JP6925958B2 - Abrasive liquid composition - Google Patents

Description

The present disclosure relates to a polishing liquid composition, and a method for producing a substrate and a polishing method using the same.

In recent years, magnetic disk drives have become smaller and larger in capacity, and higher recording densities are required. In order to increase the recording density, the unit recording area is reduced, and the detection sensitivity of the weakened magnetic signal is improved. Therefore, technological development for lowering the floating height of the magnetic head is underway. For magnetic disk substrates, in order to reduce the levitation of the magnetic head and secure the recording area, improvement of smoothness and flatness represented by reduction of surface roughness, waviness, and end face sagging, and scratches, protrusions, pits, etc. The demand for defect reduction represented by the reduction of defects is becoming stricter. In response to such demands, polishing liquid compositions containing a copolymer having a functional group such as a carboxyl group or a sulfonic acid group have been proposed (for example, Patent Documents 1 and 2).

Patent Document 1 describes scratches and the like by using an anionic surfactant having a repeating unit and a sulfonic acid (salt) group in the molecule and further having an aromatic group in the main chain of the repeating unit. Disclosed is a polishing agent composition which can reduce defects, has less foaming in the polishing process, and can be efficiently polished.

Patent Document 2 describes a polishing solution composition capable of reducing scratches and waviness without impairing productivity by using a water-soluble polymer having a sulfonic acid group and having an aromatic ring in each of the main chain and the side chain. Disclose the thing.

Japanese Unexamined Patent Publication No. 2010-135052 Japanese Unexamined Patent Publication No. 2012-135863

As the capacity of magnetic disk drives increases, the required characteristics for the surface quality of the substrate are becoming more stringent, and the development of a polishing liquid composition capable of reducing scratches and waviness on the surface of the substrate is required.

Therefore, the present disclosure provides, in one aspect, a polishing liquid composition capable of reducing scratches on the surface of the substrate after polishing and short-wavelength waviness in continuous use of the polishing pad.

［式（Ｉ）中、Ｒ₁は、ＣＨ₃、ＣＯＯＨ及びＨから選ばれる少なくとも１種であり、ｋは、１〜２であり、Ｘは、アルカリ金属、アルカリ土類金属、有機カチオン、及び水素原子から選ばれる少なくとも１種であり、ｍ、ｎは、ｍ＋ｎ＝１とした場合のモル分率であって、０≦ｍ≦０．４である。］ The present disclosure is, in one aspect, a polishing liquid composition containing an abrasive, a water-soluble polymer, and an aqueous medium, wherein the water-soluble polymer has a structure represented by the following general formula (I). , Concerning abrasive composition.

[In formula (I), R ₁ is _{at least one selected from CH 3} , COOH and H, k is 1-2, and X is an alkali metal, an alkaline earth metal, an organic cation, and It is at least one selected from hydrogen atoms, and m and n are mole fractions when m + n = 1, and 0 ≦ m ≦ 0.4. ]

In another aspect of the present disclosure, the polishing liquid composition of the present disclosure is supplied to the surface to be polished of the substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and / or the substrate to be polished is brought into contact with the surface to be polished. The present invention relates to a method for manufacturing a substrate, which comprises a step of moving and polishing.

In another aspect of the present disclosure, the polishing liquid composition of the present disclosure is supplied to the surface to be polished of the substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and / or the substrate to be polished is brought into contact with the surface to be polished. It relates to a method of polishing a substrate, including moving and polishing.

According to the polishing liquid composition of the present disclosure, a substrate in which scratches on the surface of the substrate after polishing and short wavelength waviness in continuous use of the polishing pad are reduced, preferably a magnetic disk substrate, and more preferably a magnetic disk of a perpendicular magnetic recording method. The effect of being able to manufacture a substrate can be achieved.

The present disclosure is based on the finding that by using a polishing liquid composition containing a predetermined water-soluble polymer, scratches on the surface of a substrate after polishing and short-wavelength waviness in continuous use of a polishing pad can be reduced.

That is, the present disclosure is, in one aspect, a polishing liquid composition containing an abrasive, a water-soluble polymer, and an aqueous medium, wherein the water-soluble polymer is represented by the general formula (I). (Hereinafter, also referred to as "abrasive liquid composition of the present disclosure").

The mechanism of the manifestation of the effects of the present disclosure is not clear, but it is inferred as follows.
Usually, scratches can be reduced by softening the polishing pad. However, the polishing pad generally contains a mixture of parts having different hardness, and when the soft part is excessively softened, the pore diameter becomes large and the pressure distribution becomes uneven, which accelerates the wear of the polishing pad. However, it is thought that it will lead to worsening of short wavelength swell.
On the other hand, in the present disclosure, the predetermined water-soluble polymer in the polishing liquid composition selectively softens the hard portion of the polishing pad and suppresses the soft portion from being excessively softened, so that the polishing pad is prevented from being excessively softened. It is considered that the wear of the material is suppressed. As a result, it is considered that short-wavelength waviness on the substrate surface during continuous use of the polishing pad can be reduced while reducing scratches.
However, the present disclosure may not be construed as limited to these mechanisms.

In the present disclosure, the "waviness" of the substrate means the unevenness of the substrate surface having a wavelength longer than the roughness. In the present disclosure, the "short wavelength swell" means a swell observed at a wavelength of, for example, 80 to 500 nm. By reducing the short-wavelength waviness of the surface of the substrate after polishing, the floating height of the magnetic head can be lowered in the magnetic disk drive, and the recording density of the magnetic disk can be improved. The short wavelength swell on the surface of the substrate can be measured, for example, by the method described in Examples.

[Abrasive (Component A)]
As the polishing material (hereinafter, also referred to as “component A”) contained in the polishing liquid composition of the present disclosure, a polishing material generally used for polishing can be used, and a metal, metal or semi-metal can be used. Carbides, nitrides, oxides, boroides, diamonds and the like. The metal or metalloid element is derived from Group 8 of 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A or 8 of the periodic table (long periodic table). Specific examples of component A include silicon oxide (hereinafter referred to as silica), aluminum oxide (hereinafter referred to as alumina), silicon carbide, diamond, manganese oxide, magnesium oxide, zinc oxide, titanium oxide, and cerium oxide (hereinafter referred to as ceria). ), Zirconium oxide and the like, and it is preferable to use one or more of these from the viewpoint of improving the polishing rate. Among them, silica, alumina, titanium oxide, ceria, zirconium oxide and the like are suitable for polishing substrates for precision parts such as substrates for semiconductor devices and magnetic disk substrates. From the viewpoint of reducing scratches and short wavelength waviness, as the component A, at least one selected from colloidal silica, colloidal ceria, and colloidal alumina is preferable, and colloidal silica is more preferable. The component A may be one kind alone or a combination of two or more kinds. Component A substantially does not contain fine particles having a diamond structure having a median diameter of 4 to 100 nm when measured with a particle size distribution meter based on laser light diffraction / scattering in one or more embodiments. It may be. The fact that the fine particles having the diamond structure are not substantially contained means that the content of the fine particles in the component A is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably from the viewpoint of scratch reduction. Is substantially 0% by mass.

