TW201307543A - Neutralized salt for slurry, cleaning liquid for electronic materials, polishing method and manufacturing method of electronic materials - Google Patents

Abstract

The invention is a specific neutralized salt (AB) used in a polishing step to polish an intermediate body of an electronic material by using a polishing pad, a slurry for the electronic material containing the neutralized salt (AB), a polishing method of polishing the intermediate body of the electronic material by using the slurry for the electronic material, and a manufacturing method of the electronic material containing a step of polishing the intermediate body of the electronic material by using the slurry for the electronic material. Herein, the neutralized salt (AB) is a salt containing an acid compound (A) having at least one acid group (X) within a molecule and a basic compound (B) containing nitrogen whose changing heat of formation in a proton addition reaction is from 10 kcal/mol to 152 kcal/mol. The neutralized salt (AB) is a neutralized salt whose changing heat (Q1) of formation of the acid group (X) in an acidic dissociation reaction is from 3 kcal/mol to 200 kcal/mol.

Description

Neutralizing salt for polishing liquid, polishing liquid for electronic material, polishing method, and manufacturing method of electronic material

The present invention relates to a neutralizing salt used in a polishing step, a polishing liquid for an electronic material containing the neutralizing salt, a polishing method for polishing an intermediate of an electronic material using the polishing liquid for the electronic material, and a polishing method comprising using the polishing A method of producing an electronic material in a step of grinding an intermediate of an electronic material.

More specifically, the present invention relates to a polishing step for use in a step of manufacturing an electronic material, which has a good durability of a polishing rate and an improved surface quality of an electronic material, and contains the neutralized salt. The polishing method for the electronic material, the polishing method for polishing the electronic material intermediate using the polishing liquid for the electronic material, and the method for producing the electronic material including the step of polishing the electronic material intermediate by the polishing method.

Electronic materials, especially magnetic disks, are becoming smaller and higher in capacity year by year, and the distance between the magnetic head and the disk substrate becomes smaller and smaller. Therefore, there is a need for a substrate in which, in the cleaning step after the polishing step in the production of the magnetic disk substrate, particles such as polishing particles for polishing or generated polishing particles are not generated as much as possible. In addition, reduction in surface defects such as scratches or pits, surface undulations, and indentation is demanding in recent years. Further, in order to cope with the demand in recent years, not only the quality of the above-mentioned substrate but also the efficiency of production is required, and specifically, the durability of the polishing rate is strongly required.

The disk manufacturing step includes a lapping step as a step of chamfering a board for a substrate, and a planarized substrate is produced. The substrate manufacturing step of the step, and the media step as a step of forming a magnetic layer on the substrate.

In these steps, in the polishing step, in order to coarsely chamfer the substrate, a polishing pad and a polishing liquid for fixing a diamond such as diamond by a resin are used to polish the main surface or the end surface of the substrate, followed by polishing After the cleaning process of the main surface or the end surface of the substrate is removed in the subsequent cleaning step, the drying step is performed, and then the processed substrate is transported to the substrate manufacturing step.

Further, in the substrate manufacturing step, in order to planarize the substrate, polishing using a polishing pad and a polishing liquid containing abrasive particles such as colloidal silica or cerium oxide is performed in the subsequent cleaning step. After the particles of the polishing particles on the surface of the substrate or the generated polishing particles are removed, the processed substrate is bundled in a predetermined container and then transported to the media step through a drying step.

Since the abrasive particles or the generated abrasive grains in the polishing liquid are very fine, they are likely to aggregate, and these aggregates may affect the surface quality of the substrate in the step of polishing the substrate. For example, electrical resistance is sometimes generated between the agglomerates and the substrate and scratches are generated on the substrate. The scratches generated on the substrate are, for example, a cause of poor adhesion between the magnetic film and the substrate in the subsequent media step, and may be a cause of hindering the increase in the capacity of the magnetic disk.

Therefore, in order to reduce the occurrence of the above-mentioned scratches or to suppress the decrease in the polishing rate, a polishing liquid containing an azole such as benzotriazole or maleic acid has been proposed (for example, Patent Document 1 and Patent No. Literature 2).

Moreover, in order to improve the durability of the polishing rate, a polishing liquid containing an aromatic sulfonate has been proposed (for example, Patent Document 3).

Further, in order to reduce the adhesion of particles to the surface of the substrate, a polishing liquid containing hydroxyethyl cellulose has been proposed (for example, Patent Document 4).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1]

Japanese Patent Laid-Open No. 2007-92064

[Patent Document 2]

Japanese Patent Laid-Open Publication No. 2005-138197

[Patent Document 3]

Japanese Patent Laid-Open No. 08-109389

[Patent Document 4]

Japanese Patent Laid-Open No. 11-116942

However, the effect of suppressing scratches or adhesion of particles during polishing in the conventional polishing liquid represented by Patent Document 1 to Patent Document 4 is not sufficient, and it is not possible to cope with the substrate quality which is allowed to achieve high capacity. The slurry. Further, although the polishing liquid of Patent Document 2 has a slight effect on the durability of the polishing rate, it is not sufficient, and it is not a polishing liquid that satisfies the quality of the substrate after polishing.

Accordingly, it is an object of the present invention to provide a material, a polishing liquid for an electronic material containing the material, a polishing method for polishing an intermediate of an electronic material using the polishing liquid for the electronic material, and an intermediate of the electronic material using the polishing method Manufacturer of electronic materials for the step of grinding According to the method, in the polishing step in the step of manufacturing the electronic material, the substrate has fewer defects such as scratches than the previous polishing liquid, and in the subsequent cleaning step, the polishing debris generated by the polishing can be easily removed. Further, the polishing rate in the polishing step can be maintained.

The present inventors conducted studies in order to achieve the above object, and as a result, have completed the present invention.

That is, the present invention is a specific neutralizing salt (AB) for a step of polishing an electronic material intermediate using a polishing pad, a polishing liquid for an electronic material containing the neutralized salt (AB), and the use of the electronic material. A polishing method in which a polishing liquid grinds an electronic material intermediate, and a method of producing an electronic material including a step of polishing an electronic material intermediate by the polishing method.

Here, the neutralizing salt (AB) is an acidic compound (A) having at least one acid group (X) in the molecule, and the heat of formation (Q2) in the proton addition reaction is 10 kcal/mol to 152 kcal/ a salt of a nitrogen-containing basic compound (B), which is a neutralized salt having a heat generation change (Q1) of 3 kcal/mol to 200 kcal/mol in the acid dissociation reaction of the above acid group (X).

The neutralized salt of the present invention used in the grinding step has an effect of particularly reducing surface defects generated on the surface of the object to be polished in the grinding step. Further, it has an effect of reducing the adhesion of particles during polishing and easily removing the particles from the substrate in the subsequent washing step. Further, the polishing liquid for an electronic material containing the neutralized salt is superior to the conventional polishing liquid in that the polishing rate is excellent in addition to the above effects. Therefore, it can be stably produced An electronic material that causes surface defects such as scratches or pits and/or small residual particles.

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

The electronic material in the present invention is not particularly limited as long as it is an electronic material produced by a step including a step of polishing using a polishing pad in the production step.

For example, (1) a substrate for a magnetic disk such as a glass substrate for a hard disk or an aluminum substrate for a hard disk for nickel-phosphorus (Ni-P) plating, and (2) a semiconductor substrate such as a semiconductor element or a germanium wafer, (3) a compound semiconductor substrate such as a SiC substrate, a GaAs substrate, a GaN substrate, or an AlGaAs substrate, or (4) a sapphire substrate or the like for a light emitting diode (LED).

Among these, from the viewpoint of improving production efficiency, a substrate for a magnetic disk, specifically, a glass substrate for a hard disk or an aluminum substrate for a hard disk on which nickel-phosphorus (Ni-P) is plated is used.

The term "electronic material intermediate" refers to a material to be polished before the electronic material. For example, in the case of a glass substrate for a hard disk, it means a glass substrate before lapping or coarsening with ruthenium oxide or the like. Glass substrate before polishing or before precision polishing by colloidal cerium oxide or the like A glass substrate or the like, the electronic material before the polishing process refers to an electronic material intermediate.

The grinding step in the present invention refers to a step of processing a material into a flat shape using a grindstone or abrasive particles, which includes, for example, a polishing step of coarse chamfering using a polishing pad to which a grindstone is fixed, or a flattening using a grinding particle precisely The grinding step.

The polishing pad in the present invention refers to a pad made of a polyurethane resin or a polyester resin, and includes a pad to which a grindstone such as diamond is fixed on the surface. Further, it may be of a foam type or a suede type, and mats of various hardnesses may be used. These polishing pads are not particularly limited, and commercially available polishing pads can be used.

The polishing pad is attached to the flat plate of the polishing apparatus and used in the polishing step of performing the rough chamfering process described above or the polishing step in which the polishing particles are precisely planarized.

The neutralized salt (AB) in the present invention is characterized by comprising a neutralized salt (AB1) of the acidic compound (A1) and the compound (B), and/or a polymer (A2) and a compound (B) as an acidic compound. Neutralize the salt (AB2).

The neutralizing salt (AB1) is an acid group (X1) having an acid having a thermal change (Q1) of 3 kcal/mol to 200 kcal/mol in at least one acid dissociation reaction, and a carbon number of 1 to 36, respectively. The acidic compound (A1) of the hydrophobic group (Y), and the neutralized salt of the compound (B) having a heat generation change (Q2) in the proton addition reaction of 10 kcal/mol to 152 kcal/mol, and is (X1) Neutralizing at least one selected from the group consisting of a sulfonic acid group, a sulfuric acid group, a carboxyl group, a carboxymethoxy group, a carboxyethoxy group, a (di)carboxymethylamino group, and a (di)carboxyethylamino group Salt, neutralized salt (AB2) has at least one acid group in the molecule The polymer (A2) as the acidic compound of (X2) and the neutralized salt of the compound (B) having a heat of formation change (Q2) in the proton addition reaction of 10 kcal/mol to 152 kcal/mol.

