. pKa can be determined by the above method.

The weight average molecular weight (hereinafter abbreviated as Mw) of the polymer (A2) is preferably from 300 to 200,000, more preferably from 1,000 to 100, from the viewpoint of improving surface quality such as scratch reduction and low foaming properties. , 000.
The weight average molecular weight is a value measured by gel permeation chromatography (hereinafter abbreviated as GPC) at 40 ° C. using polyethylene oxide as a standard substance. For example, apparatus main body: HLC-8120 manufactured by Tosoh Corporation, column: TSKgel G5000 PWXL, G3000 PW XL manufactured by Tosoh Corporation, detector: differential refractometer detector built in the apparatus main body, eluent: 0.2 M sulfuric anhydride Sodium, 10% acetonitrile buffer, eluent flow rate: 0.8 ml / min, column temperature: 40 ° C., sample: 1.0 wt% eluent solution, injection volume: 100 μl, standard substance: TSK manufactured by Tosoh Corporation It can be measured under the conditions of SE-30, SE-15, SE-8, and SE-5.

Next, the compound (B) constituting the neutralized salts (AB1) and (AB2) will be described.
In the present invention, a compound (B) having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol is used.
In the present invention, the change in heat of formation (Q2) in the proton addition reaction means the difference between the heat of formation of B and the heat of formation of H ⁺ B in the proton addition reaction of the compound (B) represented by the following formula (4). .
B + H ⁺ → H ⁺ B (4)

That is, Q2 is represented by the following formula (5).
_{^{_{Q2 = Δ f H o H +}}} B -Δ f H o B (5)
_{^{_{Wherein, Δ f H o H + B}}} , Δ f H o B are respectively ^a representing the generated heat in a vacuum for ^H + B, B. ]

As described above, the value of the heat of formation (Δ _f H ^o ) can be calculated using the semiempirical molecular orbital method (MOPAC PM3 method).
In addition, the position where H ⁺ is added in calculating the heat of formation of H ⁺ B is on the nitrogen atom contained in the compound (B). When there are a plurality of nitrogen atoms, the heat of formation is calculated for each nitrogen atom, and the value when the difference between the heat of formation of B and the heat of formation of H ⁺ B is minimized is defined as the change in heat generation (Q2). .

The change in heat of formation (Q2) (kcal / mol, 25 ° C.) in the proton addition reaction of compound (B) is 10 to 152, preferably 30 to 148, more preferably 40 from the viewpoint of lowering the zeta potential. To 145, particularly preferably 50 to 143, most preferably 100 to 141.

The compound (B) is not limited as long as the change in heat of formation (Q2) in the proton addition reaction is in the range of 10 to 152 kcal / mol. For example, the compound (B-1) having at least one guanidine skeleton in the molecule And a compound (B-2) having at least one amidine skeleton in the molecule.

The molecular volume (nm ³ ) of the compound (B) is preferably from 0.025 to 0.7, more preferably from 0.050 to 0.5, particularly preferably from 0.12 to 0.5 from the viewpoint of lowering the zeta potential. 0.36.
Here, the molecular volume refers to the volume of the space formed on the isoelectronic density surface of the molecule, and is the molecular force field method MM2 (Allinger, NL, J. Am. Chem. Soc., 99, 8127 (1977). ))) And an optimized structure calculated using PM3 (Stewart, J. J. P., J. Am. Chem. Soc., 10, 221 (1989)), which is a semi-empirical molecular orbital method. it can. For example, after using the above-mentioned “CAChe Worksystem 6.01” manufactured by Fujitsu Limited, the structure is optimized in the same manner, and then the calculation is performed by “PM3 geometry” which is a semi-empirical molecular orbital method on “Project Leader”. it can. As a result of the calculation, when a plurality of molecular volume values are obtained, the maximum value is used.

Specific examples of the compound (B-1) include guanidine {guanidine (Q2 = 147 kcal / mol, molecular volume = 0.062 nm ³ ), methylguanidine (Q2 = 144 kcal / mol, molecular volume = 0.084 nm ³ ), tetra Methyl guanidine (Q2 = 145 kcal / mol, molecular volume = 0.147 nm ³ ), ethyl guanidine (Q2 = 142 kcal / mol, molecular volume = 0.104 nm ³ ), phenyl guanidine (Q2 = 141 kcal / mol, molecular volume = 0. 139 nm ³ ), etc.}, monocyclic guanidine [2-amino-imidazole {2-amino-1H-imidazole (Q2 = 146 kcal / mol, molecular volume = 0.080 nm ³ ), 2-dimethylamino-1H-imidazole (Q2 = 138 kcal / mol, molecular volume 0.113nm ³⁾ such}], polycyclic guanidine {1,3,4,6,7,8-hexahydro -2H- pyrimido [1,2-a] pyrimidine (hereinafter TBD abbreviated) (Q2 = 147kcal / mol, molecular volume = 0.159 nm ³ ), 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido [1,2-a] pyrimidine (hereinafter abbreviated as MTBD) (Q2 = 139 kcal) / Mol, molecular volume = 0.180 nm ³ ), etc.}.

Specific examples of the compound (B-2) include imidazole {1H-imidazole (Q2 = 147 kcal / mol, molecular volume = 0.067 nm ³ ), 2-methyl-1H-imidazole (Q2 = 144 kcal / mol, molecular volume = 0.113 nm ³ ), 2-ethyl-1H-imidazole (Q2 = 143 kcal / mol, molecular volume = 0.113 nm ³ ), 4,5-dihydro-1H-imidazole (Q2 = 147 kcal / mol, molecular volume = 0.0.1). 113 nm ³ ), 2-methyl-4,5-dihydro-1H-imidazole (Q2 = 147 kcal / mol, molecular volume = 0.113 nm ³ ), 2-ethyl-4,5-dihydro-1H-imidazole (Q2 = 145 kcal) / mol, molecular volume = 0.119nm ³⁾ such}, represented by the following general formula (6) Such as bicyclic amidines that are mentioned.