The average particle size of the component A is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, and from the same viewpoint, preferably 100 nm or less, preferably 70 nm or less, from the viewpoint of reducing scratches and short wavelength waviness. More preferably, 40 nm or less is further preferable. Further, from the same viewpoint, the average particle size of the component A is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 70 nm or less, and further preferably 10 nm or more and 40 nm or less. In the present disclosure, the "average particle size of the abrasive" means the average particle size based on the scattering intensity distribution measured at a detection angle of 90 ° in the dynamic light scattering method. Specifically, the average particle size of the abrasive can be determined by the method described in Examples.

The content of component A in the polishing liquid composition of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and more preferably 3% by mass or more, from the viewpoint of improving the polishing rate. From the viewpoint of reducing scratches and short wavelength waviness, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is further preferable. Further, the content of the component A is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, from the viewpoint of improving the polishing rate and reducing scratches and short wavelength waviness. More preferably, it is by mass% or more and 10% by mass or less. When the component A is a combination of two or more kinds of abrasives, the content of the component A means the total content thereof.

[Water-soluble polymer (component B)]
The water-soluble polymer (hereinafter, also referred to as “component B”) used in the polishing liquid composition of the present disclosure is a compound having a composition represented by the following formula (I) from the viewpoint of reducing scratches and short wavelength waviness. be. Component B may be used alone or in combination of two or more.

In formula (I), R ₁ is at least one selected from _{CH 3, COOH and H.} k is 1 to 2. X is at least one selected from alkali metals, alkaline earth metals, organic cations, and hydrogen atoms. Examples of the organic cation include ammonium and alkylammonium such as tetramethylammonium, tetraethylammonium and tetrabutylammonium. Among these, at least one selected from alkali metal, ammonium and hydrogen atoms is preferable, and at least one selected from sodium, potassium, ammonium and hydrogen atoms is more preferable, and hydrogen atoms are more preferable from the viewpoint of reducing scratches and short wavelength waviness. Is more preferable. m and n are mole fractions when m + n = 1, and m is 0 ≦ m ≦ 0.4 and 0 ≦ m ≦ from the viewpoint of scratch reduction, short wavelength swell reduction and water solubility. 0.3 is preferable, 0 ≦ m ≦ 0.25 is more preferable, and 0.1 ≦ m ≦ 0.2 is further preferable.

In one or more embodiments, component B has a solubility of 0.01 g or more in 100 g of an aqueous solution having a pH of 3 at 20 ° C. and a solubility in 100 g of an aqueous solution having a pH of 3 or less at 20 ° C. from the viewpoint of reducing scratches and short wavelength waviness. It is preferably 0.01 g or more.

In the present disclosure, "water-soluble" means that the solubility in 100 g of water at 20 ° C. is 0.01 g or more.

Component B can be produced, for example, by polymerizing a monomer having a phenol skeleton in the main chain by a known means such as an addition condensation method in the presence of formaldehyde. From the viewpoint of improving hydrolysis resistance and storage stability in an acidic polishing solution, it is preferably produced by an addition condensation method. Therefore, one embodiment of component B includes a water-soluble polymer having a structural unit having a phenol skeleton in the main chain.

The content of the configuration represented by the formula (I) in all the constituent units constituting the component B is preferably 5 mol% or more from the viewpoint of scratch reduction and short wavelength swell reduction in one or more embodiments. 10 mol% or more is more preferable, 20 mol% or more is further preferable, and from the same viewpoint, 100 mol% or less is more preferable, 95 mol% or less is more preferable, 90 mol% or less is further preferable, and 80 mol% is more preferable. The following is more preferable. Further, from the same viewpoint, the content of the composition represented by the formula (I) represented by the formula (I) in all the constituent units of the component B is preferably 5 mol% or more and 100 mol% or less, and 5 mol% or more and 95 mol% or less. More preferably, 10 mol% or more and 90 mol% or less is further preferable, and 20 mol% or more and 80 mol% or less is further preferable.

In the present disclosure, as the content (mol%) of a certain constituent unit in all the constituent units constituting the component B, depending on the synthesis conditions, all the constituent units charged in the reaction vessel in all the steps of the synthesis of the component B are used. The amount of the compound (mol%) for introducing the structural unit charged in the reaction vessel in the compound for introduction may be used. Further, in the present disclosure, when the component B contains two or more kinds of constituent units, as the constituent ratio (molar ratio) of the two constituent units, depending on the synthesis conditions, the component B is charged into the reaction tank in all the steps of the synthesis of the component B. The compound amount ratio (molar ratio) for introducing the two constituent units may be used.

Component B may have other structural units not included in formula (I). The content of other constituent units in all the constituent units constituting the component B is preferably 10 mol% or less, more preferably 5 mol% or less, and 3 mol% or less from the viewpoint of reducing scratches and short wavelength waviness. More preferably, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable. When the component B contains, as another structural unit, a structural unit having an aromatic ring in the side chain of the phenol skeleton in the main chain, the content of the structural unit is preferably 5 mol% or less, preferably 4 mol% or less. Is more preferable, 3 mol% or less is further preferable, 2 mol% or less is further preferable, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable.

The sequence of each structural unit constituting the component B may be random, block, or graft.

The weight average molecular weight of the component B is preferably 500 or more, more preferably 1,000 or more, further preferably 1,400 or more, further preferably 1,500 or more, and 3,000 or more, from the viewpoint of reducing scratches and short wavelength waviness. The above is more preferable, 4,500 or more is further preferable, 5,000 or more is further preferable, 8,000 or more is further preferable, 10,000 or more is further preferable, and from the same viewpoint, 1,000,000 or less. Is more preferable, 75,000,000 or less is more preferable, 500,000 or less is further preferable, 250,000 or less is further preferable, 120,000 or less is further preferable, 100,000 or less is further preferable, and 75,000 or less is further preferable. , 50,000 or less is further preferable, 40,000 or less is further preferable, 30,000 or less is further preferable, 25,000 or less is further preferable, and 20,000 or less is further preferable. Further, from the same viewpoint, the weight average molecular weight of the component B is preferably 500 or more and 1,000,000 or less, more preferably 1,000 or more and 750,000 or less, and further preferably 1,400 or more and 500,000 or less. More preferably 1,500 or more and 250,000 or less, further preferably 3,000 or more and 100,000 or less, further preferably 4,500 or more and 75,000 or less, further preferably 5,000 or more and 50,000 or less, 8, It is more preferably 000 or more and 30,000 or less, and further preferably 10,000 or more and 20,000 or less. In the present disclosure, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the conditions described in Examples.

The surface tension of component B is preferably 45 mN / m or more, more preferably 55 mN / m or more, further preferably 65 mN / m or more, further preferably 71 mN / m or more, and even more preferably 72 mN / m, from the viewpoint of reducing scratches and short wavelength waviness. M or more is more preferable, and from the same viewpoint, 90 mN / m or less is preferable, 80 mN / m or less is more preferable, 77 mN / m or less is further preferable, and 74 mN / m or less is further preferable. Further, from the same viewpoint, the surface tension of the component B is preferably 45 mN / m or more and 90 mN / m or less, more preferably 55 mN / m or more and 80 mN / m or less, further preferably 65 mN / m or more and 77 mN / m or less, and 71 mN. It is more preferably / m or more and 74 mN / m or less, and further preferably 72 mN / m or more and 74 mN / m or less. In the present disclosure, the surface tension of component B is the surface tension of a 0.005 mass% aqueous solution of component B at 20 ° C. and pH 1.5, and can be determined by the method described in Examples.