The acidic compound (A1) is an acid group (X1) having an acid having a heat generation change (Q1) of 3 kcal/mol to 200 kcal/mol in at least one acid dissociation reaction, and a hydrophobic group having a carbon number of 1 to 36, respectively. In the group (Y), the polymer (A2) is one having at least one acid group (X2) in the molecule. The heat of formation (Q1) in the acid dissociation reaction of the acid group (X2) is also from 3 kcal/mol to 200 kcal/mol.

The heat of formation (Q1) in the acid dissociation reaction of the acid group (X1) and the acid group (X2) is the heat of formation of HX in the acid dissociation reaction of the acid (HX) represented by the following formula (1). the difference in heat of formation ^- and X.

HX → H ⁺ +X ^- (1)

Further, the heat of formation in the acid dissociation reaction of the acid group (X1) is a value obtained by assuming that the hydrophobic group (Y) is a hydrogen atom.

Further, the heat of formation in the acid dissociation reaction of the acid group (X2) is a value obtained by assuming that the polymer chain to which the acid group (X2) is bonded is assumed to be a hydrogen atom.

For example, in the case of a sulfonic acid group (-SO ₃ H), it is a value calculated as H-SO ₃ H; in the case of a sulfate group (-OSO ₃ H), it is as H-OSO ₃ H is a calculated value; in the case of a carboxyl group (-COOH), it is a value calculated as H-COOH; in the case of a carboxylmethoxy group (-OCH ₂ COOH), it is used as an H-OCH ₂ COOH calculated value; in the case of carboxyethoxy (-OCH ₂ CH ₂ COOH), it is calculated as H-OCH ₂ CH ₂ COOH; (2) carboxymethylamino group ( In the case of -NRCH ₂ COOH or -N(CH ₂ COOH) ₂ ), it is a value calculated as H-NHCH ₂ COOH; (2) carboxyethylamino group (-NRCH ₂ CH ₂ COOH or -N) In the case of (CH ₂ CH ₂ COOH) ₂ ), it is a value calculated as H-NHCH ₂ CH ₂ COOH. Further, R represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms (methyl group, ethyl group, propyl group, butyl group, octyl group, decyl group, decyl group, dodecyl group, etc.).

That is, the generation heat change (Q1) is represented by the following formula (2).

Q1=△ _f H ^o _HX -△ _f H ^o _X- (2)

[In the formula, Δ _f H ^o _HX and Δ _f H ^o _X- respectively represent the heat of formation in the vacuum of HX and X ⁻ , respectively].

Here, the value of the generated heat (Δ _f H ^o ) can be used in the semi-empirical experience described in J. Chem. Soc. Perkin Trans. 2, p. 923 (1995). Molecular orbital method (MOPAC PM3 method) to calculate.

The generated heat value can be calculated as heat of formation in vacuum (25 ° C) using, for example, "CA Che Worksystem 6.01" manufactured by Fujitsu Co., Ltd. In other words, the value of the generated heat can be obtained by writing the molecular structure to be calculated on the "Work Space", and optimizing the structure by using "MM2 geometry" as the molecular force field method, and using it as a half. The "PM3 geometry" of the empirical molecular orbital method is calculated.

Further, the heat generation change (Q1) (kcal/mol, 25 ° C) in the acid dissociation reaction of the acid group (X1) or the acid group (X2) is from 3 to 200, and the zeta potential is lowered. For example, it is preferably 10 to 150, more preferably 15 to 100, more preferably 20 to 80, and particularly preferably 20 to 65.

Examples of the acid group (X2) include a sulfonic acid group (-SO ₃ H) (Q1 = 32 kcal/mol), a sulfate group (-OSO ₃ H) (Q1 = 46 kcal/mol), and a carboxyl group (-COOH). (Q1=21 kcal/mol), carboxymethoxy (-OCH ₂ COOH) (Q1=19 kcal/mol), carboxyethoxy (-OCH ₂ CH ₂ COOH) (Q1=20 kcal/mol), ( b) Carboxymethylamino (-NRCH ₂ COOH or -N(CH ₂ COOH) ₂ ) (Q1 = 26 kcal / mol), (b) carboxyethylamino group (-NRCH ₂ CH ₂ COOH or -N (CH ₂ CH ₂ COOH) ₂ ) (Q1 = 20 kcal / mol) and the like.

Among these acid groups, a viewpoint of preventing re-adhesion of particles and industrially easy production, etc., is preferably a sulfonic acid group, a sulfuric acid group or a carboxyl group, and the viewpoint of preventing hydrolysis of the neutralized salt (AB2). More preferably, it is a sulfonic acid group or a carboxyl group.

Examples of the acid group (X1) include a sulfonic acid group, a sulfuric acid group, a carboxyl group, a carboxymethoxy group, a carboxyethoxy group, a (di)carboxymethylamino group, and (ii) in the acid group (X2) exemplified above. Carboxyethylamino group and the like.

Among these acid groups, a sulfonic acid group, a sulfuric acid group, a carboxymethoxy group or a carboxyethoxy group is preferable in terms of prevention of re-adhesion of particles and industrially easy production, and the like, thereby preventing neutralization salts. The viewpoint of hydrolysis of (AB1) or the like is more preferably a sulfonic acid group, a carboxymethoxy group or a carboxyethoxy group, and particularly preferably a sulfonic acid group.

The hydrophobic group (Y) in the acidic compound (A1) includes an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and the like.

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). .

The alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group or a dodecyl group.

Examples of the alkenyl group include a n-propenyl group, an isopropenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, an undecyl group, and a dodecenyl group.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aromatic ring-containing hydrocarbon group include an aromatic hydrocarbon having a carbon number of 7 to 36, and examples thereof include methylphenyl group, ethylphenyl group, n-propylphenyl group or isopropylphenyl group, and butylphenyl group. Pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, nonylphenyl, undecylphenyl, dodecylphenyl, octylnaphthyl, anthranylnaphthyl , dodecylnaphthyl and the like.

Among the hydrophobic groups (Y), an aliphatic hydrocarbon group or an aromatic ring-containing hydrocarbon group is preferred, and more preferably an octyl group, a decyl group, a fluorenyl group, an eleven group, a dodecyl group, an octylphenyl group or a nonylphenyl group. , dodecylphenyl, octylnaphthyl, nonylnaphthyl, dodecylnaphthyl, especially preferably octyl, decyl, dodecyl, octylphenyl, dodecylphenyl, octylnaphthalene base.

The hydrophobic group (Y) has a carbon number of 1 to 36, more preferably 4 to 24, and particularly preferably 8 to 24. Some or all of the hydrogen atoms of the hydrophobic groups may be other atoms (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) or a functional group (hydroxyl group, amine group, mercapto group, perfluoroalkyl group, carboxyl group, or an organic group containing an ether bond, a guanamine bond, or an ester bond) Further, the functional group may contain one or more oxyalkylene groups.

The acidic compound (A1) includes the following compounds and the like.

Compound having a sulfonic acid group (A1-1)

For example, alkylsulfonic acid (octylsulfonic acid, mercaptosulfonic acid, dodecylsulfonic acid, myristylsulfonic acid, hexadecanosulfonic acid, stearylsulfonic acid, etc.), benzenesulfonic acid, alkyl Benzenesulfonic acid (toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, behenylbenzenesulfonic acid, etc.), naphthalenesulfonic acid, sulfonic acid succinic acid, alkylnaphthalenesulfonic acid (methylnaphthalenesulfonic acid) Acid, dodecylnaphthalenesulfonic acid, behenylnaphthalenesulfonic acid, etc.), polyoxyalkylene alkyl ether sulfonic acid (polyoxyethylene octyl ether sulfonic acid, polyoxyethylene lauryl ether sulfonic acid, etc.), α- Olefinic acid sulfonic acid, alkyl adenyl amino ethyl sulfonic acid, and the like.

Compound having a sulfate group (A1-2)

Examples thereof include alkyl sulfates (octyl sulfate, mercaptosulfate, dodecyl sulfate, myristyl sulfate, hexadecan sulfate, stearyl sulfate, etc.), polyoxyalkylene oxides Ether ether sulfate (polyoxyethylene octyl ether sulfate, polyoxyethylene lauryl ether sulfate, etc.), polyoxyalkylene alkyl aryl ether sulfate (polyoxyethylene octyl phenyl ether sulfate, polyoxyethylene) Mercaptophenyl ether sulfate, etc., mercaptoguanamine alkyl sulfate, and the like.

Among these, alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, sulfonic acid succinic acid, polyoxyalkylene alkyl ether sulfonic acid, polyoxyalkylene alkyl group are preferred. Aryl ether sulfonic acid, α-olefin sulfonic acid, alkyl mercapto amino ethyl sulfonic acid, alkyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl aryl Ethyl ether sulfate, mercaptoguanamine alkyl sulfate, more preferably alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, sulfonic acid succinic acid, polyoxyalkylene alkyl ether sulfonate An acid, a polyoxyalkylene alkyl aryl ether sulfonic acid, an alpha olefin sulfonic acid, an alkyl decyl amino ethyl sulfonic acid.

The Hydrophile-Lipophile Balance (HLB) value of the acidic compound (A1) is preferably from 5 to 30, more preferably from 7 to 17, more preferably from 9 to 16, and particularly preferably from 10 to 15, preferably. It is 10.5~14.5.

Further, in the present invention, the HLB value is a value calculated by the Oda method and using the formula (3) (Introduction of Fujimoto Takehiko, Introduction to Surfactant (Sanyo Chemical Industry Co., Ltd.), p212 (2007)) .

HLB=10×(inorganic/organic) (3)

In addition, the organicity and the inorganicity in the formula are the total values of the values defined for the atoms and functional groups of the respective constituent molecules, and the values described in the above documents can be used.

The pKa of the acidic compound (A1) is preferably 8.0 or less, and more preferably 7.0 or less, and particularly preferably 5.5 or less, and most preferably 3.0 or less, from the viewpoint of lowering the kinematic potential. Further, it is preferably 0.5 or more. Here, pKa means the acid dissociation constant of the first stage. Further, pKa can be obtained by a known method (for example, J. Am. Chem. Soc., 1673 (1967)} or the like.

As a polymer (A2) having at least one acid group (X2), it is a pellet The polymer (A2-1) having a sulfonic acid group, the polymer having a sulfuric acid group (A2-2), or a polymer having a carboxyl group (A2-3) is preferred from the viewpoint of re-adhesion prevention property and the like. More preferably, it is a polymer (A2-1) having a sulfonic acid group or a polymer (A2-3) having a carboxyl group.