[Wherein R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an alkyl group having 6 to 30 carbon atoms. Represents an aryl group or an arylalkyl group having 7 to 30 carbon atoms, and a part or all of hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, aryl group or arylalkyl group are a hydroxyl group, an amino group, (di) Further substituted by alkyl (1 to 24 carbon) amino group, (di) hydroxyalkyl (2 to 4 carbon) amino group, mercapto group or halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) Also good. Further, two R ⁷ and two R ⁸ may be the same or different and are bonded to each other (carbon-carbon bond, ether bond, etc.) to form a ring having 4 to 12 carbon atoms. Also good. m and n each independently represent an integer of 1 to 12. ]

Examples of the alkyl group having 1 to 24 carbon atoms or the alkenyl group having 2 to 24 carbon atoms include those having 1 to 24 carbon atoms among the alkyl groups and alkenyl groups exemplified for the hydrophobic group (Y).
The alkynyl group having 2 to 30 carbon atoms may be linear or branched, and is ethynyl, 1-propynyl, 2-propynyl, 1- or 2-dodecynyl, 1- or 2-tridecynyl, 1- or 2 -Tetradecynyl, 1- or 2-hexadecynyl, 1- or 2-stearinyl, 1- or 2-nonadecynyl, 1- or 2-eicosinyl, 1- or 2-tetracosinyl and the like.

Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and methylnaphthyl.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 7-phenylheptyl, 8-phenyloctyl, 10 -Phenyldecyl, 12-phenyldodecyl, naphthylmethyl, naphthylethyl and the like.

When two R ⁷ or two R ⁸ are bonded to each other to form a ring having 4 to 12 carbon atoms, two R ⁷ or two R ⁸ are divalent organic groups (alkylene having 4 to 12 carbon atoms). Group).
Examples of the alkylene group having 4 to 12 carbon atoms include butylene, pentylene, hexylene, heptylene, octylene, decylene and dodecylene, and these alkylene groups may be bonded by an ether bond or the like.

Specific examples of the compound represented by the general formula (6) include 1,8-diazabicyclo [5.4.0] undecene-7 (hereinafter abbreviated as DBU. DBU is a registered trademark of Sun Apro). (Q2 = 137 kcal / mol, molecular volume = 0.185 nm ³ ), 1,5-diazabicyclo [4.3.0] nonene-5 (hereinafter abbreviated as DBN) (Q2 = 141 kcal / mol, molecular volume = 0.146 nm) ³ ), 1,8-diazabicyclo [5.3.0] decene-7 (Q2 = 142 kcal / mol, molecular volume = 0.166 nm ³ ), 1,4-diazabicyclo [3.3.0] octene-4 ( Q2 = 146 kcal / mol, molecular volume = 0.126 nm ³ ) and the like.

Preferred from the viewpoint of zeta potential and the like as compound (B) are guanidine, methylguanidine, ethylguanidine, (B-2) of (B-1), DBU and DBN, and more preferably DBU. Or DBN.
A compound (B) may be used independently and may be used as a 2 or more types of mixture.

The pKa of the compound (B) is preferably 11 to 40, more preferably 11.5 to 30, particularly preferably 12 to 25 from the viewpoint of lowering the zeta potential.
In addition, pKa of compound (B) is a known method {for example, Can. J. et al. Chem. 65, 626 (1987)} and the like.

In the present invention, the neutralized salt (AB1) of the acidic compound (A1) and the compound (B) and the neutralized salt (AB2) of the polymer (A2) and the compound (B) are the acid group (X1) or (X2 ) May be partially or completely neutralized with (B).

Specific examples of the neutralized salt (AB1) include the following compounds.
Alkylbenzenesulfonate (toluenesulfonate guanidine salt, toluenesulfonate DBU salt, toluenesulfonate DBN salt, xylenesulfonate guanidine salt, xylenesulfonate DBU salt, xylenesulfonate DBN salt, dodecylbenzenesulfonate guanidine salt, dodecylbenzene Sulfonic acid DBU salt, dodecylbenzene sulfonic acid DBN salt, etc.), naphthalene sulfonic acid salt (naphthalene sulfonic acid guanidine salt, naphthalene sulfonic acid DBU salt, naphthalene sulfonic acid DBN salt etc.), alkyl naphthalene sulfonic acid salt (methyl naphthalene sulfonic acid guanidine) Salt, methyl naphthalene sulfonic acid DBU salt, methyl naphthalene sulfonic acid DBN salt, dodecyl naphthalene sulfonic acid guanidine salt, dodecyl naphthalene sulfonic acid DB Salts, such as dodecyl naphthalenesulfonate DBN salt), and the like.

Specific examples of the neutralized salt (AB2) include the following compounds.
Polyacrylate (polyacrylic acid DBU salt, polyacrylic acid DBN salt, etc.), polystyrene sulfonate (polystyrene sulfonic acid guanidine salt, polystyrene sulfonic acid DBU salt, polystyrene sulfonic acid DBN salt, etc.), naphthalene sulfonic acid formaldehyde condensate Salts of naphthalene sulfonic acid formaldehyde condensate guanidine salt, naphthalene sulfonic acid formaldehyde condensate DBU salt, naphthalene sulfonic acid formaldehyde condensate DBN salt, etc., alkyl naphthalene sulfonic acid formaldehyde condensate salt (methyl naphthalene sulfonic acid formaldehyde condensate guanidine Salt, methyl naphthalene sulfonic acid formaldehyde condensate DBU salt, methyl naphthalene sulfonic acid formaldehyde condensate DBN salt, methyl naphthalene Sulfonic acid formaldehyde condensate TBD salt, methyl naphthalene sulfonic acid formaldehyde condensate MTBD salt, octyl naphthalene sulfonic acid formaldehyde condensate guanidine salt, octyl naphthalene sulfonic acid formaldehyde condensate DBU salt, octyl naphthalene sulfonic acid formaldehyde condensate DBN salt, etc.) Naphthalenesulfonic acid-alkylnaphthalene-formaldehyde condensate salt (naphthalenesulfonic acid-octylnaphthalene-formaldehyde condensate guanidine salt, naphthalenesulfonic acid-octylnaphthalene-formaldehyde condensate DBU salt, naphthalenesulfonic acid-octylnaphthalene-formaldehyde condensate DBN Salt, etc.). (AB1) and (AB2) may be single or a mixture of two or more.

The neutralized salt (AB1) is preferably such that the ratio {Q2 / (Q1 × p)} of (Q1) and (Q2) satisfies the formula (7) from the viewpoint of reducing the zeta potential, and more preferably It is preferable to satisfy the formula (8), particularly preferably the formula (9), and most preferably the formula (10).
0.01 ≦ {Q2 / (Q1 × p)} ≦ 3.0 (7)
0.1 ≦ {Q2 / (Q1 × p)} ≦ 2.5 (8)
0.2 ≦ {Q2 / (Q1 × p)} ≦ 2.3 (9)
0.5 ≦ {Q2 / (Q1 × p)} ≦ 2.2 (10)
[Wherein, p represents the number of acid groups (X) necessary for neutralizing the basic compound (B). ]

The weight average molecular weight (Mw) of the neutralized salt (AB2) is preferably 1,000 to 1,000,000, more preferably 1,000 to 1,000, from the viewpoint of improving surface quality such as scratch reduction and low foaming properties. 200,000, particularly preferably 3,000 to 100,000. In addition, Mw of neutralization salt (AB2) is a value obtained by GPC similarly to a polymer (A2).