The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more, more preferably 0.25 MPa or more, further preferably 0.30 MPa or more, and scratch reduction from the viewpoint of reducing short wavelength swell. From the viewpoint, 0.50 MPa or less is preferable, 0.40 MPa or less is more preferable, and 0.35 MPa or less is further preferable. Further, from the viewpoint of reducing scratches and short wavelength waviness, the storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more and 0.50 MPa or less, more preferably 0.25 MPa or more and 0.40 MPa or less, and 0. .30 MPa or more and 0.35 MPa or less is more preferable. In the present disclosure, the storage elastic modulus can be determined by the method described in Examples.

The content of component B in the polishing liquid composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and 0.006% by mass from the viewpoint of reducing scratches and short wavelength waviness. The above is more preferable, and from the viewpoint of improving the polishing speed, 10% by mass or less is preferable, 1% by mass or less is more preferable, and 0.1% by mass or less is further preferable. Further, from the viewpoint of reducing scratches and short wavelength waviness and improving the polishing speed, the content of component B is preferably 0.001% by mass or more and 10% by mass or less, and more preferably 0.003% by mass or more and 1% by mass or less. More preferably, it is 0.006% by mass or more and 0.1% by mass or less.

The mass ratio of component B to component A in the polishing liquid composition of the present disclosure (content of component B / content of component A) is preferably 0.0001 or more, preferably 0, from the viewpoint of reducing scratches and short wavelength waviness. More preferably .0005 or more, further preferably 0.001 or more, and from the same viewpoint, 0.2 or less is more preferable, 0.05 or less is more preferable, and 0.01 or less is further preferable. Further, from the same viewpoint, the mass ratio of the component B to the component A is preferably 0.0001 or more and 0.2 or less, more preferably 0.0005 or more and 0.05 or less, and further preferably 0.001 or more and 0.01 or less. preferable.

[Residual monomer content in water-soluble polymer]
The content of formaldehyde, which is a residual monomer in component B, is preferably 0 ppm or more than 0 ppm and 10000 ppm or less, more preferably 0 ppm or more than 0 ppm and 6000 ppm or less, and further preferably 0 ppm or 0 ppm, from the viewpoint of reducing scratches and short wavelength waviness. It is more than 5000 ppm or less, more preferably 0 ppm or more than 0 ppm and 3000 ppm or less, still more preferably 0 ppm or more than 0 ppm and 2000 ppm or less, still more preferably 0 ppm or more than 0 ppm and 1000 ppm or less. The residual formaldehyde content shall be a value measured under the conditions described in Examples using high performance liquid chromatography (HPLC). Further, the residual formaldehyde may be reduced by reacting with sulfite, hydrogen cyanide or a salt thereof, ammonium hydroxide, alcohol or the like by a known method.

[Aqueous medium]
Examples of the aqueous medium contained in the polishing liquid composition of the present disclosure include distilled water, ion-exchanged water, water such as pure water and ultrapure water, or a mixed solvent of water and a solvent. Examples of the solvent include a solvent that can be mixed with water (for example, an alcohol such as ethanol). When the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium may not be particularly limited as long as the effects of the present disclosure are not hindered, and from the viewpoint of economy, for example, , 95% by mass or more is preferable, 98% by mass or more is more preferable, and substantially 100% by mass is further preferable. From the viewpoint of surface cleanliness of the substrate to be polished, ion-exchanged water and ultrapure water are preferable, and ultrapure water is more preferable as the water-based medium. The content of the aqueous medium in the polishing liquid composition of the present disclosure can be the residue of component A and component B, and any component described below, which is blended as needed.

[Acid (component C)]
The polishing liquid composition of the present disclosure may further contain at least one selected from an acid and a salt thereof (hereinafter, also referred to as "component C") from the viewpoint of improving the polishing speed. Component C may be used alone or in combination of two or more. The component C includes, for example, an inorganic acid such as nitrate, sulfuric acid, sulfite, persulfate, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphate, tripolyphosphate, and amide sulfate, and 2-aminoethylphosphonic acid. , 1-Hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethane-1,1,-diphosphonic acid, ethane-1, 1,2-Triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid , Methanhydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, organic phosphonic acid such as α-methylphosphonosuccinic acid, glutamate, picolinic acid, aspartic acid Aminocarboxylic acids such as citric acid, tartaric acid, oxalic acid, nitroacetic acid, maleic acid, carboxylic acids such as oxaloacetate and the like can be mentioned. Of these, at least one of an inorganic acid and an organic phosphonic acid is preferable from the viewpoint of reducing scratches and short-wavelength waviness. Among the inorganic acids, at least one selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid and phosphoric acid is preferable, and at least one of phosphoric acid and sulfuric acid is more preferable. Among organic phosphonic acids, at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and salts thereof. Species are preferred, with at least one of 1-hydroxyethylidene-1,1-diphosphonic acid and aminotri (methylenephosphonic acid) being more preferred.

The salt when the salt of the acid is used is not particularly limited, and specific examples thereof include metal, ammonium, and alkylammonium. Specific examples of the metal include metals belonging to Group 8 of the periodic table (long-period type) 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A. Among these, a salt with a metal belonging to Group 1A or ammonium is preferable from the viewpoint of reducing scratches on the surface of the substrate after polishing.

The content of component C in the polishing liquid composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and 0, from the viewpoint of improving the polishing speed, reducing scratches and short wavelength waviness. It is more preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less. Further, from the same viewpoint, the content of the component C is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 4% by mass or less, and 0.05% by mass or more and 3% by mass or less. The following is more preferable.

[Oxidizing agent (component D)]
The polishing liquid composition of the present disclosure may further contain an oxidizing agent (hereinafter, also referred to as “component D”) from the viewpoint of improving the polishing rate, reducing scratches and short-wavelength waviness. Component D may be used alone or in combination of two or more. Examples of the component D include peroxides, permanganic acid or salts thereof, chromic acid or salts thereof, peroxo acid or salts thereof, oxygen acid or salts thereof, metal salts, nitric acids, sulfuric acids and the like.

Examples of the peroxide include hydrogen peroxide, sodium peroxide, barium peroxide and the like. Examples of permanganate or a salt thereof include potassium permanganate and the like. Examples of chromic acid or a salt thereof include chromic acid metal salt, dichromic acid metal salt and the like. Examples of peroxoic acid or a salt thereof include peroxodisulfuric acid, ammonium peroxodisulfate, metal salt peroxodisulfate, peroxophosphate, peroxosulfate, sodium peroxoborate, peroxy acid, peracetic acid, perbenzoic acid, perphthalic acid and the like. Be done. Examples of the oxygen acid or a salt thereof include hypochlorous acid, hypobromous acid, hypobromous acid, chloric acid, bromic acid, iodic acid, sodium hypochlorite, calcium hypochlorite and the like. Examples of the metal salts include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, iron (III) citrate, iron (III) ammonium sulfate and the like.