As the polymer (A2-1) having a sulfonic acid group, a polymer (A2-1-1) obtained by radical polymerization using an unsaturated monomer (aX-1) having a sulfonic acid group is exemplified. A polymer (A2-1-2) obtained by a polycondensation reaction with formaldehyde using an aromatic compound (aY-1) having a sulfonic acid group in the molecule.

The polymer (A2-2) having a sulfuric acid group may, for example, be a polymer (A2-2-1) obtained by radical polymerization using an unsaturated monomer (aX-2) having a sulfate group.

The polymer (A2-3) having a carboxyl group and a polymer (A2-3-1) obtained by radical polymerization using an unsaturated monomer having a carboxyl group (A2-3) can be used.

Among the polymers (A2), a polymer having a carboxyl group (A2-3) and a polymer having a sulfonic acid group (A2-1) are preferable from the viewpoint of the prevention of particle re-adhesion, and the like. (A2-3-1), (A2-1-1) or (A2-1-2).

The polymer (A2) used in the present invention may be used singly or as a mixture of two or more kinds.

Examples of the unsaturated monomer (aX-1) having a sulfonic acid group include aliphatic unsaturated sulfonic acids (vinylsulfonic acid, (meth)allylsulfonic acid, etc.) having a carbon number of 2 to 20, Aromatic unsaturated sulfonic acid having a carbon number of 6 to 24 (styrenesulfonic acid, p-nonylstyrenesulfonic acid, etc.), sulfonic acid group-containing (meth) acrylate {2-(Methyl)acryloxyethoxyethanesulfonic acid, 2-(methyl)propenyloxypropanesulfonic acid, 3-(methyl)acryloxypropanesulfonic acid, 2-(methyl)propene醯oxybutanesulfonic acid, 4-(methyl)propene decyloxybutanesulfonic acid, 2-(methyl)propenyloxy-2,2-dimethylethanesulfonic acid, p-(methyl)propene fluorene Oxymethylbenzenesulfonic acid, etc., sulfonic acid group-containing (meth) acrylamide {2-(methyl) propylene decyl ethane sulfonic acid, 2-(methyl) acryl decylamino group - 2,2-dimethylethanesulfonic acid, etc.}.

Among these, from the viewpoints of polymerizability and hydrolysis resistance in water, etc., an aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms and an aromatic unsaturated sulfonic acid having 6 to 24 carbon atoms are preferable. Acid or sulfonic acid group-containing (meth) acrylamide, more preferably vinyl sulfonic acid, styrene sulfonic acid or 2-(methyl) propylene decylamino-2,2-dimethylethane sulfonic acid .

Examples of the unsaturated monomer (aX-2) having a sulfate group include a sulfate of a hydroxyl group-containing monomer.

Among these, from the viewpoint of polymerizability and the like, a sulfate of a hydroxyl group-containing (meth) acrylate is preferable, and 2-hydroxyethyl (meth)acrylate or (meth)acrylic acid 2 is more preferable. Sulfate of -hydroxypropyl ester.

As the unsaturated monomer (aX-3) having a carboxyl group, an unsaturated monocarboxylic acid {(meth)acrylic acid, vinylbenzoic acid, allyl acetic acid, (iso)crotonic acid ((iso) )crotonic acid), cinnamic acid and 2-carboxyethyl acrylate, etc., unsaturated dicarboxylic acid or anhydride of unsaturated dicarboxylic acid {maleic acid (anhydride), fumaric acid, itaconic acid ( Anhydride), citraconic acid (anhydride), mesaconic acid, etc.

Among these, unsaturated monocarboxylic acid (unsaturated monocarbonic acid) is preferred from the viewpoints of polymerizability and hydrolysis resistance in water. Acid), an anhydride of an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid, more preferably (meth)acrylic acid, maleic acid (anhydride), fumaric acid ) or itaconic acid (anhydride).

A polymer (A2-1-1) to a polymer (A2-3-1) obtained by radical polymerization using an unsaturated monomer and an unsaturated monomer having a sulfonic acid group (aX-1) The unsaturated polymerizable monomer (aX-2) having a sulfuric acid group or a radically polymerizable unsaturated monomer other than the unsaturated monomer (aX-3) having a carboxyl group is copolymerized.

The monomer (aX-1) to the monomer (aX-3) may be used singly or as a mixture of two or more kinds. In the case of a copolymer, it may be any structure of a random copolymer or a block copolymer.

Specific examples of the polymer (A2-1-1) include polystyrenesulfonic acid, styrene/styrenesulfonic acid copolymer, and poly{2-(methyl)acrylenylamino-2,2. - dimethylethanesulfonic acid}, 2-(methyl)propenylamino-2,2-dimethylethanesulfonic acid/styrene copolymer, 2-(methyl)propenylamino-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 sulfate (meth)acrylate}, 2-hydroxyethyl acrylate/2-hydroxyethyl 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, and 2-hydroxyethyl methacrylate/(meth)acrylic acid. Copolymers, etc.

As a method of synthesizing the polymer (A2-1-1) to the polymer (A2-3-1) obtained by radical polymerization using an unsaturated monomer, a known radical polymerization method can be used. For example, the monomer (aX-1) to the monomer (aX-3) and optionally other radical polymerizable unsaturated monomers are contained in a solvent such as water or an alcohol solvent at a temperature of 30 ° C to 150 ° C. Monomer, and 0.1% by weight to 30% by weight of a radical initiator (persulfate, azobismethylmercaptopropane, azobisisobutyronitrile, etc.) relative to the monomer polymerization. If necessary, a chain transfer agent such as a mercaptan can also be used.

The aromatic compound (aY-1) having a sulfonic acid group used in the synthesis of the polymer (A2-1-2) may, for example, be an arylsulfonic acid (benzenesulfonic acid or the like) or an alkyl group (carbon). The number is 1~24) arylsulfonic acid (toluenesulfonic acid, dodecylbenzenesulfonic acid, monobutylbiphenylsulfonic acid, etc.), polycyclic aromatic sulfonic acid (naphthalenesulfonic acid, sulfonic acid, hydroxynaphthalene) Sulfonic acid, hydroxy sulfonic acid, etc.), alkyl (carbon number: 1 to 24) substituted polycyclic aromatic sulfonic acid {alkyl (carbon number: 1 to 24) naphthalenesulfonic acid (methylnaphthalenesulfonic acid, dimethyl Naphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, laurylnaphthalenesulfonic acid, tetradecylnaphthalenesulfonic acid, etc.), methylsulfonic acid, laurylsulfonic acid , bisphenol sulfonic acid, etc., phenolsulfonic acid (phenol sulfonic acid, monobutyl phenyl phenol monosulfonic acid, dibutyl phenyl phenol disulfonic acid, etc.), alkyl (carbon number 1 to 24) Phenolic sulfonic acid (cresol sulfonic acid, nonylphenol sulfonic acid, decyl phenol sulfonic acid, etc.), aromatic amino sulfonic acid (aniline sulfonic acid, etc.), lignin sulfonic acid (lignin sulfonate) An acid salt, a modified lignin sulfonic acid), a sulfonic acid group-containing compound having a triazine ring (melamine sulfonic acid, etc.), and the like.

Among these, in terms of re-adhesion prevention, etc., an alkane is preferred. Base (carbon number: 1 to 24) arylsulfonic acid, polycyclic aromatic sulfonic acid, alkyl group (carbon number: 1 to 24) substituted polycyclic aromatic sulfonic acid, more preferably dodecylbenzenesulfonic acid, naphthalene Sulfonic acid, dimethylnaphthalenesulfonic acid.

In addition to the aromatic compound (aY-1) having a sulfonic acid group, other aromatic compound (aO), urea or the like may be used as a constituent component in the polymer (A2-1-2).

Examples of the other aromatic compound (aO) include benzene, an alkylbenzene (the carbon number of the alkyl group is 1 to 20), naphthalene, an alkylnaphthalene (the carbon number of the alkyl group is 1 to 20), phenol, and cresol. , hydroxy naphthalene, aniline and the like.

Specific examples of the polymer (A2-1-2) include a naphthalenesulfonic acid formaldehyde condensate, a methylnaphthalenesulfonic acid formaldehyde condensate, a dimethylnaphthalenesulfonic acid formaldehyde condensate, and an octylnaphthalenesulfonic acid formaldehyde condensation. , naphthalenesulfonic acid-methylnaphthalene-formaldehyde condensate, naphthalenesulfonic acid-octylnaphthalene-formaldehyde condensate, hydroxynaphthalenesulfonic acid formaldehyde condensate, hydroxynaphthalenesulfonic acid-cresolsulfonic acid-formaldehyde condensate, sulfonate An acid formaldehyde condensate, a melamine sulfonic acid formaldehyde condensate, an aniline sulfonic acid-phenol-formaldehyde condensate, and the like.

As a method of synthesizing the polymer (A2-1-2), a known method can be used. For example, the above-mentioned method may be mentioned: the above-mentioned aromatic compound (aY-1) having a sulfonic acid group, and optionally other compound (aO) or urea, an acid (sulfuric acid or the like) or a base (hydrogen hydroxide) used as a catalyst. Add sodium or the like to the reaction vessel, and add a predetermined amount of aqueous formaldehyde solution (for example, 37 wt% aqueous solution) over a period of 1 hour to 4 hours under stirring at 70 ° C to 90 ° C. After the dropwise addition, the mixture is stirred under reflux for 3 hours. 30 hours and cooling.

Further, a compound (aY-1) may be used as a compound (aY-1) by neutralizing a part or all of a sulfonic acid group by using the compound (B) in advance. Neutralized salt (AB2) was obtained directly at the same time as (A2-1-2).

When other compounds (aO) are used, the molar ratio {(aY-1)/(aO)} of (aY-1) and (aO) is preferably from 1 to 99/99 to 1, more preferably from 10 to 90. /90~10, especially good is 30~85/70~15, the best is 50~80/50~20.

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

Further, (aY-1) or (aO) may be used as a mixture of two or more kinds.