The polishing liquid for electronic material of the present invention may contain at least one of neutralized salts (AB1) and (AB2), but contains neutralized salt (AB2) from the viewpoint of improving surface quality such as scratch reduction. Those are preferred.

The neutralized salt (AB1) or (AB2) can be obtained by a neutralization reaction between the acidic compound (A1) or polymer (A2) and the nitrogen-containing basic compound (B). For example, an aqueous solution of (A1) and / or (A2) is charged into a reaction vessel capable of temperature control and stirring, and (B) (aqueous solution if necessary) is added at room temperature (about 25 ° C.) with stirring to mix uniformly. can do. Further, for example, it can be obtained by mixing (A1) and / or (A2) and (B) simultaneously or separately into a reaction vessel preliminarily charged with water and mixing them uniformly. The concentration during the neutralization reaction can be appropriately selected depending on the purpose.

Since the polishing liquid for electronic materials of the present invention has a high degree of dissociation of the acid groups (X1) and (X2), the zeta potential of the particles and the substrate can be effectively lowered, and the reattachment of particles can be prevented. it can.

The concentration of the neutralized salt (AB) in the polishing slurry for electronic materials is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the weight of the polishing solution.

The water that is an essential component of the polishing liquid for electronic materials of the present invention is preferably pure water having an electrical resistivity of 18 MΩ · cm or more from the viewpoint of cleanliness, ultrapure water, ion exchange water, reverse osmosis water (RO water). And distilled water.

Another embodiment of the present invention is a polishing liquid for use in a step of polishing an electronic material intermediate using a polishing pad, which is a polishing liquid for an electronic material that requires neutralization salt (AB) and water as essential. .

The polishing liquid for electronic materials of the present invention may contain abrasive particles (C) in addition to the neutralized salt (AB) and water described above. By containing the abrasive particles (C), an electronic material excellent in flatness can be produced.

As the abrasive particles (C) in the present invention, commercially available abrasive particles for polishing electronic materials can be used and are not particularly limited. Examples of the material for the abrasive particles (C) include colloidal silica, cerium oxide, alumina, zirconium oxide, diamond, manganese oxide, titanium oxide, silicon carbide, and boron nitride. From the viewpoint of the effect of reducing scratches, colloidal is preferable. Silica, cerium oxide, alumina or diamond.

The average particle diameter of the abrasive particles (C) varies depending on the abrasive particles used. In the case of colloidal silica, it is usually 5 nm to 100 nm, and in the case of cerium oxide, it is 0.1 μm to 3.0 μm. This is preferable from the viewpoint of substrate productivity.

The abrasive particles (C) in the polishing liquid for electronic materials is 0 to 20% by weight, preferably 0.5 to 20% by weight, based on the weight in the polishing liquid.

The polishing liquid for electronic materials of the present invention may contain a surfactant (D) other than the neutralized salt (AB) and water described above, in addition to the neutralized salt (AB). By containing the surfactant (D), it can be used in the lapping step.

Examples of the surfactant (D) in the present invention include nonionic surfactants (D1) and anionic surfactants (D2) other than neutralized salts (AB).

Nonionic surfactant (D1) includes higher alcohol alkylene having 8 to 18 carbon atoms (2 to 4 carbon atoms) oxide adduct (D11), polyoxyethylene polyoxypropylene copolymer (D12), 8 carbon atoms. Examples include an alkylene oxide adduct (D13) of aliphatic amine of ˜36, a polyhydric alcohol type nonionic surfactant (D14), and the like.

Examples of the higher alcohol alkylene (carbon number 2 to 4) oxide adduct (D11) having 8 to 18 carbon atoms include octyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, and the like. Can be mentioned.

The polyoxyethylene polyoxypropylene copolymer (D12) may be a block type or a random type.

Examples of the alkylene oxide adduct (D13) of an aliphatic amine having 8 to 36 carbon atoms include an alkylene oxide adduct (D131) of an aliphatic primary amine having 8 to 24 carbon atoms, or an aliphatic oxide having 8 to 36 carbon atoms. An alkylene oxide adduct (D132) of a group secondary amine.

The starting aliphatic primary amine in the alkylene oxide adduct (D131) of an aliphatic primary amine having 8 to 24 carbon atoms may be linear, branched or cyclic, and may have a saturated or unsaturated bond. It is an aliphatic primary amine having 8 to 24 carbon atoms.
Specific examples of the aliphatic primary amine include laurylamine, octylamine, decylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine , Heicosylamine, docosylamine, tricosylamine, tetracosylamine, octadecenylamine or octadecadienylamine, and mixtures thereof beef tallow amine, hardened tallow amine, coconut oil amine, palm oil amine or soybean oil amine Mention may be made of aliphatic primary amines derived from iso-animal vegetable oils. As the aliphatic primary amine, one kind or a mixture of two or more kinds may be used.

The starting aliphatic secondary amine in the alkylene oxide adduct (D132) of an aliphatic secondary amine having 8 to 36 carbon atoms may be linear, branched or cyclic, and may have a saturated or unsaturated bond. It is an aliphatic secondary amine having 8 to 36 carbon atoms.
Specific examples of the aliphatic secondary amine include dioctylamine, dibutylamine, dihexylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, Mention may be made of diheptadecylamine or dioctadecylamine.
As the aliphatic secondary amine, one kind or a mixture of two or more kinds may be used.

Examples of the starting alkylene oxide in the aliphatic amine alkylene oxide adduct (D13) of the present invention include alkylene oxides having 2 to 12 carbon atoms, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, Examples include tetrahydrofuran and 3-methyltetrahydrofuran. Of these, ethylene oxide and 1,2-propylene oxide are preferable from the viewpoint of availability. These alkylene oxides may use only 1 type and may use 2 or more types together. When using 2 or more types together, random or a block may be sufficient.

The average number of moles of alkylene oxide added in (D131) or (D132) is preferably 3 to 100 moles, more preferably 3 to 70 moles, and particularly preferably 3 to 40 moles per mole of amine.