As the component D, at least one selected from hydrogen peroxide, iron nitrate (III), peracetic acid, ammonium peroxodisulfate, iron (III) sulfate and iron (III) sulfate from the viewpoint of reducing scratches and short-wavelength waviness. Is preferable. Of these, hydrogen peroxide is more preferable from the viewpoint that metal ions do not adhere to the surface, it is used for general purposes, and it is inexpensive.

The content of component D in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more from the viewpoint of improving the polishing speed. It is preferable, and from the viewpoint of scratch and reduction of short wavelength waviness, 4% by mass or less is preferable, 2% by mass or less is more preferable, and 1% by mass or less is further preferable. Further, from the viewpoint of improving the polishing speed and reducing scratches and short wavelength waviness, the content of the component D is preferably 0.01% by mass or more and 4% by mass or less, and more preferably 0.05% by mass or more and 2% by mass or less. It is more preferably 0.1% by mass or more and 1% by mass or less.

[Other ingredients]
The polishing liquid composition of the present disclosure may contain other components if necessary. Examples of other components include thickeners, dispersants, rust inhibitors, basic substances, surfactants and the like. The content of the other components in the polishing liquid composition of the present disclosure is preferably 0% by mass or more, more preferably more than 0% by mass, further preferably 0.1% by mass or more, and 10% by mass or less. It is preferably 5% by mass or less, and more preferably 5% by mass or less. More specifically, the content of other components is preferably 0% by mass or more and 10% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less. .. However, the polishing liquid composition of the present disclosure can exhibit the effect of reducing scratches and short-wavelength waviness without containing other components, particularly a surfactant. Further, the polishing liquid composition of the present disclosure can contain alumina abrasive grains and can be used in a rough polishing step prior to the final polishing step.

[Formaldehyde content in polishing liquid composition]
The formaldehyde content in the polishing liquid composition of the present disclosure is preferably more than 0.00 ppm or 0.00 ppm and 10.0 ppm or less, more preferably 0.00 ppm or 0.00 ppm, from the viewpoint of reducing scratches and short wavelength waviness. More than 5.0 ppm or less, more preferably 0.00 ppm or more than 0.00 ppm and 4.0 ppm or less, still more preferably 0.00 ppm or more than 0.00 ppm and 3.0 ppm or less, still more preferably 0.00 ppm or More than 0.00 ppm and 1.0 ppm or less, even more preferably 0.00 ppm or more than 0.00 ppm and 0.55 ppm or less, even more preferably 0.00 ppm or more than 0.00 ppm and 0.5 ppm or less, even more preferably. It is more than 0.00 ppm or 0.00 ppm and 0.4 ppm or less, and even more preferably more than 0.00 ppm or 0.00 ppm and 0.1 ppm or less. The formaldehyde content in the polishing liquid composition can be measured by using high performance liquid chromatography (HPLC) in the same manner as the formaldehyde content which is a residual monomer in the above-mentioned component B.

[PH of polishing liquid composition]
From the viewpoint of improving the polishing rate, the pH of the polishing liquid composition of the present disclosure is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, further preferably 2.5 or less, and scratch and short. From the viewpoint of reducing wavelength swell, 0.5 or more is preferable, 0.8 or more is more preferable, 1 or more is further preferable, and 1.2 or more is further preferable. Further, from the viewpoint of improving the polishing speed and reducing scratches and short wavelength waviness, the pH is preferably 0.5 or more and 4 or less, more preferably 0.8 or more and 3.5 or less, further preferably 1 or more and 3 or less. More preferably 2 or more and 2.5 or less. The pH can be adjusted by using the above-mentioned acid (component C), a known pH adjuster, or the like. In the present disclosure, the pH is the pH of the polishing liquid composition at 25 ° C. and can be measured using a pH meter. For example, the pH is set to a value 2 minutes after the electrode of the pH meter is immersed in the polishing liquid composition. be able to.

[Manufacturing method of polishing liquid composition]
The polishing liquid composition of the present disclosure can be produced, for example, by blending component A, component B and an aqueous medium, and if desired, component C, component D and other components by a known method. That is, the present disclosure relates to a method for producing an abrasive liquid composition, which comprises, in other embodiments, at least a step of blending component A, component B and an aqueous medium. In the present disclosure, "blending" includes mixing component A, component B and an aqueous medium, and optionally component C, component D and other components simultaneously or in any order. The compounding can be performed using, for example, a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill. The abrasive of component A may be mixed in the state of a concentrated slurry, or may be diluted with water or the like and then mixed. The preferable blending amount of each component in the method for producing the abrasive slurry and the polishing liquid composition can be the same as the preferable content of each component in the polishing liquid composition of the present disclosure described above.

In the present disclosure, the "content of each component in the polishing liquid composition" means the content of each component at the time when the polishing liquid composition is used for polishing. The polishing liquid composition of the present disclosure may be stored and supplied in a concentrated state as long as the storage stability is not impaired. In this case, it is preferable in that the manufacturing and transportation costs can be further reduced. The concentrate of the polishing liquid composition of the present disclosure may be appropriately diluted with the above-mentioned aqueous medium at the time of use, if necessary.

The polishing liquid composition of the present disclosure can be suitably used for manufacturing a substrate for precision parts. For example, it is suitable for polishing magnetic disk substrates such as magnetic disks, magneto-optical disks, optical disks, photomask substrates, optical lenses, optical mirrors, optical prisms, semiconductor substrates, etc., and in particular, polishing magnetic disk substrates. Suitable for. In the manufacture of a semiconductor substrate, the polishing liquid of the present disclosure is used in a silicon wafer (bare wafer) polishing step, an embedded element separation membrane forming step, an interlayer insulating film flattening step, an embedded metal wiring forming step, an embedded capacitor forming step, and the like. The composition can be used.

[Abrasive liquid kit]
The present disclosure relates to a kit for producing the polishing liquid composition of the present disclosure (hereinafter, also referred to as "polishing liquid kit of the present disclosure") in another aspect. As one embodiment of the polishing liquid kit of the present disclosure, for example, a polishing liquid kit containing a polishing material dispersion liquid containing the component A and an aqueous medium and an additive aqueous solution containing the component B in a state where they are not mixed with each other. Two-component abrasive liquid composition) can be mentioned. The abrasive dispersion and the additive aqueous solution are mixed at the time of use and diluted with an aqueous medium if necessary. The abrasive dispersion liquid and the additive aqueous solution may each contain the above-mentioned optional components (component C, component D and other components), if necessary.