The pKa of the polymer (A2) is preferably 8.0 or less, and more preferably 7.0 or less, and particularly preferably 5.5 or less, and most preferably 3.0 or less, from the viewpoint of lowering the kinematic potential. The pKa can be obtained 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 100,000, from the viewpoint of improvement in surface quality such as reduction of scratches and low foaming properties.

The weight average molecular weight is a value obtained by measuring gel permeation chromatography (hereinafter abbreviated as GPC (Gel Permeation Chromatography)) and measuring polyethylene oxide as a standard substance at 40 °C. For example, the device body: HLC-8120 manufactured by Tosoh Co., Ltd., pipe column: TSK gel G5000 PWXL, G3000 PW XL manufactured by Tosoh Co., Ltd., detector: differential refractometer detector built in the body of the device, dissolving solution : 0.2 M anhydrous sodium sulfate, 10% acetonitrile buffer, flow rate of the solution: 0.8 ml/min, column temperature: 40 ° C, sample: 1.0 wt% of the solution of the solution, injection amount: 100 μl, standard substance: Tosoh (Stock) manufactured by TSK SE-30, SE-15, SE-8, SE-5.

Next, the compound (B) constituting the neutralized salt (AB1) and the neutralized salt (AB2) will be described.

In the present invention, as the compound (B), a compound having a heat generation change (Q2) in the proton addition reaction of 10 kcal/mol to 152 kcal/mol is used.

In the present invention, the heat of formation (Q2) in the proton addition reaction means the heat of formation of B and the H ⁺ B in the proton addition reaction of the compound (B) represented by the following formula (4). Generate a difference in heat.

B+H ⁺ → H ⁺ B (4)

That is, Q2 is represented by the following formula (5).

Q2=△ _f H ^o _H+B -△ _f H ^o _B (5)

[wherein, Δ _f H ^o _H+B and Δ _f H ^o _B sequentially represent heat of formation in vacuum in H ⁺ B and B, respectively].

As described above, the value of the generated heat (Δ _f H ^o ) can be calculated using the semi-empirical molecular orbital method (MOPAC PM3 method).

Further, the position at which H ^{+ is} added when the heat of formation of H ⁺ B is calculated is on the nitrogen atom contained in the compound (B). In addition, when a plurality of nitrogen atoms are present, heat of generation is calculated for each nitrogen atom, and a value obtained when the difference between the heat of generation of B and the heat of formation of H ⁺ B is minimized is referred to as a heat generation change (Q2).

Heat generation change in the proton addition reaction of compound (B) (Q2) (kcal/mol, 25 ° C) is 10 to 152. From the viewpoint of lowering the dynamic potential, etc., it is preferably 30 to 148, more preferably 40 to 145, particularly preferably 50 to 143, and most preferably 100 to 152. 141.

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

The molecular volume (nm ³ ) of the compound (B) is preferably from 0.025 to 0.7, and more preferably from 0.050 to 0.5, particularly preferably from 0.12 to 0.36, from the viewpoint of lowering the potential.

Here, the molecular volume refers to the volume of the space formed on the isoelectric density plane of the molecule, and can be used according to the molecular force field method of MM2 (Allinger, NL, J. Am. Chem. Soc (American Journal of Chemistry) , 99, 8127 (1977)), and optimized structure for calculation as a semi-empirical molecular orbital method of PM3 (Stewart, JJP, J. Am. Chem. Soc., 10, 221 (1989)). And get. For example, "CAChe Worksystem 6.01" manufactured by Fujitsu Co., Ltd. can be used, and the structure is optimized in the same manner. Then, "PM3 geometry" which is a semi-empirical molecular orbital method is used for calculation on "Project Leader". Furthermore, in the case where the result of the calculation is that a value of a plurality of molecular volumes is obtained, the maximum value is used.

Specific examples of the compound (B-1) include 胍{胍(Q2=147 kcal/mol, molecular volume=0.062 nm ³ ), methyl hydrazine (Q2=144 kcal/mol, molecular volume=0.084 nm ^{3 )} ), tetramethyl hydrazine (Q2 = 145 kcal / mol, molecular volume = 0.147 nm ³ ), ethyl hydrazine (Q2 = 142 kcal / mol, molecular volume = 0.104 nm ³ ), phenyl hydrazine (Q2 = 141 kcal / Mol, molecular volume = 0.139 nm ³ ), etc., monocyclic 胍 [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=0.113 nm ³ ), etc.}, polycyclic 胍{1,3,4,6,7,8-hexahydro-2H-pyrimidine Pyrimido [1,2-a]pyrimidine (hereinafter abbreviated as TBD) (Q2=147 kcal/mol, molecular volume=0.159 nm ³ ), 1,3,4,6,7,8-six Hydrogen-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 ), and 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 = 0.113 nm ³ ), 2-methyl-4,5-dihydro-1H-imidazole (Q2=147 kcal/mol, molecular volume=0.113 nm ³ ), 2-ethyl-4,5-di Hydrogen-1H-imidazole (Q2=145 kcal/mol, molecular volume=0.119 nm ³ ), etc., a 2-ring type oxime represented by the following general formula (6).

[Chemical 1]

In the formula, R ⁷ and R ⁸ each independently represent 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, and a carbon number of 6 An aryl group of ~30, or an arylalkyl group having a carbon number of 7 to 30, a part or all of a hydrogen atom in an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an arylalkyl group may further be a hydroxyl group or an amine group. (2) an alkyl group (having a carbon number of 1 to 24) an amine group, a (di)hydroxyalkyl group (having a carbon number of 2 to 4) an amine group, a mercapto group or a halogen atom (a fluorine atom, a chlorine atom, or a bromine group) Substituted by atom, iodine atom). Further, two R ⁷ and two R ⁸ may be the same or different, and may be bonded to each other (carbon-carbon bond, ether bond, or the like) to form a ring having 4 to 12 carbon atoms. m and n mutually represent an integer of 1 to 12}.

The alkyl group having 1 to 24 carbon atoms or the alkenyl group having 2 to 24 carbon atoms is exemplified by an alkyl group or an alkenyl group exemplified in the hydrophobic group (Y), and an alkyl group having 1 to 24 carbon atoms. Or alkenyl.

The alkynyl group having 2 to 30 carbon atoms may be any of a linear chain and a branched form, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-dodecynyl group or a 2- Dodecynyl, 1-tridecynyl or 2-tridecynyl, 1-tetradecynyl or 2-tetradecynyl, 1-hexadecenyl or 2-hexadecenyl, 1-ten Octa-yl or 2-octadecynyl, 1-nonenyl or 2-nonenyl, 1-eicosyl or 2- Eicosyl, 1-tetracosyl or 2-tetradecynyl.

Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a methylnaphthyl group.

Examples of the arylalkyl group having a carbon number of 7 to 30 include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 5-phenylpentyl group, and a 6-benzene group. Hexyl, 7-phenylheptyl, 8-phenyloctyl, 10-phenylindenyl, 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 a carbon number of 4 to 12, two R ⁷ or two R ⁸ form a divalent organic group (a hydrocarbon having a carbon number of 4 to 12) Base, etc.).

Examples of the alkylene group having a carbon number of 4 to 12 include a butyl group, a pentyl group, a hexyl group, a heptyl group, a octyl group, a decyl group, a dodecyl group, and the like. It can also be bonded by an ether bond or the like.

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

As the compound (B), a preferred compound is ruthenium, methyl hydrazine, ethyl hydrazine in (B-1), DBU in (B-2), and the like. DBN, better for DBU or DBN.

The compound (B) may be used singly or as a mixture of two or more kinds.

Further, the pKa of the compound (B) is preferably from 11 to 40, and more preferably from 11.5 to 30, particularly preferably from 12 to 25, from the viewpoint of lowering the potential.

Further, the pKa of the compound (B) can be obtained by a known method (for example, Can. J. Chem. 65, 626 (1987)} or the like.

In the present invention, the neutralized salt (AB1) of the acidic compound (A1) and the compound (B), the neutralized salt of the polymer (A2) and the compound (B) (AB2) are as long as the acid group (X1) or the acid group ( Part or all of X2) may be neutralized by (B).

Specific examples of the neutralized salt (AB1) include the following compounds and the like.

The alkylbenzenesulfonate (p-toluenesulfonate, toluenesulfonic acid DBU salt, toluenesulfonic acid DBN salt, xylene sulfonic acid guanidine salt, xylene sulfonic acid DBU salt, two Toluenesulfonic acid DBN salt, dodecylbenzenesulfonate phosphonium salt, dodecylbenzenesulfonic acid DBU salt, dodecylbenzenesulfonic acid DBN salt, etc.), naphthalenesulfonate (naphthalenesulfonate phosphonium salt, naphthalenesulfonic acid DBU) Salt, naphthalenesulfonic acid DBN salt, etc.), alkylnaphthalenesulfonate (methylnaphthalenesulfonate sulfonium salt, methylnaphthalenesulfonic acid DBU salt, methylnaphthalenesulfonic acid DBN salt, dodecylnaphthalenesulfonate sulfonium salt, DBU salt of dodecylnaphthalenesulfonic acid, DBN salt of dodecylnaphthalenesulfonic acid, etc.).

Specific examples of the neutralized salt (AB2) include the following compounds and the like.

Examples thereof include polyacrylate (polyacrylic acid DBU salt, polyacrylic acid DBN salt, etc.), polystyrene sulfonate (polystyrene sulfonate sulfonium salt, polyphenylene) a salt of a naphthalenesulfonic acid formaldehyde condensate (a naphthalenesulfonic acid formaldehyde condensate sulfonium salt, a naphthalene sulfonic acid formaldehyde condensate DBU salt, a naphthalenesulfonic acid formaldehyde condensate DBN) Salt, etc.), a salt of an alkylnaphthalenesulfonic acid formaldehyde condensate (methylnaphthalenesulfonic acid formaldehyde condensate sulfonium salt, methylnaphthalenesulfonic acid formaldehyde condensate DBU salt, methylnaphthalenesulfonic acid formaldehyde condensate DBN salt, methyl group Naphthalenesulfonic acid formaldehyde condensate TBD salt, methylnaphthalenesulfonic acid formaldehyde condensate MTBD salt, octylnaphthalenesulfonic acid formaldehyde condensate sulfonium salt, octylnaphthalenesulfonic acid formaldehyde condensate DBU salt, octylnaphthalenesulfonic acid formaldehyde condensate Salt of DBN salt, etc., naphthalenesulfonic acid-alkylnaphthalene-formaldehyde condensate (naphthalenesulfonic acid-octylnaphthalene-formaldehyde condensate sulfonium salt, naphthalenesulfonic acid-octylnaphthalene-formaldehyde condensate DBU salt, naphthalenesulfonic acid - octyl naphthalene-formaldehyde condensate DBN salt, etc.). (AB1) and (AB2) may be a single compound or a mixture of two or more.