As a method for producing (D131) and (D132), a known method or the like can be used.
Specifically, the above-mentioned aliphatic primary amine or aliphatic secondary amine is charged into a stirrable pressure vessel, sufficiently substituted with an inert gas (nitrogen, argon, etc.), then dehydrated under reduced pressure, A method in which the alkylene oxide is added and reacted at a reaction temperature of about 80 to 160 ° C. can be used. Moreover, you may use a well-known catalyst as needed at the time of reaction. The catalyst may be added from the beginning of the reaction or from the middle.
Examples of the catalyst include a metal atom-free catalyst (a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, and a third such as tetramethylethylenediamine and 1,8-diazabicyclo [5.4.0] undecene-7. Secondary amines) and metal atom-containing catalysts (alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides and alkaline earth metal oxides).

The concentration of the aliphatic amine alkylene oxide adduct (D13) in actual use is 0.001 to 10% by weight based on the weight in the polishing liquid.

Examples of the polyhydric alcohol type nonionic surfactant (D14) include glycerin ethylene oxide adduct and sorbitan ethylene oxide adduct.

Examples of the anionic surfactant (D2) include fatty acid surfactants (fatty acid (salt) having 8 to 18 carbon atoms or ether carboxylic acid (salt) of an aliphatic alcohol having 8 to 18 carbon atoms); phosphate ester Surfactants [phosphoric mono- or diesters (salts) of higher alcohols having 8 to 24 carbon atoms, or phosphoric mono- or diesters (salts) of alkylene oxide adducts of higher alcohols having 8 to 24 carbon atoms, etc.] .

Of the anionic surfactant (D2), a fatty acid amine salt is preferable from the viewpoint of lubricity, and the fatty acid amine salt is a fatty acid amine salt having 8 to 22 carbon atoms (for example, oleic acid) completely or completely with an amine. The thing which neutralized a part is mentioned.
Examples of the amine include primary amines such as monoethanolamine; secondary amines such as diethanolamine; tertiary amines such as triethanolamine.

The concentration of the surfactant (D) in the polishing liquid for electronic materials is usually 0 to 90% by weight, preferably 0.001 to 80% by weight, more preferably 0.01 to 20% by weight. In addition, the weight ratio of the neutralized salt (AB) to the weight of the surfactant (D) is 0.001 to 1.

The polishing liquid for electronic materials of the present invention may contain an organic reducing agent (E) as necessary. By mix | blending an organic reducing agent (E), the adhesion prevention property with respect to a particle can be improved after grinding | polishing.

Examples of the organic reducing agent (E) include phenols (E1) and reductones (E2).
As the organic reducing agent (E), a commercially available organic reducing agent can be used, and phenols (E1) and reductones (E2) are preferable from the viewpoint of polishing rate.

Examples of the phenols (E1) include compounds represented by the following general formula (11).

[Wherein, X ¹ to X ⁵ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group or an alkyl group. ]

Specific examples of the phenols (E1) represented by the general formula (11) include phenols in which all of X ¹ to X ⁵ are hydrogen; polyhydric phenol compounds such as pyrocatechol, resorcinol, hydroquinone and pyrogallol (E11 ); Phenolic compounds containing carboxyl groups such as 2-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dicarboxyphenol, and 2,4,6-tricarboxyphenol (E12); gallic acid, etc. A polyhydric phenol compound containing a carboxyl group (E13); a phenolic compound containing an amino group such as 4-aminophenol (E14); a phenolic compound containing an alkyl group such as cresol (E15); or a salt thereof. It is done.

Of these, from the viewpoints of polishing rate and particle adhesion prevention, polyhydric phenol compounds (E11) and polyhydric phenol compounds containing carboxyl groups (E13) are preferred, and more preferred are polyhydric phenols containing carboxyl groups. Compound (E13), specifically, gallic acid or a salt thereof.

The reductones (E2) may be any compound having a ketoenediol group represented by the following general formula (12) in the molecule.

Specific examples of reductones (E2) include ascorbic acid (L-form, DL-form, D-form), isoascorbic acid, erythorbic acid, or esters thereof (L-ascorbic acid sulfate, L-ascorbine). Acid phosphate ester, L-ascorbic acid 2-glucoside, L-ascorbic acid palmitic acid ester, tetraisopalmitic acid L-ascorbyl, ascorbic acid isopalmitate, erythorbic acid phosphoric acid ester, erythorbic acid palmitic acid ester, tetraisopalmitin Erysovir acid); or a salt thereof.

Of these, L-ascorbic acid, isoascorbic acid, esters of L-ascorbic acid or esters of isoascorbic acid, or salts thereof are preferred from the viewpoint of polishing rate and particle adhesion prevention, and more preferably L-ascorbic acid or a salt thereof.

Examples of the salts of (E1) and (E2) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary ammonium salts. Is mentioned.

The concentration of the organic reducing agent (E) in the polishing liquid during use is preferably 0.01 to 1% by weight from the viewpoint of preventing adhesion of particles.

In addition to the aforementioned substances, the polishing liquid of the present invention includes inorganic acids (nitric acid, sulfuric acid, phosphoric acid, etc.), chelating agents (phosphonic acid-based chelating agents [hydroxyethylidene diphosphonic acid (HEDP) or salts thereof, methyl diphosphones). Acid or salt thereof, aminotri (methylenephosphonic acid) or salt thereof]; carboxylic acid chelating agent [diethylenetriaminepentaacetic acid (DTPA) or salt thereof, ethylenediaminetetraacetic acid (EDTA) or salt thereof, hydroxyethyliminodiacetic acid ( HIDA) or a salt thereof, citric acid or a salt thereof, gluconic acid or a salt thereof]), a stabilizer (for example, p-toluenesulfonate), a rust inhibitor (benzotriazole, mercaptobenzotriazole, cyclohexylamine ethylene oxide) An additive such as an adduct may be contained. As these additives, those conventionally used as polishing liquids can be used, and are not particularly limited.

The polishing method of the present invention is a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material of the present invention in the production process of the electronic material.

Another embodiment of the present invention is an electronic material manufacturing method including a step of polishing an electronic material intermediate using the above-described polishing liquid in the polishing step.