[Substrate to be polished]
Examples of the material of the substrate to be polished by the polishing liquid composition of the present disclosure include metals or semi-metals such as silicon, aluminum, nickel, tungsten, copper, tantalum, and titanium, alloys thereof, glass, and the like. Examples thereof include glassy substances such as glassy carbon and amorphous carbon, ceramic materials such as alumina, silicon dioxide, silicon nitride, tantalum nitride and titanium carbide, and resins such as polyimide resin. Of these, metals such as aluminum, nickel, tungsten, and copper, and substrates to be polished and glass substrates containing alloys containing these metals as main components are preferable. Among them, it is suitable for a Ni-P-plated aluminum alloy substrate and an electroless silicate glass substrate, and a Ni-P-plated aluminum alloy substrate is more suitable. The aluminosilicate glass substrate includes those having a crystal structure and those having undergone a chemical strengthening treatment. The chemical strengthening treatment may be performed after polishing.

Further, according to the present disclosure, in addition to scratching the surface of the substrate after polishing, it is possible to provide a substrate in which the waviness of the surface of the substrate after polishing is reduced, so that a magnetic disk substrate that requires a high degree of surface smoothness, particularly It can be suitably used for manufacturing a magnetic disk substrate of a perpendicular magnetic recording system. Therefore, the polishing liquid composition of the present disclosure may be a polishing liquid composition for a magnetic disk substrate in one or more embodiments. When the polishing liquid composition of the present disclosure is a polishing liquid composition for a magnetic disk substrate, the substrate to be polished includes a substrate used for manufacturing a magnetic disk substrate, and specifically, Ni-P plated. An aluminum alloy substrate is preferably mentioned. In the present disclosure, the "Ni-P plated aluminum alloy substrate" refers to an aluminum alloy substrate surface that has been ground and then electroless Ni-P plated. Generally, a magnetic disk is manufactured by polishing a substrate to be polished that has undergone a grinding step through a rough polishing step and a finish polishing step, and then through a magnetic layer forming step. When manufacturing a magnetic disk substrate, the polishing liquid composition of the present disclosure is preferably used for polishing in the finish polishing step.

The shape of the substrate to be polished is not particularly limited, and may be, for example, a shape having a flat portion such as a disk shape, a plate shape, a slab shape, or a prism shape, or a shape having a curved surface portion such as a lens. Above all, a disk-shaped substrate to be polished is suitable. In the case of a disk-shaped substrate to be polished, its outer diameter is, for example, about 2 to 95 mm, and its thickness is, for example, about 0.5 to 2 mm.

[Substrate manufacturing method]
In another aspect, the present disclosure is also referred to as a step of polishing a substrate to be polished while bringing the above-mentioned polishing liquid composition of the present disclosure into contact with a polishing pad (hereinafter, "polishing step using the polishing liquid composition of the present disclosure"). The present invention relates to a substrate manufacturing method (hereinafter, also referred to as “the substrate manufacturing method of the present disclosure”) including the above. This makes it possible to provide a substrate in which the surface waviness of the substrate after polishing is reduced in addition to the scratches on the surface of the substrate after polishing. The substrate manufacturing method of the present disclosure is suitable for a method for manufacturing a magnetic disk substrate, and is particularly suitable for a method for manufacturing a magnetic disk substrate for a perpendicular magnetic recording method. Therefore, the substrate manufacturing method of the present disclosure is, as another aspect, a method of manufacturing a substrate including a polishing step using the polishing liquid composition of the present disclosure, preferably a method of manufacturing a magnetic disk substrate, and more preferably. This is a method for manufacturing a magnetic disk substrate for a perpendicular magnetic recording method.

As a specific example of the method of polishing the substrate to be polished using the polishing liquid composition of the present disclosure, the substrate to be polished is sandwiched between a platen to which a polishing pad such as a non-woven organic polymer-based polishing cloth is attached. Examples thereof include a method of polishing the substrate to be polished by moving the platen or the substrate to be polished while supplying the disclosed polishing liquid composition to the polishing machine.

When the polishing step of the substrate to be polished is performed in multiple steps, the polishing step using the polishing liquid composition of the present disclosure is preferably performed in the second and subsequent steps, and in the final polishing step (for example, the finish polishing step). More preferably done. At that time, in order to avoid mixing of the abrasive material and the polishing liquid composition in the previous process, different polishing machines may be used, and when different polishing machines are used, each polishing process is to be polished. It is preferable to clean the substrate. The polishing liquid composition of the present disclosure can also be used in circulation polishing in which the used polishing liquid is reused. The polishing machine is not particularly limited, and a known polishing machine for polishing a substrate can be used.

The polishing pad used in the polishing process using the polishing liquid composition of the present disclosure is not particularly limited, and a suede type, a non-woven fabric type, a polyurethane independent foam type, or a two-layer type in which these are laminated may be used. Can be used.

The average opening diameter of the surface member of the polishing pad is preferably 50 μm or less, more preferably 45 μm or less, further preferably 40 μm or less, further preferably 35 μm or less, and the polishing liquid retention of the pad from the viewpoint of scratch reduction and pad life. From the above viewpoint, 0.01 μm or more is preferable, 0.1 μm or more is more preferable, 1 μm or more is further preferable, and 10 μm or more is further preferable. The maximum value of the opening diameter of the polishing pad is preferably 100 μm or less, more preferably 70 μm or less, further preferably 60 μm or less, still more preferably 50 μm or less, from the viewpoint of maintaining the polishing rate.

The polishing load in the polishing process using the polishing liquid composition of the present disclosure is preferably 5.9 kPa or more, more preferably 6.9 kPa or more, and further preferably 7.5 kPa or more, from the viewpoint of ensuring the polishing rate and reducing short wavelength waviness. It is preferable, and from the viewpoint of scratch reduction, 20 kPa or less is preferable, 18 kPa or less is more preferable, and 16 kPa or less is further preferable. In the present disclosure, the polishing load means the pressure of the surface plate applied to the polishing surface of the substrate to be polished during polishing. The polishing load can be adjusted by applying an air pressure or a weight to at least one of the surface plate and the substrate to be polished.

In the polishing process using the polishing liquid composition of the present disclosure, the supply speed of the polishing liquid composition of the present disclosure is preferably 0.05 to 15 mL / min per ^{1 cm 2 of the substrate to be polished from the viewpoint of scratch reduction.} , 0.06 to 10 mL / min, more preferably 0.07 to 1 mL / min, even more preferably 0.07 to 0.5 mL / min.

Examples of the method of supplying the polishing liquid composition of the present disclosure to the polishing machine include a method of continuously supplying the polishing liquid composition using a pump or the like. When supplying the polishing liquid composition to the polishing machine, in addition to the method of supplying it as one liquid containing all the components, in consideration of the stability of the polishing liquid composition, etc., it is divided into a plurality of compounding component liquids. It can also be supplied in two or more liquids. In the latter case, for example, the plurality of compounding component liquids are mixed in the supply pipe or on the substrate to be polished to obtain the polishing liquid composition of the present disclosure.

[Polishing method]
The present disclosure also includes a method for polishing a substrate (hereinafter, also referred to as "the polishing method of the present disclosure"), which comprises polishing the substrate to be polished while bringing the above-mentioned polishing liquid composition of the present disclosure into contact with a polishing pad in another aspect. Regarding). The polishing of the substrate to be polished using the polishing liquid composition of the present disclosure in the polishing method of the present disclosure is, for example, finish polishing.
By using the polishing method of the present disclosure, a substrate in which waviness of the surface of the substrate after polishing is reduced in addition to scratches on the surface of the substrate after polishing is provided. The specific polishing method and conditions can be the same as the substrate manufacturing method of the present disclosure described above.