The neutralization salt (AB1) preferably has a ratio of (Q1) to (Q2) {Q2/(Q1×p)} satisfying the formula (7), and more preferably satisfies the formula (8). ), especially to satisfy the formula (9), and the best is to satisfy 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)

p: represents the number of acid groups (X) required to neutralize the basic compound (B).

The weight average molecular weight (Mw) of the neutralized salt (AB2) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 200,000, and particularly preferably 3,000, from the viewpoint of improvement in surface quality such as scratch reduction and low foaming property. ~100,000. Further, the Mw of the neutralized salt (AB2) is a value obtained by GPC in the same manner as the polymer (A2).

The polishing liquid for an electronic material of the present invention may contain at least one of a neutralizing salt (AB1) and a neutralizing salt (AB2). However, it is preferable to contain a polishing material such as a reduction in scratch quality. Neutralize the salt (AB2).

The neutralized salt (AB1) or the neutralized salt (AB2) can be obtained by a neutralization reaction of the acidic compound (A1) or the polymer (A2) with the nitrogen-containing basic compound (B). For example, an aqueous solution of (A1) and/or (A2) may be added to a reaction vessel capable of temperature adjustment and stirring, and (B) may be supplied at room temperature (about 25 ° C) while stirring (if necessary, an aqueous solution) ) and then mix evenly. In addition, for example, it can be obtained by simultaneously (or adding) (A1) and/or (A2) and (B) while stirring in a reaction vessel to which water is added in advance, and then uniformly mixing. The concentration at the time of the neutralization reaction can be appropriately selected depending on the purpose.

Since the polishing liquid for an electronic material of the present invention has a large degree of dissociation of the acid group (X1) and the acid group (X2), the dynamic potential of the particles and the substrate can be effectively reduced, and the re-adhesion of the particles can be prevented.

The concentration of the neutralizing salt (AB) in the polishing liquid for electronic materials is 0.001 wt% to 10 wt%, preferably 0.01 wt%, depending on the weight of the polishing liquid. 5 wt%.

The water which is an essential component of the polishing liquid for electronic materials of the present invention preferably has a specific resistance of 18 MΩ from the viewpoint of cleanliness. Examples of the pure water of cm or more include ultrapure water, ion exchange water, reverse osmosis water, distilled water, and the like.

Another embodiment of the present invention is a polishing liquid for a step of polishing an electronic material intermediate using a polishing pad, and is a polishing liquid for an electronic material containing a neutralizing salt (AB) and water as essential components.

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

As the abrasive particles (C) in the present invention, commercially available abrasive particles for polishing an electronic material can be used, and it is not particularly limited. Examples of the material of the abrasive particles (C) include colloidal silica, cerium oxide, alumina, zirconia, diamond, manganese oxide, titanium oxide, and strontium carbide. Boron nitride or the like is preferably colloidal cerium oxide, cerium oxide, aluminum oxide or diamond from the viewpoint of the effect of reducing scratches.

The average particle diameter of the abrasive particles (C) varies depending on the polishing particles to be used, and in the case of colloidal cerium oxide, it is usually 5 nm to 100 nm. In the case of cerium oxide, the productivity of the substrate for electronic materials is used. From the viewpoint, it is preferably from 0.1 μm to 3.0 μm.

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

In the polishing liquid for an electronic material of the present invention, in addition to the above-mentioned neutralized salt (AB) or water, a surfactant (D) other than the neutralized salt (AB) may be contained. It can be used in the polishing step by containing a surfactant (D).

The surfactant (D) in the present invention includes an anionic surfactant (D2) other than the nonionic surfactant (D1) and the neutralized salt (AB).

Examples of the nonionic surfactant (D1) include a higher alcohol alkylene (carbon number of 2 to 4) oxide additive (D11) having a carbon number of 8 to 18. ), polyoxyethylene polyoxypropylene copolymer (D12), an alkylamine oxide additive (D13) of an aliphatic amine having a carbon number of 8 to 36 Or a polyol type nonionic surfactant (D14) or the like.

As a higher alcohol alkyl group (carbon number: 2 to 4) oxide adduct (D11) having a carbon number of 8 to 18, an oxirane ethylene oxide adduct, lauryl alcohol epoxy B, An alkane adduct, an ethylene oxide adduct of stearyl alcohol, and the like.

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

The alkylene oxide adduct (D13) of the aliphatic amine having a carbon number of 8 to 36 may, for example, be an alkylene oxide adduct of an aliphatic primary amine having a carbon number of 8 to 24 (D131). Or an alkylene oxide adduct (D132) of an aliphatic secondary amine having a carbon number of 8 to 36.

Alkyl oxide adducts of aliphatic primary amines having a carbon number of 8 to 24 The aliphatic primary amine of the starting material in (D131) may be linear, branched or cyclic, and is an aliphatic primary amine having 8 to 24 carbon atoms which may have a saturated bond or an unsaturated bond.

Specific examples of the aliphatic primary amine include: laurylamine, octylamine, decylamine, undecylamine, tridecylamine, tetradecylamine, pentaamine, hexadecylamine, heptadecylamine, octadecylamine, and ten. Nine amine, behenylamine, behenylamine, dodecaamine, behenylamine, tetracosylamine, octadecylamine or octadecadienamine, or tallow amine, hardening as a mixture of these An aliphatic primary amine of a source of automatic vegetable oil such as tallow amine, coconut oleylamine, palm oleylamine or soybean oil amine. The aliphatic primary amine may be used alone or in a mixture of two or more.

The aliphatic secondary amine of the raw material of the alkylamine oxide adduct (D132) having an aliphatic carbon number of 8 to 36 may be linear, branched or cyclic, and may have a saturated bond. Or an aliphatic secondary amine having an unsaturated bond having a carbon number of 8 to 36.

Specific examples of the aliphatic secondary amine include dioctylamine, dibutylamine, dihexylamine, didecylamine, di-undecylamine, di-dodecylamine, di-tridecanamine, and di-tenth. Tetraamine, di-pentadecylamine, di-hexadecylamine, di-heptadecylamine or di-octadecylamine.

The aliphatic secondary amine may be used alone or in a mixture of two or more.

The alkylene oxide as a raw material in the alkylene oxide adduct (D13) of the aliphatic amine of the present invention may, for example, be an alkylene oxide having a carbon number of 2 to 12, such as ethylene oxide. 1,2-propylene oxide, 1,2-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, and the like. Among these, from the viewpoint of availability, ethylene oxide and 1,2-propylene oxide are preferred. These alkylenes The base oxide may be used alone or in combination of two or more. When two or more types are used in combination, they may be random or block.

The average addition mole number of the alkylene oxide in (D131) or (D132) is preferably from 3 moles to 100 moles, more preferably from 3 moles to 70 moles, relative to the amine 1 mole. Very good for 3 moles ~ 40 moles.

As a method of producing (D131) and (D132), a known method or the like can be used.

Specifically, a method in which the above aliphatic primary amine or aliphatic secondary amine is added to a pressure-resistant container that can be stirred and sufficiently replaced with an inert gas (nitrogen gas, argon gas, etc.) can be used. Dehydration is carried out by pressing, and then the above alkylene oxide is introduced at a reaction temperature of about 80 ° C to 160 ° C to carry out the reaction. Further, at the time of the reaction, a known catalyst may be used as needed. The catalyst can be added initially from the reaction or added from the middle.

Examples of the catalyst include a catalyst containing no metal atom (quaternary ammonium hydroxide such as tetramethylammonium hydroxide, and tetramethylethylenediamine or 1,8-diguanidine) [5.4.0] A tertiary amine such as undecene-7 or the like, and a catalyst containing a metal atom (alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxide, and alkaline earth metal oxide).

The concentration of the alkylamine oxide adduct (D13) of the aliphatic amine in actual use is 0.001 wt% to 10 wt%, based on the weight of the slurry.

The polyhydric alcohol type nonionic surfactant (D14) may, for example, be a glycerin ethylene oxide adduct or a sorbitan ethylene oxide adduct.

Examples of the anionic surfactant (D2) include a fatty acid-based surfactant (a fatty acid (salt) having a carbon number of 8 to 18 or a carbon number of 8 to 18 An ether carboxylic acid (salt) of an aliphatic alcohol, etc.]; a phosphate ester surfactant [a mono- or di-ester (salt) of a higher alcohol having a carbon number of 8 to 24, or a higher alcohol having a carbon number of 8 to 24. A mono- or di-ester (salt) of an alkylene oxide adduct.

Among the anionic surfactants (D2), a fatty acid amine salt is preferred from the viewpoint of lubricity, and a fatty acid amine salt is a fatty acid having a carbon number of 8 to 22 (for example, oleic acid). Completely neutralize or neutralize a part of it.

Examples of the amine include a primary amine such as monoethanolamine; a secondary amine such as diethanolamine; and a tertiary amine such as triethanolamine.

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

In the polishing liquid for an electronic material of the present invention, an organic reducing agent (E) may be contained as needed. By blending the organic reducing agent (E), adhesion prevention to particles can be improved after polishing.

Examples of the organic reducing agent (E) include phenols (E1) and reduced ketones (E2).

As the organic reducing agent (E), a commercially available organic reducing agent can be used, and from the viewpoint of the polishing rate, a phenol (E1) or a reducing ketone (E2) is preferable.

The phenol (E1) is a compound represented by the following formula (11).