As an example of the manufacturing process (part) of the electronic material using the polishing liquid of the present invention, a lapping process of a hard disk glass substrate will be described below as an example.
(1) A glass substrate is set on a carrier of a polishing apparatus, and the glass substrate is sandwiched by a surface plate to which a polishing pad to which a diamond grindstone is fixed is attached.
(2) While supplying the polishing liquid of the present invention to the surface plate, a load is applied to rotate the surface plate and the carrier.
(3) After confirming that a certain film thickness has been polished, the rotation is stopped.
(4) Remove the glass substrate from the carrier and rinse with running water.
(5) After rinsing with running water, the substrate is dried.

As another example, a substrate process for a hard disk glass substrate will be described below as an example.
(1) The above-mentioned lapped glass substrate is set on a carrier of a polishing apparatus, and the glass substrate is sandwiched by a surface plate to which a polyurethane polishing pad is attached.
(2) A load is applied while supplying the polishing liquid of the present invention containing cerium oxide, and the surface plate and the carrier are rotated.
(3) After confirming that a certain film thickness has been polished, the rotation is stopped.
(4) The glass substrate is rinsed with running water, taken out from the carrier, and dipped or scrubbed with a cleaning agent.
(5) A glass substrate rinsed with running water is set on a carrier of a polishing apparatus and polished in the same manner as described above using the polishing liquid of the present invention containing colloidal silica.
(6) Rinse and rinse the substrate after polishing and rinse with running water again.
(7) Dry and pack.

A commercially available polishing apparatus can be used as the polishing apparatus, and is not particularly limited.

As the polishing conditions such as the number of rotations, polishing time, number of oscillations, load, etc., the conditions for polishing with a conventional polishing liquid can be used.

Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1 (Production of polyacrylic acid DBU salt)
A reaction vessel capable of temperature control and stirring was charged with 300 parts of isopropyl alcohol and 100 parts of ultrapure water, and the reaction vessel was purged with nitrogen, and then heated to 75 ° C. While stirring at 30 rpm, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropyl alcohol solution of dimethyl 2,2′-azobisisobutyrate were simultaneously added dropwise over 3.5 hours.
After completion of the dropwise addition, the mixture was stirred at 75 ° C. for 5 hours, and then ultrapure water was intermittently added so that the system did not solidify, and the mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected. The obtained polyacrylic acid aqueous solution was neutralized with 450 parts of DBU until the pH became 7.0, and the concentration was adjusted with ultrapure water to obtain a 40% aqueous solution of polyacrylic acid DBU salt (AB-1). .
The Mw of the polyacrylic acid DBU salt was 10,000.

Production Example 2 (Production of naphthalenesulfonic acid formaldehyde condensate DBU salt)
A reaction vessel with stirring was charged with 21 parts of naphthalenesulfonic acid and 10 parts of ultrapure water, and 8 parts of 37% formaldehyde was added dropwise over 3 hours while maintaining the temperature in the system at 80 ° C. with stirring. After completion of the dropwise addition, the temperature was raised to 105 ° C. and reacted for 25 hours, then cooled to room temperature (about 25 ° C.), DBU was gradually added while adjusting to 25 ° C. in a water bath, and adjusted to pH 6.5 (DBU). Use about 15 parts). Ultrapure water was added to adjust the solid content to 40% to obtain a 40% aqueous solution of DBU salt (AB-2) of naphthalenesulfonic acid formaldehyde condensate as an anionic surfactant. The Mw of the DBU salt of (AB-2) was 5,000.

Production Example 3 (Production of polystyrene sulfonic acid guanidine salt)
100 parts of ethylene dichloride was charged into a reaction vessel with stirring capable of temperature control and refluxing, and after purging with nitrogen under stirring, the temperature was raised to 90 ° C. to reflux ethylene dichloride. 120 parts of styrene and an initiator solution prepared by dissolving 1.7 parts of 2,2′-azobisisobutyronitrile in 20 parts of ethylene dichloride are dropped into the reaction vessel separately for 6 hours, and the dropping is completed. Thereafter, polymerization was further performed for 1 hour. After the polymerization, the mixture was cooled to 20 ° C. under a nitrogen seal, 105 parts of anhydrous sulfuric acid was added dropwise over 10 hours while controlling the temperature at 20 ° C., and a sulfonation reaction was further carried out for 3 hours after the completion of the addition. After the reaction, the solvent was distilled off and solidified, and then 345 parts of ultrapure water was added and dissolved to obtain a polystyrenesulfonic acid aqueous solution. The obtained polystyrene sulfonic acid aqueous solution was neutralized with guanidine until the pH reached 7, and the concentration was adjusted with ultrapure water, whereby 40% of polystyrene sulfonic acid guanidine salt (AB-3) as an anionic surfactant was obtained. An aqueous solution was obtained. In addition, Mw of (AB-3) was 40,000, and the sulfonation rate was 97%.

Production Example 4 (Production of polystyrene sulfonic acid guanidine salt)
80 parts of ethylene dichloride was charged into a reaction vessel with stirring capable of temperature control and refluxing, and the temperature was raised to 90 ° C. after stirring and purging with nitrogen, thereby refluxing ethylene dichloride. 200 parts of styrene and an initiator solution prepared by dissolving 1.0 part of 2,2′-azobisisobutyronitrile in 20 parts of ethylene dichloride were dropped into the reaction vessel separately over 6 hours, and the addition was completed. Thereafter, polymerization was further performed for 1 hour. After the polymerization, the mixture was cooled to 20 ° C. under a nitrogen seal, 105 parts of anhydrous sulfuric acid was added dropwise over 10 hours while controlling the temperature at 20 ° C., and a sulfonation reaction was further carried out for 3 hours after the completion of the addition. After the reaction, the solvent was distilled off and solidified, and then 345 parts of ultrapure water was added and dissolved to obtain a polystyrenesulfonic acid aqueous solution. The obtained polystyrene sulfonic acid aqueous solution was neutralized with guanidine until the pH became 7, and the concentration was adjusted with ultrapure water, whereby 40% of polystyrene sulfonic acid guanidine salt (AB-4) as an anionic surfactant was obtained. An aqueous solution was obtained. In addition, Mw of (AB-4) was 224,000, and the sulfonation rate was 97%.

Production Example 5 (Production of dodecylbenzenesulfonic acid DBU salt)
A reaction vessel with temperature control and stirring is charged with 100 parts of a 10% aqueous solution of dodecylbenzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., HLB: 7.4), and 4.7 parts of DBU with temperature control and stirring at 25 ° C. Was slowly added and stirred for 10 minutes to obtain a 14% aqueous solution of dodecylbenzenesulfonic acid DBU salt (AB-5) (pH at 25 ° C. = 6.5).