［式（Ｉ）中、Ｒ₁は、ＣＨ₃、ＣＯＯＨ及びＨから選ばれる少なくとも１種であり、ｋは、１〜２であり、Ｘは、アルカリ金属、アルカリ土類金属、有機カチオン、及び水素原子から選ばれる少なくとも１種であり、ｍ、ｎは、ｍ＋ｎ＝１とした場合のモル分率であって、０≦ｍ≦０．４である。］ The present disclosure further relates to one or more embodiments below.
<1> An abrasive liquid composition containing an abrasive (component A), a water-soluble polymer (component B), and an aqueous medium.
A polishing liquid composition in which the water-soluble polymer (component B) has a structure represented by the following general formula (I).

[In formula (I), R ₁ is _{at least one selected from CH 3} , COOH and H, k is 1-2, and X is an alkali metal, an alkaline earth metal, an organic cation, and It is at least one selected from hydrogen atoms, and m and n are mole fractions when m + n = 1, and 0 ≦ m ≦ 0.4. ]

<2> Described in <1>, wherein the component A substantially does not contain fine particles having a diamond structure having a median diameter of 4 to 100 nm when measured with a particle size distribution meter based on laser light diffraction / scattering. Abrasive liquid composition.
<3> The polishing liquid composition according to <1> or <2>, wherein the average particle size of the component A is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more.
<4> The polishing liquid composition according to any one of <1> to <3>, wherein the average particle size of the component A is preferably 100 nm or less, more preferably 70 nm or less, still more preferably 40 nm or less.
<5> The polishing liquid composition according to any one of <1> to <4>, wherein the average particle size of the component A is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 70 nm or less, and further preferably 10 nm or more and 40 nm or less. thing.
<6> The polishing liquid composition according to any one of <1> to <5>, wherein the component A is silica.
<7> The polishing liquid according to any one of <1> to <6>, wherein the content of the component A is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. Composition.
<8> The polishing liquid composition according to any one of <1> to <7>, wherein the content of the component A is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. ..
<9> The content of the component A is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, further preferably 3% by mass or more and 10% by mass or less, <1>. The polishing liquid composition according to any one of <8>.
<10> The content of the structural unit having an aromatic ring in the side chain of the phenol skeleton constituting the main chain in the component B is preferably 5 mol% or less, more preferably 4 mol% or less, and 3 mol% or less. The polishing liquid composition according to any one of <1> to <9>, wherein 2 mol% or less is further preferable, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable.
<11> m is 0 ≦ m ≦ 0.4, preferably 0 ≦ m ≦ 0.3, more preferably 0 ≦ m ≦ 0.25, and even more preferably 0 ≦ m ≦ 0.2. The polishing liquid composition according to any one of 1> to <10>.
<12> The content of the composition represented by the formula (I) in all the constituent units constituting the component B is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. , The polishing liquid composition according to any one of <1> to <11>.
<13> The content of the composition represented by the formula (I) in all the constituent units constituting the component B is preferably 100 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less. , 80 mol% or less, more preferably, the polishing liquid composition according to any one of <1> to <12>.
<14> The content of the composition represented by the formula (I) represented by the formula (I) in all the constituent units of the component B is preferably 5 mol% or more and 100 mol% or less, more preferably 5 mol% or more and 95 mol% or less, and 10 The polishing liquid composition according to any one of <1> to <13>, more preferably mol% or more and 90 mol% or less, still more preferably 20 mol% or more and 80 mol% or less.
<15> The weight average molecular weight of the component B is preferably 500 or more, more preferably 1,000 or more, further preferably 1,400 or more, further preferably 1,500 or more, further preferably 3,000 or more, 4, The polishing liquid composition according to any one of <1> to <14>, wherein 500 or more is more preferable, 5,000 or more is further preferable, 8,000 or more is further preferable, and 10,000 or more is further preferable.
<16> The weight average molecular weight of component B is preferably 1,000,000 or less, more preferably 75,000,000 or less, further preferably 500,000 or less, further preferably 250,000 or less, and further preferably 120,000 or less. Preferably, 100,000 or less is further preferable, 75,000 or less is further preferable, 50,000 or less is further preferable, 40,000 or less is further preferable, 30,000 or less is further preferable, and 25,000 or less is further preferable. The polishing liquid composition according to any one of <1> to <15>, more preferably 20,000 or less.
<17> The weight average molecular weight of component B is preferably 500 or more and 1,000,000 or less, more preferably 1,000 or more and 750,000 or less, further preferably 1,400 or more and 500,000 or less, and 1,500 or more. 250,000 or less is more preferable, 3,000 or more and 100,000 or less is further preferable, 4,500 or more and 75,000 or less is further preferable, 5,000 or more and 50,000 or less is further preferable, and 8,000 or more and 30, The polishing liquid composition according to any one of <1> to <16>, more preferably 000 or less, still more preferably 10,000 or more and 20,000 or less.
<18> The surface tension of component B is preferably 45 mN / m or more, more preferably 55 mN / m or more, further preferably 65 mN / m or more, further preferably 71 mN / m or more, further preferably 72 mN / m or more. The polishing liquid composition according to any one of 1> to <17>.
<19> The surface tension of component B is preferably 90 mN / m or less, more preferably 80 mN / m or less, further preferably 77 mN / m or less, further preferably 74 mN / m or less, any of <1> to <18>. The polishing liquid composition described in Crab.
<20> The surface tension of component B is preferably 45 mN / m or more and 90 mN / m or less, more preferably 55 mN / m or more and 80 mN / m or less, further preferably 65 mN / m or more and 77 mN / m or less, and 71 mN / m or more and 74 mN. The polishing liquid composition according to any one of <1> to <19>, wherein / m or less is more preferable, and 72 mN / m or more and 74 mN / m or less is further preferable.
<21> The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more, more preferably 0.25 MPa or more, further preferably 0.30 MPa or more, any of <1> to <20>. The polishing liquid composition according to.
<22> The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.50 MPa or less, more preferably 0.40 MPa or less, further preferably 0.35 MPa or less, any of <1> to <21>. The polishing liquid composition according to.
<23> The storage elastic modulus of the polishing pad infiltrated with component B is preferably 0.15 MPa or more and 0.50 MPa or less, more preferably 0.25 MPa or more and 0.40 MPa or less, and further preferably 0.30 MPa or more and 0.35 MPa or less. The polishing liquid composition according to any one of <1> to <22>, which is preferable.
<24> The content of the component B is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, still more preferably 0.006% by mass or more, any of <1> to <23>. The abrasive composition according to the above.
<25> The polishing liquid according to any one of <1> to <24>, wherein the content of the component B is preferably 10% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less. Composition.
<26> The content of component B is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.003% by mass or more and 1% by mass or less, and 0.006% by mass or more and 0.1% by mass or less. The polishing liquid composition according to any one of <1> to <25>, which is more preferable.
<27> The mass ratio of component B to component A (content of component B / content of component A) is preferably 0.0001 or more, more preferably 0.0005 or more, still more preferably 0.001 or more. The polishing liquid composition according to any one of 1> to <26>.
<28> The polishing according to any one of <1> to <27>, wherein the mass ratio of the component B to the component A is preferably 0.2 or less, more preferably 0.05 or less, still more preferably 0.01 or less. Liquid composition.
<29> The mass ratio of the component B to the component A is preferably 0.0001 or more and 0.2 or less, more preferably 0.0005 or more and 0.05 or less, further preferably 0.001 or more and 0.01 or less, <1. > To <28>.
<30> The polishing liquid composition according to any one of <1> to <29>, further comprising at least one (component C) selected from an acid and a salt thereof.
<31> The polishing liquid composition according to any one of <1> to <30>, further containing an oxidizing agent (component D).
<32> The pH of the polishing liquid composition is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, still more preferably 2.5 or less, according to any one of <1> to <31>. Abrasive liquid composition.
<33> The pH of the polishing liquid composition is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1 or more, further preferably 1.2 or more, any of <1> to <32>. The polishing liquid composition according to.
<34> The pH of the polishing liquid composition is preferably 0.5 or more and 4 or less, more preferably 0.8 or more and 3.5 or less, further preferably 1 or more and 3 or less, and further preferably 1.2 or more and 2.5 or less. The polishing liquid composition according to any one of <1> to <33>, which is preferable.