[Chemical 2]

[wherein, X ¹ to X ⁵ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, an amine group or an alkyl group]

Specific examples of the phenol (E1) represented by the formula (11) include phenol in which X ¹ to X ⁵ are hydrogen, pyrocatechol, resorcinol, and Polyphenolic compounds (E11) such as hydroquinone and pyrogallol; 2-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dicarboxyphenol, and 2, a carboxyl group-containing phenol compound (E12) such as 4,6-tricarboxyphenol; a carboxyl group-containing polyphenol compound (E13) such as gallic acid; and an amine group-containing phenol compound (E14) such as 4-aminophenol; An alkyl group-containing phenol compound (E15) such as cresol; or a salt thereof.

Among these, a polyphenol-based compound (E11), a carboxyl group-containing polyphenol compound (E13), and more preferably a carboxyl group-containing polyphenol compound are preferable from the viewpoint of the polishing rate and the adhesion prevention property of the particles ( E13), specifically gallic acid or a salt thereof.

The reductone (E2) may be a compound having a ketenediol group represented by the following formula (12) in the molecule.

[Chemical 3]

Specific examples of the reducing ketone (E2) include ascorbic acid (L-form, DL-form, D-form), Isoascorbic acid, Erythorbic acid, or an ester (L). - Ascorbyl sulfate, L-ascorbyl phosphate, L-ascorbic acid 2-glucoside, L-ascorbyl palmitate, L-ascorbyl tetraisopalmitate, ascorbic acid , isoascorbyl phosphate, isoascorbyl palmitate, tetraisopalmitate Etc); or some of these salts.

Among these, from the viewpoint of the polishing rate and the adhesion prevention property of the particles, L-ascorbic acid, isoerythorbic acid, an ester of L-ascorbic acid or an ester of isoascorbic acid, or a salt thereof is preferable. More preferably, it is L-ascorbic acid or a salt thereof.

Examples of the salts of the above (E1) and (E2) include an alkali metal salt (such as a sodium salt or a potassium salt), an alkaline earth metal salt (such as a calcium salt or a magnesium salt), an ammonium salt, an amine salt or a quaternary ammonium salt. .

The concentration of the organic reducing agent (E) in the polishing liquid at the time of use is preferably 0.01 wt% to 1 wt% from the viewpoint of adhesion prevention of particles.

In addition to the above, the polishing liquid of the present invention may contain a mineral acid (nitric acid, sulfuric acid, phosphoric acid, etc.) or a chelating agent (phosphonic acid-based chelating agent [hydroxyethylidene diphosphonic acid (HEDP) or a salt thereof, Methyldiphosphonic acid or a salt thereof, aminotris(methylenephosphonic acid) or a salt thereof, etc.; carboxylic acid chelating agent [diethylenetriamine-5 Acetic acid (DTPA) or a salt thereof, ethylenediaminetetraacetic acid (EDTA) or a salt thereof, hydroxyethyliminodiacetic acid (HIDA) or a salt thereof, citric acid or a salt thereof, gluconic acid or a salt thereof, etc.), Additives such as stabilizers (for example, p-toluenesulfonate) and rust inhibitors (benzotriazole, mercaptobenzotriazole, cyclohexylamine ethylene oxide adduct, etc.). These additives can be used as the polishing liquid, and are not particularly limited.

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

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

As an example of the manufacturing step (partial) of the electronic material using the polishing liquid of the present invention, the polishing step of the hard disk glass substrate will be described below as an example.

(1) The glass substrate is placed on a carrier of the polishing apparatus, and the glass substrate is sandwiched by a flat plate to which a polishing pad to which a diamond grindstone is attached is attached.

(2) While the polishing liquid of the present invention is supplied onto a flat plate, a load is applied to rotate the flat plate and the carrier.

(3) Confirm that the fixed film thickness has been polished and then stop the rotation.

(4) The glass substrate was taken out from the carrier and rinsed with running water.

(5) After the water is rinsed, the substrate is dried.

Further, as another example, the substrate step of the hard disk glass substrate will be described below as an example.

(1) The glass substrate to be polished is placed on a carrier of a polishing apparatus, and the glass substrate is sandwiched by a flat plate to which a polishing pad made of polyurethane is attached.

(2) While supplying the polishing liquid of the present invention containing cerium oxide, a flat plate and a carrier are rotated while applying a load.

(3) Confirm that the fixed film thickness has been polished and then stop the rotation.

(4) The glass substrate is subjected to running water rinsing, and then taken out from the carrier, and immersed or scrubbed with a cleaning agent.

(5) The water-washed glass substrate is placed on a carrier of the polishing apparatus, and the polishing liquid of the present invention containing colloidal cerium oxide is used in the same manner as described above.

(6) The polished substrate is rinsed, washed, and then rinsed again.

(7) Dry and bundle.

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

The polishing conditions such as the number of revolutions, the polishing time, the number of wobbles, and the load can be used when the polishing is performed by the previous polishing liquid.

[Example]

Hereinafter, the present invention will be further illustrated by examples and comparative examples, but the present invention is not limited to the examples and comparative examples. Hereinafter, unless otherwise specified, % means wt%, and parts means parts by weight.

Production Example 1 (Production of Polyacrylic Acid DBU Salt)

300 parts of isopropyl alcohol and 100 parts of ultrapure water can be added to adjust the temperature and In the stirred reaction vessel, the inside of the reaction vessel was replaced with nitrogen, and then the temperature was raised to 75 °C. Under stirring at 30 rpm, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropanol 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 introduced so as not to be solidified in the system, and a mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected. The obtained polyacrylic acid aqueous solution was neutralized to pH 7.0 with 450 parts of DBU, and then the concentration was adjusted with ultrapure water, whereby a 40% aqueous solution of polyacrylic acid DBU salt (AB-1) was obtained.

Further, the Mw of the polyacrylic acid DBU salt was 10,000.

Production Example 2 (Production of naphthalenesulfonic acid formaldehyde condensate DBU salt)

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

Production Example 3 (Production of sulfonium sulfonate sulfonate)

100 parts of ethylene dichloride is added to a stirred reaction vessel which can be tempered and refluxed, and after nitrogen substitution with stirring, the temperature is raised to At 90 ° C, ethylene dichloride was refluxed. An initiator solution obtained by dissolving 120 parts of styrene and 1.7 parts of 2,2'-azobisisobutyronitrile in 20 parts of ethylene dichloride in advance was separately dropped into the reaction vessel over 6 hours. After the completion of the dropwise addition, the polymerization was further carried out for 1 hour. After the polymerization, the mixture was cooled to 20 ° C under a nitrogen atmosphere, and then 105 parts of sulfuric anhydride was added dropwise over 10 hours while the temperature was controlled to 20 ° C. After the completion of the dropwise addition, the sulfonation reaction was further carried out for 3 hours. After the reaction, the solvent was distilled off and solidified, and then 345 parts of ultrapure water was added and dissolved to obtain an aqueous solution of polystyrenesulfonic acid. The obtained polystyrenesulfonic acid aqueous solution was neutralized to a pH of 7 by hydrazine, and then the concentration was adjusted with ultrapure water, thereby obtaining a polystyrene sulfonate sulfonium salt (AB-3) as an anionic surfactant. 40% aqueous solution. Further, (AB-3) had a Mw of 40,000 and a sulfonation ratio of 97%.

Production Example 4 (Production of sulfonium polystyrene sulfonate)

80 parts of ethylene dichloride was added to a stirred reaction vessel which was temperature-controlled and refluxed, and after nitrogen substitution with stirring, the temperature was raised to 90 ° C, and then ethylene dichloride was refluxed. 200 parts of styrene and 200 parts of 2,2'-azobisisobutyronitrile previously dissolved in 20 parts of ethylene dichloride were separately added to the reaction vessel over 6 hours. After the completion of the dropwise addition, the polymerization was further carried out for 1 hour. After the polymerization, the mixture was cooled to 20 ° C under a nitrogen atmosphere, and then 105 parts of sulfuric anhydride was added dropwise over 10 hours while the temperature was controlled to 20 ° C. After the completion of the dropwise addition, the sulfonation reaction was further carried out for 3 hours. After the reaction, the solvent was distilled off and solidified, and then 345 parts of ultrapure water was added and dissolved to obtain an aqueous solution of polystyrenesulfonic acid. The obtained polystyrenesulfonic acid aqueous solution is neutralized to a pH of 7 by using hydrazine, Then, the concentration adjustment was carried out using ultrapure water, whereby a 40% aqueous solution of a polystyrene sulfonate sulfonium salt (AB-4) as an anionic surfactant was obtained. Further, (AB-4) had a Mw of 224,000 and a sulfonation ratio of 97%.

Production Example 5 (Production of Dodecylbenzenesulfonic Acid DBU Salt)

100 parts of a 10% aqueous solution of dodecylbenzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., HLB: 7.4) was added to a reaction vessel which was temperature-controlled and stirred, and the mixture was stirred while being adjusted to 25 ° C while stirring. 4.7 parts of DBU was slowly added while stirring for 10 minutes to obtain a 14% aqueous solution of DBU salt of dodecylbenzenesulfonic acid (AB-5) (pH = 6.5 at 25 ° C).

Production Example 6 (Production of Aliphatic Amine Ethylene Oxide Additive)

185 parts (1.0 moles) of laurylamine and 3.6 parts (0.01 moles) of 25% TMAH aqueous solution were added to a stainless steel autoclave equipped with a stirring device and a temperature control device at 100 ° C, 4 kPa. Dehydration was carried out for 30 minutes under reduced pressure below. While controlling the reaction temperature to 100 ° C, 308 parts (7.0 mole parts) of ethylene oxide was added dropwise over 3 hours, and then aged at 100 ° C for 3 hours. Further, the mixture was stirred at 150 ° C for 2 hours under reduced pressure of 2.6 kPa or less to decompose and remove the remaining TMAH to obtain a laurylamine ethylene oxide 7 molar addition product as a nonionic surfactant ( D-2) 490 parts.

Comparative Production Example 1 (manufacture of sodium polyacrylate)

300 parts of isopropyl alcohol and 100 parts of ultrapure water were placed in a reaction vessel which was temperature-controlled and stirred, and the inside of the reaction vessel was replaced with nitrogen, and then the temperature was raised to 75 °C. Under stirring at 30 rpm, 407 parts of 75% aqueous solution of acrylic acid and 2,2'-azobisisobutyric acid were simultaneously added dropwise over 3.5 hours. 95 parts of a 15% isopropanol solution of dimethyl ester.