Production Example 6 (Production of aliphatic amine ethylene oxide adduct)
185 parts (1.0 mole part) of laurylamine and 3.6 parts (0.01 mole part) of 25% TMAH aqueous solution were charged into a stainless steel autoclave equipped with a stirrer and a temperature controller, and 100 ° C., 4 kPa or less. For 30 minutes under reduced pressure. 308 parts (7.0 mole parts) of ethylene oxide was added dropwise over 3 hours while controlling the reaction temperature at 100 ° C., and then aged at 100 ° C. for 3 hours. Further, the mixture was stirred at 150 ° C. for 2 hours under a reduced pressure of 2.6 kPa or less to decompose and remove the remaining TMAH, and a nonionic surfactant laurylamine ethylene oxide 7 mol adduct (D-2) 490 parts were obtained.

Comparative Production Example 1 (Production of polyacrylic acid Na salt)
A reaction vessel capable of temperature control and stirring was charged with 300 parts of isopropyl alcohol and 100 parts of ultrapure water, and the reaction vessel was purged with nitrogen, and then heated to 75 ° C. While stirring at 30 rpm, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropyl alcohol solution of dimethyl 2,2′-azobisisobutyrate were simultaneously added dropwise over 3.5 hours.
After completion of the dropwise addition, the mixture was stirred at 75 ° C. for 5 hours, and then ultrapure water was intermittently added so that the system did not solidify, and the mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected. The resulting polyacrylic acid aqueous solution was neutralized with 70 parts of sodium hydroxide until the pH became 7.0, and the concentration was adjusted with ultrapure water, whereby 40% of polyacrylic acid Na salt (AB′-1) was obtained. An aqueous solution was obtained.
In addition, Mw of polyacrylic acid Na salt was 10,000.

Examples 1 to 49 and Comparative Examples 1 to 19
Each component was blended so as to be a total of 100 parts with the composition described in Tables 1 to 6, and stirred for 20 minutes at 25 ° C. with a magnetic stirrer at 40 rpm to obtain the polishing liquid of the present invention and the polishing for comparison. A liquid was obtained.
The following abrasive particles were used in the table.
Colloidal silica slurry: “COMPOL80” manufactured by Fujimi Incorporated (average particle size 80 nm, active ingredient concentration 40% by weight)
Cerium oxide: “HS-8005” manufactured by Showa Denko KK (average particle size 0.5 μm)
Alumina: “WA # 20000” manufactured by Fujimi Incorporated (average particle size 0.4 μm)
Diamond: “1/10 PCS-WB2” manufactured by Nano Factor Co., Ltd. (average particle size 100 nm)
Polyoxyethylene polyoxypropylene copolymer: New Pole GEP2800 manufactured by Sanyo Chemical Industries
Dioleyl phosphate Na salt: NAS-546 manufactured by Sanyo Chemical Industries
Aromatic sulfonate: hydroxynaphthyl sulfonic acid Na salt reagent was used.

As evaluation of the performance of the polishing liquid, evaluation tests of scratch reduction performance, particle adhesion reduction performance, and polishing rate sustainability performance were performed by the following methods.
This evaluation was conducted in a clean room of class 1,000 (FED-STD-209D, US Federal Standard, 1988) to prevent contamination from the atmosphere.

[Evaluation 1 When polishing glass substrate with polishing liquid containing colloidal silica]
<Evaluation of scratch reduction performance>
The polishing liquids of Examples 1 to 8 and the polishing liquids of Comparative Examples 1 to 3 were further diluted 10 times with ion exchange water to obtain test liquids.
(1) A 2.5-inch glass substrate for a magnetic disk and a polyurethane polishing pad (manufactured by Fujibow Co., Ltd., “H9900S”) were set in a polishing apparatus (manufactured by Nano Factor Co., Ltd., “FACT-200”).
(2) The number of rotations was set to 30 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 50 g weight / cm ² , and the above test solution was polished for 5 minutes while being poured onto the substrate at a rate of 1 mL / second.
(3) The polished glass substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed, and then removed from the polishing apparatus and dried by nitrogen blowing to prepare an evaluation substrate.
(4) A surface inspection device (made by Vision Cytec Co., Ltd.) that emphasizes and inspects fine scratches on the surface by applying light to scratches on the evaluation substrate and condensing and amplifying the weak scattered light generated. Using “MicroMax VMX-6100SK”), the evaluation substrate surface was arbitrarily selected at five locations (10 mm × 10 mm square), the number of scratches within the range was counted, and the average value at the five locations was calculated.
The average number of scratches on the substrate of Comparative Example 1 (blank) was 50.

The number of scratches on each substrate was compared with the number of scratches on the substrate of Comparative Example 1 (blank), and the effect of suppressing the generation of scratches on the substrate surface was evaluated and determined according to the following criteria.
The results are shown in Table 1.
5: Less than 20% of blanks (50 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Evaluation of particle adhesion reduction performance>
(1) An evaluation substrate similar to the evaluation of scratch reduction performance was prepared.
(2) The above surface inspection apparatus capable of inspecting fine residues on the surface by applying light to residual particles on the evaluation substrate, emphasizing and amplifying the weak scattered light generated and amplifying it. Using the evaluation substrate surface arbitrarily, select 5 locations (10mm x 10mm square), and count the number of particles in the range with image analysis software (Mitani Corporation, WinRoof) to calculate the average value of 5 locations did.
The number of particles on the substrate of Comparative Example 1 (blank) was 1950.

The number of particles on each substrate was compared with the number of particles on the substrate of Comparative Example 1, and the effect of reducing the adhesion of particles in the polishing process was evaluated and determined according to the following criteria.
The results are shown in Table 1.
5: Less than 20% of blanks (1950 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Evaluation of polishing rate sustainability>
(1) A 2.5-inch glass disk for magnetic disk and a polishing pad made of polyurethane resin (manufactured by Fujibow Co., Ltd., “H9900S”) and a polishing apparatus (manufactured by Nano Factor Co., Ltd., “FACT-200”) Set.
(2) The number of rotations was set to 30 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 50 g weight / cm ² , and the above test solution was polished on the substrate at a rate of 1 mL / second for 30 minutes.
(3) The polished glass substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed with nitrogen blow, and weighed.