Hereinafter, the present disclosure will be described in more detail by way of examples, but these are exemplary and the present disclosure is not limited to these examples.

1. 1. Preparation of polishing liquid composition Component A (coloidal silica, average particle size 26 nm), component B or non-component B (water-soluble polymers B1 to 17 shown in Table 1-1 and Table 1-2), component C (sulfuric acid) , Component D (hydrogen peroxide solution, concentration 35% by mass) and ion-exchanged water were mixed and stirred to prepare polishing liquid compositions (pH 1.5) of Examples 1 to 11 and Comparative Examples 1 to 7. .. The pH value of the polishing liquid composition at 25 ° C. is a value measured using a pH meter (manufactured by Toa Denpa Kogyo Co., Ltd., "HM-30G", and the electrode of the pH meter is immersed in the polishing liquid composition for 2 minutes. The latter values were adopted. The content (effective content) of each component in each polishing liquid composition was 5% by mass for component A, 0.006% by mass for component B or non-component B, and 0.4 for component C. The mass% and the component D were 0.3 mass%.

The following were used as the water-soluble polymers B1 to B17 of the component B and the non-component B used in the preparation of the polishing liquid composition. The configurations of the water-soluble polymers B1 to B17 are shown in Tables 1-1 and 1-2. In the configurations shown in Table 1-1 and Table 1-2, m and n indicate mole fractions when m + n = 1, respectively.
<Component B: Water-soluble polymer>
B1 to B5: Formaldehyde condensate of phenol sulfonic acid (synthesized under alkaline conditions) (pPhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B6 to B7: Formaldehyde condensate of phenol sulfonic acid (synthesized under acidic conditions) (pPhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B8: Formaldehyde condensate of resorcinol sulfonic acid (ResS, manufactured by Konishi Chemical Industry Co., Ltd.)
B9: Phenol / phenol sulfonic acid copolymer (Ph / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B10: Cresol / phenol sulfonic acid copolymer (cresol / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B11: Benzoic acid / phenol sulfonic acid copolymer (benzoic acid / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
<Non-component B: water-soluble polymer>
B12: Bisphenol S / Phenol Sulfonic Acid Copolymer (BisS / PhS, manufactured by Konishi Chemical Industry Co., Ltd.)
B13: Ligno sulfonic acid compound (trade name: Pearlex NP, manufactured by Nippon Paper Chemicals Co., Ltd.)
B14: Aromatic aminosulfonic acid compound (trade name: Floric SF200S, manufactured by Floric)
B15: Sodium phenol sulfonate (monomer) (manufactured by Konishi Chemical Industry Co., Ltd.)
B16: Phenol resin powder (p-Ph, trade name: Belpearl S-890, manufactured by Air Water Inc.)
B17: Polystyrene / polystyrene sulfonic acid copolymer sodium salt (St / SS, manufactured by Kao Corporation)
Here, the solubility of B1 to B15 and B17 in 100 g of an aqueous solution having a pH of 3 at 20 ° C. is 0.01 g or more and B16 is less than 0.01 g.

2. Measurement method of various parameters (1) Weight average molecular weight of water-soluble polymer (component B and non-component B) The weight average molecular weight of component B and non-component B is measured by gel permeation chromatography (GPC) method under the following conditions. bottom. The measurement results are shown in Table 1-1 and Table 1-2.
<Measurement conditions>
Column: TSKgel GMPWXL + TSKgel GMPWXL (manufactured by Tosoh)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 7/3 (volume ratio)
Temperature: 40 ° C
Flow velocity: 1.0 mL / min Sample size: 2 mg / mL
Detector: RI
Standard substance: Sodium polystyrene sulfonate (weight average molecular weight: 1,100, 3,610, 14,900, 152,000, manufactured by POLMER STANDARDS SERVICE)

(2) Surface tension of water-soluble polymer (component B and non-component B) A 0.05% by mass aqueous solution (solid content of 0.05% by mass) of the water-soluble polymer (component B and non-component B) The pH of the water-soluble polymer diluted with pure water) was adjusted to 1.5. Sulfuric acid was used for pH adjustment. Then, a pH-adjusted aqueous solution (20 ° C.) is placed in a chalet, and a tensiometer (“CBVP-Z” manufactured by Kyowa Surface Chemistry Co., Ltd.) is used by the Wilhelmi method (a method of immersing a platinum plate and pulling it up at a constant speed). The surface tension was measured using. The results are shown in Table 1-1 and Table 1-2.

(3) Residual formaldehyde of water-soluble polymers (component B and non-component B) and content of formaldehyde in the polishing liquid composition Residual formaldehyde contained in the water-soluble polymers of component B and non-component B, and The content of formaldehyde in the polishing liquid composition was measured under the following conditions by the acetylacetone derivatization-post-column HPLC method using high performance liquid chromatography (HPLC). The results of residual formaldehyde in the water-soluble polymer are shown in Table 1-1 and Table 1-2.
<Measurement conditions>
Column: Hitachi-Inertsil ODS-3 (5 μm)
Eluent: A: 60 mmol / L Na ₂ HPO ₄ (pH 2.1 / H ₃ PO ₄ ), B: 80% acetonitrile aqueous solution Inclined condition: B: 0% (0-10min), 100% (10.1-20min) , 0% (20.1-30min)
Reaction solution: C: Acetylacetone solution Flow rate: A, B: 1.0 mL / min, C: 0.5 mL / min Column temperature: 25 ° C.
Sample size: 50 μL
Reaction temperature: 90 ° C
Detector: Wavelength 414 nm Visible light

(4) Storage elastic modulus of polishing pad immersed in water-soluble polymer (component B and non-component B) First, 1 mass of each water-soluble polymer (component B, non-component B) prepared to pH 1.5 with sulfuric acid. Prepare 100 g of% aqueous solution. Then, about 0.06 g of a CF4301N pad (manufactured by Fujibo) without a PET sheet punched out at 24φ is added to the prepared aqueous polymer solution, stirred at room temperature for 30 minutes, and allowed to stand at 60 ° C. for 24 hours. .. Then, the resin sheet is washed twice (10 seconds) with an ion-exchanged water shower, dried, punched into a disk shape having a diameter of 8 mm, and the storage elastic modulus is determined by dynamic viscoelasticity measurement. The measurement results are shown in Table 2.
<Measurement conditions>
DMS measuring device: ARES-G2 (TA Instrument Japan Inc.)
DMS measurement conditions: strain 0.01 to 50%, frequency 10 Hz, modulation temperature region 25 ° C., and storage elastic modulus G'read values at strain 40%.