After completion of the dropwise addition, the mixture was stirred at 75 ° C for 5 hours, and then ultrapure water was intermittently introduced so as not to be solidified in the system, and a mixture of water and isopropyl alcohol was distilled off until isopropyl alcohol could not be detected. The obtained polyacrylic acid aqueous solution was neutralized to pH 7.0 with 70 parts of sodium hydroxide, and then the concentration was adjusted with ultrapure water, whereby a 40% aqueous solution of a sodium polyacrylate salt (AB'-1) was obtained.

Further, the Mw of the sodium polyacrylate salt was 10,000.

Example 1 to Example 49, and Comparative Example 1 to Comparative Example 19

The components described in Tables 1 to 6 were blended so as to become 100 parts in total, and then stirred at 40 ° C for 20 minutes at 25 ° C using a magnetic stirrer to obtain the slurry of the present invention and used for the same. Compare the slurry.

Further, the abrasive particles in the table used the following abrasive particles.

Colloidal cerium oxide slurry: "COMPOL80" manufactured (average particle size 80 nm, active ingredient concentration 40 wt%)

Cerium oxide: "HS-8005" manufactured by Showa Denko (average particle size 0.5 μm)

Alumina: "WA#20000" manufactured (average particle size 0.4 μm)

Diamond: "1/10 PCS-WB2" manufactured by Nanofactor (average particle size is 100 nm)

Polyoxyethylene polyoxypropylene copolymer: Sanyo Chemical Industry Co., Ltd. Newpole GEP2800

Dioleyl phosphate sodium salt: NAS-546 manufactured by Sanyo Chemical Industry Co., Ltd.

Aromatic sulfonate: A reagent using sodium hydroxy naphthylsulfonate.

As a performance evaluation of the polishing liquid, an evaluation test of scratch reduction performance, particle adhesion reduction performance, and polishing rate sustainability performance was carried out by the following method.

Furthermore, in order to prevent contamination from the atmosphere, the evaluation was carried out in a clean room of class 1,000 (FED-STD-209D, US Federal Standard, 1988).

[Evaluation 1: Polishing of a glass substrate by using a polishing liquid prepared with colloidal cerium oxide] <Evaluation of scratch reduction performance>

Further, the polishing liquids of Examples 1 to 8 and the polishing liquids of Comparative Examples 1 to 3 were diluted 10 times with ion-exchanged water to obtain a test liquid.

(1) A 2.5-inch disk-based glass substrate and a polishing pad made of urethane (manufactured by Fujibo Co., Ltd., "H9900S") were placed in a polishing apparatus (manufactured by Nanofactor, "FACT-200"). in.

(2) The rotation speed was set to 30 rpm, the number of oscillations was set to 60 times/min, the pressing pressure was set to 50 g/cm ² , and the test liquid was injected onto the substrate at a rate of 1 mL/sec while grinding. 5 minutes.

(3) The polished glass substrate was taken out from the polishing apparatus, washed with running water for 1 minute, and then rinsed. Then, the substrate was removed from the polishing apparatus, and nitrogen gas was blown and dried to prepare a substrate for evaluation.

(4) illuminating the scratches on the substrate for evaluation, concentrating and amplifying the generated scattered light, thereby emphasizing the fine scratches on the surface, and then Using a surface inspection apparatus ("MicroMax VMX-6100SK" manufactured by Vision Psytech Co., Ltd.), which can inspect the surface of the scratches, arbitrarily select five parts (10 mm × 10 mm square) of the surface of the evaluation substrate and count the range thereof. The number of scratches in the inside, and then the average value of the five parts was calculated.

Further, the average number of scratches on the substrate of Comparative Example 1 (blank) was 50.

The number of scratches on each of the substrates was compared with the number of scratches on the substrate of Comparative Example 1 (blank), and the effect of suppressing the occurrence of scratches on the surface of the substrate was evaluated based on the following criteria.

The results are shown in Table 1.

5: 20% of the blank (50)

4:20%~ less than 40%

3:40%~ less than 60%

2:60%~ less than 80%

1:80% or more

<Evaluation of particle adhesion reduction performance>

(1) A substrate for evaluation similar to the evaluation of the scratch reduction performance was produced.

(2) illuminating the residual particles on the substrate for evaluation, concentrating and amplifying the generated scattered light, thereby emphasizing the surface, and then optionally using the surface inspection device capable of inspecting the surface of the surface Five parts of the surface of the evaluation substrate (10 mm × 10 mm square) were selected, and the number of particles in the range was counted by an image analysis software (manufactured by Sangu Corporation, WinRoof), and the average value of the five parts was calculated.

Further, the number of particles on the substrate of Comparative Example 1 (blank) was 1,950. The number of particles on each of the substrates was compared with the number of particles on the substrate of Comparative Example 1, and the effect of reducing the adhesion of the particles in the polishing step was evaluated based on the following criteria.

The results are shown in Table 1.

5: 20% of the blank (1950)

4:20%~ less than 40%

3:40%~ less than 60%

2:60%~ less than 80%

1:80% or more

<Evaluation of the continuous performance of the grinding speed>

(1) A glass substrate for a disk having a weight of 2.5 Å and a polishing pad made of a polyurethane resin ("H9900S" manufactured by Fujisawa Co., Ltd.) were placed in a polishing apparatus (manufactured by Nanofactor, "FACT-200" ")in.

(2) The rotation speed was set to 30 rpm, the number of oscillations was set to 60 times/min, the pressing pressure was set to 50 g/cm ² , and the test liquid was injected onto the substrate at a rate of 1 mL/sec while grinding. 30 minutes.

(3) The polished glass substrate was taken out from the polishing apparatus, washed with running water for 1 minute, rinsed, and then nitrogen-dried, dried, and subjected to weight measurement.

(1) to (3) were repeated 10 times, and the weight change amounts of the first time and the tenth time were compared, and the evaluation of the polishing rate continuous performance was determined based on the following criteria. (the first weight change amount / the tenth time weight change amount × 100)

The results are shown in Table 1.

5:80% or more

4:60%~ less than 80%

3:40%~ less than 60%

2:20%~ less than 40%

1: less than 20%

[Evaluation 2: Polishing of Aluminum Substrate by Using a Polishing Solution Prepared with Colloidal Cerium Oxide] <Evaluation of scratch reduction performance>

Further, the polishing liquids of Examples 9 to 16 and the polishing liquids of Comparative Examples 4 to 6 were diluted 10 times with ion-exchanged water to obtain a test liquid.

(1) A 3.5-inch disk aluminum substrate and a polishing pad made of urethane ("H9900S" manufactured by Fujifilm Co., Ltd.) were placed in a polishing apparatus (manufactured by Nanofactor, "FACT-200").

(2) The rotation speed was set to 30 rpm, the number of oscillations was set to 60 times/min, the pressing pressure was set to 50 g/cm ² , and the test liquid was injected onto the substrate at a rate of 1 mL/sec while grinding. 5 minutes.

(3) The polished aluminum substrate was taken out from the polishing apparatus, washed with running water for 1 minute, and then rinsed. Then, the substrate was removed from the polishing apparatus, and nitrogen gas was blown and dried to prepare a substrate for evaluation.

(4) Illuminating the scratches on the evaluation substrate, concentrating and amplifying the generated scattered light, thereby emphasizing the fine scratches on the surface, and then using the surface inspection of the fine scratches of the inspectable surface The device ("MicroMax VMX-6100SK" manufactured by Vision Psytech Co., Ltd.) was arbitrarily selected from five parts (10 mm × 10 mm square) on the surface of the evaluation substrate, and the number of scratches in the range was counted, and then five parts were calculated. average value.

Further, the average number of scratches on the substrate of Comparative Example 4 was 100.

The number of scratches on each of the substrates was compared with the number of scratches on the substrate of Comparative Example 4, and the effect of suppressing the occurrence of scratches on the surface of the substrate was evaluated based on the following criteria.

The results are shown in Table 2.

5: 20% of the blank (100)

4:20%~ less than 40%

3:40%~ less than 60%

2:60%~ less than 80%

1:80% or more

<Evaluation of particle adhesion reduction performance>

(1) A substrate for evaluation similar to the evaluation of the scratch reduction performance was produced.

(2) illuminating the residual particles on the substrate for evaluation, concentrating and amplifying the generated scattered light, thereby emphasizing the surface, and then optionally using the surface inspection device capable of inspecting the surface of the surface Five parts of the surface of the evaluation substrate (10 mm × 10 mm square) were selected, and the number of particles in the range was counted by an image analysis software (manufactured by Sangu Corporation, WinRoof), and the average value of the five parts was calculated.

Further, the number of particles on the substrate of Comparative Example 4 was 1,200.

The number of particles on each of the substrates was compared with the number of particles on the substrate of Comparative Example 4, and the effect of reducing the adhesion of the particles in the polishing step was evaluated based on the following criteria.

The results are shown in Table 2.

5: 20% of the blank (1200)

4:20%~ less than 40%

3:40%~ less than 60%

2:60%~ less than 80%

1:80% or more

<Evaluation of the continuous performance of the grinding speed>

(1) A 3.5-inch disk aluminum substrate and a polishing pad made of a polyurethane resin ("H9900S" manufactured by Fujisawa Co., Ltd.) were placed in a polishing apparatus (manufactured by Nanofactor, "FACT-200". ")in.

(2) The rotation speed was set to 30 rpm, the number of oscillations was set to 60 times/min, the pressing pressure was set to 50 g/cm ² , and the test liquid was injected onto the substrate at a rate of 1 mL/sec while grinding. 30 minutes.

(3) The polished aluminum substrate was taken out from the polishing apparatus, washed with running water for 1 minute, rinsed, and then nitrogen-dried, dried, and subjected to weight measurement.

(1) to (3) were repeated 10 times, and the weight change amounts of the first time and the tenth time were compared, and the evaluation of the polishing rate continuous performance was determined based on the following criteria. (the first weight change amount / the tenth time weight change amount × 100)

The results are shown in Table 2.

5:80% or more

4:60%~ less than 80%

3:40%~ less than 60%

2:20%~ less than 40%

1: less than 20%

[Evaluation 3: Polishing of a glass substrate by using a polishing liquid prepared with cerium oxide]

Further, the polishing liquids of Examples 17 to 24 and the polishing liquids of Comparative Examples 7 to 9 were diluted 10 times with ion-exchanged water to obtain a test liquid.