(1) to (3) were repeated 10 times, and the weight change amount of the first time and the 10th time was compared, and the evaluation of the polishing rate sustainability performance was determined according to the following criteria. (First weight change / 10th weight change × 100)
The results are shown in Table 1.
5: 80% or more 4: 60% to less than 80% 3: 40% to less than 60% 2: 20% to less than 40% 1: less than 20%

[Evaluation 2: When polishing an aluminum substrate with a polishing liquid containing colloidal silica]
<Evaluation of scratch reduction performance>
The polishing liquids of Examples 9 to 16 and the polishing liquids of Comparative Examples 4 to 6 were further diluted 10 times with ion-exchanged water to obtain test liquids.
(1) A 3.5-inch aluminum substrate for a magnetic disk and a polyurethane resin polishing pad (Fujibow Co., Ltd., “H9900S”) were set in a polishing apparatus (Nano Factor Co., Ltd., “FACT-200”).
(2) The number of rotations was set to 30 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 50 g weight / cm ² , and the above test solution was polished for 5 minutes while being poured onto the substrate at a rate of 1 mL / second.
(3) The polished aluminum substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed, and then removed from the polishing apparatus and dried by nitrogen blowing to prepare an evaluation substrate.
(4) A surface inspection device (made by Vision Cytec Co., Ltd.) that emphasizes and inspects fine scratches on the surface by applying light to scratches on the evaluation substrate and condensing and amplifying the weak scattered light generated. Using “MicroMax VMX-6100SK”), the evaluation substrate surface was arbitrarily selected at five locations (10 mm × 10 mm square), the number of scratches within the range was counted, and the average value at the five locations was calculated.
The average number of scratches on the substrate of Comparative Example 4 was 100.

The number of scratches on each substrate was compared with the number of scratches on the substrate of Comparative Example 4, and the effect of suppressing the generation of scratches on the substrate surface was evaluated and determined according to the following criteria.
The results are shown in Table 2.
5: Less than 20% of blank (100 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Evaluation of particle adhesion reduction performance>
(1) An evaluation substrate similar to the evaluation of scratch reduction performance was prepared.
(2) The above surface inspection apparatus capable of inspecting fine residues on the surface by applying light to residual particles on the evaluation substrate, emphasizing and amplifying the weak scattered light generated and amplifying it. Using the evaluation substrate surface arbitrarily, select 5 locations (10mm x 10mm square), and count the number of particles in the range with image analysis software (Mitani Corporation, WinRoof) to calculate the average value of 5 locations did.
The number of particles on the substrate of Comparative Example 4 was 1200.

The number of particles on each substrate was compared with the number of particles on the substrate of Comparative Example 4, and the effect of reducing the adhesion of particles in the polishing process was evaluated and determined according to the following criteria.
The results are shown in Table 2.
5: Less than 20% of blanks (1200) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Evaluation of polishing rate sustainability>
(1) Weighed 3.5 inch aluminum substrate for magnetic disk and polyurethane polishing pad (manufactured by Fujibow Co., Ltd., “H9900S”) on a polishing apparatus (manufactured by Nano Factor Co., Ltd., “FACT-200”) I set it.
(2) The number of rotations was set to 30 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 50 g weight / cm ² , and the above test solution was polished on the substrate at a rate of 1 mL / second for 30 minutes.
(3) The polished aluminum substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed with nitrogen blow, and weighed.

(1) to (3) were repeated 10 times, and the weight change amount of the first time and the 10th time was compared, and the evaluation of the polishing rate sustainability performance was determined according to the following criteria. (First weight change / 10th weight change × 100)
The results are shown in Table 2.
5: 80% or more 4: 60% to less than 80% 3: 40% to less than 60% 2: 20% to less than 40% 1: less than 20%

[Evaluation 3 When polishing glass substrate with polishing liquid containing cerium oxide]
The polishing liquids of Examples 17 to 24 and the polishing liquids of Comparative Examples 7 to 9 were further diluted 10 times with ion-exchanged water to obtain test liquids.
In the same manner as in Evaluation 1, the scratch reduction performance, particle adhesion reduction performance, and polishing rate duration performance were evaluated.
The average number of scratches on the substrate of Comparative Example 7 (blank) was 70, and the number of particles on the substrate of Comparative Example 7 (blank) was 1000. The results are shown in Table 3.

[Evaluation 4 When polishing aluminum substrate with polishing liquid containing alumina]
The polishing liquids of Examples 25 to 32 and the polishing liquids of Comparative Examples 10 to 12 were further diluted 10 times with ion-exchanged water to obtain test solutions.
In the same manner as in Evaluation 2, the scratch reduction performance, particle adhesion reduction performance, and polishing rate duration performance were evaluated.
The average number of scratches on the substrate of Comparative Example 10 (blank) was 150, and the number of particles on the substrate of Comparative Example 10 (blank) was 1000. The results are shown in Table 4.

[Evaluation 5: When polishing aluminum substrate with polishing liquid containing diamond]
The polishing liquids of Examples 33 to 40 and Comparative Examples 13 to 15 were further diluted 10 times with ion-exchanged water to obtain test liquids.
In the same manner as in Evaluation 2, the scratch reduction performance, particle adhesion reduction performance, and polishing rate duration performance were evaluated.
The average number of scratches on the substrate in Comparative Example 13 (blank) was 70, and the number of particles on the substrate in Comparative Example 13 (blank) was 500. The results are shown in Table 5.

[Evaluation 6 When using a grinding wheel fixed polishing pad and polishing glass (glass wrapping) with a polishing liquid containing a nonionic surfactant]
<Evaluation of particle adhesion reduction performance>
The polishing liquids of Examples 41 to 49 and the polishing liquids of Comparative Examples 16 to 19 were further diluted 10-fold with ion exchange water to obtain test liquids.
(1) A 2.5-inch glass substrate for a magnetic disk and a diamond grinding wheel fixed polishing pad (manufactured by Sumitomo 3M Co., Ltd., “Trizact 677XA”) were set in a polishing apparatus (manufactured by Nano Factor Co., Ltd., “FACT-200”). .
(2) The number of rotations was set to 100 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 100 g weight / cm ² , and the above test solution was polished onto the substrate at a rate of 1 mL / second for 5 minutes.
(3) The polished glass substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed, and then removed from the polishing apparatus and dried by nitrogen blowing to prepare an evaluation substrate.
(4) The above surface inspection apparatus capable of inspecting fine residue on the surface by applying light to residual particles on the evaluation substrate, emphasizing and amplifying the weak scattered light generated, and amplifying it. Using the evaluation substrate surface arbitrarily, select 5 locations (10mm x 10mm square), and count the number of particles in the range with image analysis software (Mitani Corporation, WinRoof) to calculate the average value of 5 locations did.
The number of particles on the substrate of Comparative Example 16 was 4500.