(5) Average particle size of colloidal silica (component A) A standard sample was prepared by adding component A (colloidal silica) used for preparing the polishing liquid composition and sulfuric acid to ion-exchanged water and stirring the mixture. .. The contents of component A and component C in the standard sample were 1% by weight and 0.45% by weight, respectively. The area of the scattering intensity distribution obtained by the Cumulant method at a detection angle of 90 ° when this standard sample is integrated 200 times by a dynamic light scattering device (DLS-6500 manufactured by Otsuka Electronics Co., Ltd.) according to the instructions attached by the same manufacturer. The particle size was determined to be 50% of the total, and the average particle size of the colloidal silica was used. The result was 26 nm.

3. 3. Polishing Method Using the polishing liquid compositions of Examples 1 to 11 and Comparative Examples 1 to 7 prepared as described above, the following polishing substrate was polished under the polishing conditions shown below. Next, scratches on the polished substrate surface, substrate surface waviness, and polishing speed were measured and evaluated under the conditions shown below.

[Substrate to be polished]
As the substrate to be polished, a substrate obtained by roughly polishing a Ni-P-plated aluminum alloy substrate with a polishing liquid composition containing an alumina abrasive in advance was used. This substrate to be polished has a thickness of 1.27 mm, an outer diameter of 95 mm, and an inner diameter of 25 mm. The amplitude of the wavelength 0.4 to 2 mm) was 2 nm, and the amplitude of the short wavelength swell (wavelength 50 to 400 μm) was 2 nm.

[Polishing conditions (finish polishing)]
Polishing tester: Double-sided polishing machine (manufactured by Speedfam, "Double-sided 9B polishing machine")
Polishing pad: Fujibo suede type (thickness 0.9 mm, average opening diameter 30 μm)
Polishing liquid: Polishing liquid composition of Examples 1 to 11 and Comparative Examples 1 to 7 Polishing liquid composition Supply amount: 100 mL / min ( ^{Supply rate per 1 cm 2 of} substrate to be polished: 0.076 mL / min)
Lower platen rotation speed: 32.5 rpm
Polishing load: 11.8 kPa
Polishing time: 5 minutes Number of substrates charged: 10

4. Evaluation method [Measurement and evaluation of the number of scratches]
Measuring equipment: "OSA7100" manufactured by Candela Instruments
Evaluation: Four substrates were randomly selected from the substrates put into the polishing tester, and each substrate was irradiated with a laser at 10000 rpm to measure scratches. The total number of scratches (lines) on both sides of each of the four substrates was divided by 8 to calculate the number of scratches per substrate surface. The results are shown in Table 2 below as relative values with Comparative Example 1 as 100.
<Evaluation criteria>
Number of scratches (relative value): Evaluation less than 70: Occurrence is extremely suppressed and substrate yield can be expected to improve 70 or more and less than 80: Actual production possible 80 or more and less than 100: Improvement required for actual production 100 or more: Substrate yield Will drop significantly

[Short wavelength swell]
The polishing time was set so that the weight reduced by polishing was 35 mg or more and 45 mg or less, respectively, and the waviness of the polished substrate was measured under the following conditions to obtain the value of the waviness per polishing amount. The swell was measured at 4 points per surface and 3 on the front and back surfaces, and the average value was calculated as the undulation of the substrate. As the measured test substrate, the substrate obtained by polishing 500 times from the start of the polishing pad under the polishing conditions was used in the above polishing test. The results are shown in Table 2 below.
<Measurement conditions>
Measuring machine: New View 7300 (manufactured by Zygo)
Lens: 2.5x Zoom: 0.5x Measurement wavelength: 80-500μm
Measurement position: 27 mm radius from the center of the board
Analysis software: Zygo Metro Pro (manufactured by Zygo)

As shown in Table 2 above, in the polishing liquid compositions of Examples 1 to 11, scratches on the surface of the substrate were reduced while ensuring the storage elastic modulus. Comparing Example 4 with Comparative Examples 1, 2 and 7, the higher the storage elastic modulus, the more the short wavelength swell was reduced. Normally, as the number of polishings increases, the polishing pad wears and the short-wavelength swell worsens. However, the higher the storage elastic modulus, the more the polishing pad wear is suppressed, which leads to the reduction of the short-wavelength swell in the continuous use of the polishing pad. it is conceivable that.
From the above, it was found that the polishing liquid composition of the present disclosure can reduce short-wavelength waviness in continuous use of scratches and polishing pads.

According to the present disclosure, for example, a magnetic disk substrate suitable for increasing the recording density can be provided.

Claims (8)

An abrasive liquid composition containing an abrasive, a water-soluble polymer, and an aqueous medium.
A polishing liquid composition in which the water-soluble polymer has a structure represented by the following general formula (I).

[In formula (I), R ₁ is _{at least one selected from CH 3} , COOH and H, k is 1-2, and X is an alkali metal, an alkaline earth metal, an organic cation, and It is at least one selected from hydrogen atoms, and m and n are mole fractions when m + n = 1, and 0 ≦ m ≦ 0.4. ] The content of fine particles having a diamond structure having a median diameter of 4 to 100 nm as measured by a particle size distribution meter based on laser light diffraction / scattering in the abrasive is 1.0% by mass or less. , The polishing liquid composition according to claim 1. The polishing liquid composition according to claim 1 or 2, wherein the polishing material is silica. The polishing liquid composition according to claim 3, wherein the average particle size of silica is 100 nm or less. The polishing liquid composition according to any one of claims 1 to 4, further comprising an acid. The polishing liquid composition according to any one of claims 1 to 5, wherein the polishing liquid composition is a polishing liquid composition for a magnetic disk substrate. The polishing liquid composition according to any one of claims 1 to 6 is supplied to the surface to be polished of the substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and / or the substrate to be polished is moved. A method of manufacturing a substrate, which includes a step of polishing. The polishing liquid composition according to any one of claims 1 to 6 is supplied to the surface to be polished of the substrate to be polished, the polishing pad is brought into contact with the surface to be polished, and the polishing pad and / or the substrate to be polished is moved. A method of polishing a substrate, including polishing the substrate.