In the same manner as in Evaluation 1, the scratch reduction performance, the particle adhesion reduction performance, and the polishing rate sustainability performance were evaluated.

Further, 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: Polishing of Aluminum Substrate by Polishing Liquid Blended with Alumina] <Evaluation of scratch reduction performance>

Further, the polishing liquids of Examples 25 to 32 and the polishing liquids of Comparative Examples 10 to 12 were diluted 10 times with ion-exchanged water to obtain a test liquid.

Evaluation of scratch reduction performance, particle adhesion reduction performance, and polishing rate sustainability was carried out in the same manner as in Evaluation 2.

Further, 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 1,000. The results are shown in Table 4.

[Evaluation 5: Polishing of Aluminum Substrate by Polishing Liquid with Diamond]

Further, the polishing liquids of Examples 33 to 40 and the polishing liquids of Comparative Examples 13 to 15 were diluted 10 times with ion-exchanged water to obtain a test liquid.

Evaluation of scratch reduction performance, particle adhesion reduction performance, and polishing rate sustainability was carried out in the same manner as in Evaluation 2.

Further, the average number of scratches on the substrate of Comparative Example 13 (blank) was 70, and the number of particles on the substrate of Comparative Example 13 (blank) was 500. The results are shown in Table 5.

[Evaluation 6: Using a polishing pad to which a grindstone is fixed, and polishing the glass with a polishing liquid prepared with a nonionic surfactant (glass polishing)] <Evaluation of particle adhesion reduction performance>

Further, the polishing liquids of Examples 41 to 49 and the polishing liquids of Comparative Examples 16 to 19 were diluted 10 times with ion-exchanged water to obtain a test liquid.

(1) A 2.5-inch disk-based glass substrate and a polishing pad to which a diamond grindstone was attached (manufactured by Sumitomo 3M, "Trizact 677XA") were placed in a polishing apparatus (manufactured by Nanofactor, "FACT-200").

(2) The rotation speed was set to 100 rpm, the number of oscillations was set to 60 times/min, the pressing pressure was set to 100 g/cm ² , and the test liquid was injected onto the substrate at a rate of 1 mL/sec while grinding. 5 minutes.

(3) The polished glass substrate was taken out from the polishing apparatus, washed with running water for 1 minute, and then rinsed. Then, the substrate was removed from the polishing apparatus, and nitrogen gas was blown and dried to prepare a substrate for evaluation.

(4) illuminating the residual particles on the substrate for evaluation, concentrating and amplifying the generated scattered light, thereby emphasizing the surface, and then using the surface inspection device capable of inspecting the surface of the surface for inspection Five parts of the surface of the evaluation substrate (10 mm × 10 mm square) were selected, and the number of particles in the range was counted by an image analysis software (manufactured by Sangu Corporation, WinRoof), and the average value of the five parts was calculated.

Further, the number of particles on the substrate of Comparative Example 16 was 4,500.

The number of scratches on each substrate was compared with the number of scratches on the substrate of Comparative Example 16, and the reduction in the grinding step was evaluated based on the following criteria. The effect of the adhesion of the particles is determined.

The results are shown in Table 6.

5: 20% of the blank (4,500)

4:20%~ less than 40%

3:40%~ less than 60%

2:60%~ less than 80%

1:80% or more

<Evaluation of the continuous performance of the grinding speed>

(1) A 2.5-inch disk glass substrate and a diamond-polished polishing pad (manufactured by Sumitomo 3M, "Trizact677XA") were placed in a polishing apparatus (manufactured by Nanofactor, "FACT-200"). .

(2) The rotation speed was set to 100 rpm, the number of oscillations was set to 60 times/min, the pressing pressure was set to 100 g/cm ² , and the test liquid was injected onto the substrate at a rate of 1 mL/sec while grinding. 30 minutes.

(3) The polished glass substrate was taken out from the polishing apparatus, washed with running water for 1 minute, rinsed, and then nitrogen-dried, dried, and subjected to weight measurement.

(1) to (3) were repeated twice, and the weight change amount of the first time and the second time was compared, and the evaluation of the polishing rate continuous performance was determined based on the following criteria. (the first weight change amount / the second weight change amount × 100)

The results are shown in Table 6.

5:80% or more

4:60%~ less than 80%

3:40%~ less than 60%

2:20%~ less than 40%

1: less than 20%

It is understood that the polishing liquid of the present invention of Examples 1 to 49 can significantly reduce the amount of particle adhesion as compared with Comparative Examples 1 to 19, and the polishing rate can be maintained. Further, in the polishing liquids of the present invention of Examples 1 to 40, the number of scratches was significantly reduced as compared with Comparative Examples 1 to 15.

On the other hand, in the polishing liquids of Comparative Example 3, Comparative Example 6, Comparative Example 9, Comparative Example 12, Comparative Example 15, and Comparative Example 18, a certain effect of suppressing the adhesion of particles was slightly observed when compared with the blank. However, the amount of adhesion of particles which can be tolerated for increasing the capacity is not attained. Further, in the polishing liquids of Comparative Example 3, Comparative Example 6, Comparative Example 9, Comparative Example 12, and Comparative Example 15, when the amount of the polishing liquid was slightly higher than that of the blank, the effect of suppressing the occurrence of scratches was slightly observed, but it was not high. The number of scratches that can be tolerated and capacity.

Further, the polishing liquids of Comparative Example 2, Comparative Example 5, Comparative Example 8, Comparative Example 11, and Comparative Example 14 using benzotriazole, Comparative Example 1, Comparative Example 4, Comparative Example 7, Comparative Example 10, and Comparative Example 13 were used. In contrast, the number of scratches after polishing the glass substrate hardly changes, and the effect of suppressing the occurrence of scratches and adhesion to particles is small.

[Industrial availability]

The polishing liquid for an electronic material of the present invention is excellent in the effect of suppressing the occurrence of scratches in the polishing step, and is also excellent in the effect of reducing the adhesion of particles during polishing. Therefore, the polishing liquid for an electronic material including the polishing step in the production step, for example, magnetic A polishing liquid for producing a glass substrate for a disk, a Ni-P-plated aluminum substrate for a magnetic disk, a semiconductor germanium substrate, and an LED sapphire substrate can be used.

In addition, the method for producing an electronic material including the step of polishing using the polishing liquid of the present invention is a production method in which scratches during polishing are extremely small and particles are less likely to adhere during polishing, and thus can be used as a glass substrate for a magnetic disk. A method for producing a Ni-P-plated aluminum substrate for a magnetic disk, a germanium germanium substrate, and a sapphire substrate for LED.

Claims (16)

A neutralizing salt (AB) for a polishing liquid for a step of grinding an intermediate of an electronic material using a polishing pad, the neutralizing salt (AB) having at least one acid group (X) in the molecule The acidic compound (A) and the heat of formation (Q2) in the proton addition reaction are salts of the nitrogen-containing basic compound (B) of 10 kcal/mol to 152 kcal/mol, and the slurry is neutralized with a salt ( AB) is a neutralized salt in which the heat of formation (Q1) in the acid dissociation reaction of the above acid group (X) is from 3 kcal/mol to 200 kcal/mol. The neutralized salt as described in claim 1, wherein the neutralized salt (AB) has a weight average molecular weight of 1,000 to 200,000. The neutralizing salt as described in claim 1 or 2, wherein the neutralizing salt (AB) is a salt of a polymer (A2-3) having a carboxyl group. The neutralizing salt according to any one of claims 1 to 3, wherein the nitrogen-containing basic compound (B) is 1,8-dioxabicyclo[5.4.0]undecene-7 . A polishing liquid for an electronic material, which is a polishing liquid for a step of grinding an intermediate of an electronic material using a polishing pad, and which contains the neutralization as described in any one of claims 1 to 4 Salt (AB) and water are essential ingredients. The polishing liquid for an electronic material according to claim 5, further comprising abrasive particles (C). The polishing liquid for an electronic material according to the sixth aspect of the invention, wherein the abrasive particles (C) are one or more selected from the group consisting of colloidal cerium oxide, cerium oxide, aluminum oxide, and diamond. The polishing liquid for an electronic material according to claim 6 or 7, wherein the concentration of the neutralizing salt (AB) in the polishing liquid for the electronic material is 0.01 wt% to 4 wt%, and the abrasive particles (C) The concentration is from 1 wt% to 40 wt%, and the ratio of neutralizing salt (AB) to the abrasive particles (C) is from 0.001 to 0.1. The polishing liquid for an electronic material according to any one of claims 5 to 8, further comprising a higher alkyl alcohol (carbon number 2 to 4) oxide selected from the group consisting of carbon atoms 8 to 18. Adduct (D11), polyoxyethylene polyoxypropylene copolymer (D12), alkylamine adduct of aliphatic amine having a carbon number of 8 to 36 (D13) and polyol type nonionic surfactant (D14) One or more kinds of surfactants (D) in the group consisting of. The polishing liquid for an electronic material according to claim 9, wherein the surfactant (D) is an alkylene oxide adduct (D13) of an aliphatic amine having a carbon number of 8 to 36. The polishing liquid for electronic materials according to claim 9 or 10, wherein the concentration of the neutralizing salt (AB) in the polishing liquid for the electronic material is 0.01 wt% to 5 wt%, and the surfactant ( The concentration of D) is 0.01 wt% to 60 wt%, and the ratio of neutralizing salt (AB) to surfactant (D) is 0.001 to 1. The polishing liquid for an electronic material 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 reduced ketone (E2). The polishing liquid for an electronic material according to any one of claims 5 to 13, wherein the polishing liquid for the electronic material is used for a glass substrate for a hard disk or an aluminum substrate for a hard disk for nickel-phosphorus plating. Manufacturing. A polishing method for polishing an electronic material intermediate using a polishing liquid for an electronic material according to any one of claims 5 to 14 in the manufacturing step of the electronic material. A method of producing an electronic material, which is a method for producing an electronic material comprising a polishing step in a manufacturing step, comprising the step of grinding an intermediate of an electronic material by a grinding method as described in claim 15 of the patent application.