The number of particles on each substrate was compared with the number of particles on the substrate of Comparative Example 16, and the effect of reducing the adhesion of particles in the polishing process was evaluated and determined according to the following criteria.
The results are shown in Table 6.
5: Less than 20% of blanks (4500 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Evaluation of polishing rate sustainability>
(1) A 2.5 inch magnetic disk glass substrate and a diamond grinding wheel fixed polishing pad (manufactured by Sumitomo 3M Co., Ltd., “Trizact 677XA”) whose weight was measured were polished with a polishing apparatus (manufactured by Nano Factor Co., Ltd., “FACT-200”). ).
(2) The number of rotations was set to 100 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 100 g weight / cm ² , and the test solution was polished for 30 minutes while being poured onto the substrate at a rate of 1 mL / second.
(3) The polished glass substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed with nitrogen blow, and weighed.

By repeating the steps (1) to (3) twice and comparing the first and second weight changes, the evaluation of the polishing rate sustainability was determined according to the following criteria. (First weight change / second weight change × 100)
The results are shown in Table 6.
5: 80% or more 4: 60% to less than 80% 3: 40% to less than 60% 2: 20% to less than 40% 1: less than 20%

It can be seen that the polishing liquids of Examples 1 to 49 of the present invention can greatly reduce the amount of adhered particles and can maintain the polishing rate as compared with Comparative Examples 1 to 19. Further, the polishing liquids of the present invention of Examples 1 to 40 can greatly reduce the number of scratches compared to Comparative Examples 1 to 15.
On the other hand, the polishing liquids of Comparative Examples 3, 6, 9, 12, 15, and 18 have some effect of suppressing the adhesion of certain particles as compared with the blank, but the acceptable particle adhesion for high capacity is possible. It does not reach the amount. Further, the polishing liquids of Comparative Examples 3, 6, 9, 12, and 15 are somewhat effective in suppressing the occurrence of a certain scratch compared to the blank, but do not reach the number of scratches that can be allowed for higher capacity. .
Further, the polishing liquids of Comparative Examples 2, 5, 8, 11, and 14 using benzotriazole have almost the same number of scratches after polishing the glass substrate as compared with Comparative Examples 1, 4, 7, 10, and 13. The effect of suppressing the generation of scratches and particles is small.

The polishing liquid for electronic materials of the present invention is excellent in the effect of suppressing the occurrence of scratches during the polishing process, and is also excellent in the effect of reducing particle adhesion during polishing, so the polishing liquid for electronic materials including the polishing process in the manufacturing process For example, it is useful as a polishing liquid for producing glass substrates for magnetic disks, Ni-P plated aluminum substrates for magnetic disks, silicon substrates for semiconductors, and sapphire substrates for LEDs.
In addition, the method for producing an electronic material including the step of polishing using the polishing liquid of the present invention is a method for producing a magnetic disk because scratching during polishing is very small and particle adhesion during polishing is small. It can be used as a manufacturing method for glass substrates, Ni—P plated aluminum substrates for magnetic disks, silicon substrates for semiconductors, sapphire substrates for LEDs, and the like.

Claims

Neutralizing salt (AB) for polishing liquid used in the step of polishing an electronic material intermediate using a polishing pad.
(AB): an acidic compound (A) having at least one acid group (X) in the molecule, and a nitrogen-containing basic compound (B) having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol And a neutralized salt having a change in heat of formation (Q1) in the acid dissociation reaction of the acid group (X) of 3 to 200 kcal / mol.
The neutralized salt according to claim 1, wherein the weight average molecular weight of the neutralized salt (AB) is 1,000 to 200,000.
The neutralized salt according to claim 1 or 2, wherein the neutralized salt (AB) is a salt of a polymer (A2-3) having a carboxyl group.
The neutralized salt according to any one of claims 1 to 3, wherein the nitrogen-containing basic compound (B) is 1,8-diazabicyclo [5.4.0] undecene-7.
A polishing liquid for use in a step of polishing an electronic material intermediate using a polishing pad, comprising the neutralizing salt (AB) according to any one of claims 1 to 4 and water as essential components .
The polishing liquid for electronic materials according to claim 5, further comprising abrasive particles (C).
The polishing liquid for electronic materials according to claim 6, wherein the abrasive particles (C) are at least one selected from the group consisting of colloidal silica, cerium oxide, alumina and diamond.
The concentration of neutralized salt (AB) in the polishing liquid for electronic materials is 0.01 to 4% by weight and the concentration of abrasive particles (C) is 1 to 40% by weight. The polishing liquid for electronic materials according to claim 6 or 7, wherein the ratio of) is 0.001 to 0.1.
Further, higher alcohol alkylene (C2-4) oxide adduct (D11) having 8 to 18 carbon atoms, polyoxyethylene polyoxypropylene copolymer (D12), alkylene oxide addition of aliphatic amine having 8 to 36 carbon atoms The polishing slurry for electronic materials according to any one of claims 5 to 8, comprising at least one surfactant (D) selected from the group consisting of a product (D13) and a polyhydric alcohol type nonionic surfactant (D14). .
The polishing slurry for electronic materials according to claim 9, wherein the surfactant (D) is an alkylene oxide adduct (D13) of an aliphatic amine having 8 to 36 carbon atoms.
The concentration of the neutralized salt (AB) in the polishing liquid for electronic materials is 0.01 to 5% by weight and the concentration of the surfactant (D) is 0.01 to 60% by weight. The polishing liquid for electronic materials according to claim 9 or 10, wherein the ratio of the sum salt (AB) is 0.001 to 1.
The polishing slurry for electronic materials according to any one of claims 5 to 11, further comprising an organic reducing agent (E).
The polishing liquid for electronic materials according to claim 12, wherein the organic reducing agent (E) is a phenol (E1) and / or a reductone (E2).
The polishing liquid for electronic materials according to any one of claims 5 to 13, wherein the polishing liquid for electronic materials is used for producing a glass substrate for hard disks or an aluminum substrate for hard disks whose surface is nickel-phosphorous plated.
A polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material according to any one of claims 5 to 14 in a manufacturing process of the electronic material.
An electronic material manufacturing method comprising a polishing step in the manufacturing step, the method comprising the step of polishing an electronic material intermediate by the polishing method according to claim 15.