JP6383046B2 - Detergent composition for hard disk substrate - Google Patents

Description

  The present disclosure relates to a cleaning composition for a substrate for a hard disk, a method for cleaning the substrate, and a method for manufacturing a substrate for a hard disk.

  In recent years, large amounts of data such as moving images and sounds have been handled in personal computers and various electronic devices, and large-capacity information recording apparatuses are required. As a result, the demand for higher recording density for information recording media is increasing year by year. In order to cope with this, the adoption and mass production of perpendicular magnetic recording is being promoted for hard disks. In the perpendicular magnetic recording system, information recording medium substrates (hereinafter also referred to as “hard disk substrates”) are required to have higher levels of heat resistance and surface smoothness than those of current substrates. . Furthermore, the degree of cleanliness required for the hard disk substrate surface is increasing.

  Examples of the material used for the hard disk substrate include aluminum and glass whose surfaces are nickel-phosphorous plated. Recently, even in the field of semiconductor substrates, although the substrate materials are different, high cleanliness of the substrate surface is required, and various cleaning agents have been developed.

Patent Document 1 discloses a cleaning effective for cleaning a pad such as a polishing pad used for polishing, which is contaminated by solid dirt such as abrasive particles in the polishing liquid, aggregates thereof, and polishing scraps of an object to be polished. A detergent composition containing an anionic surfactant having at least one group selected from —COOR and —SO ₃ R (R represents a hydrogen atom, an inorganic base or an organic base) in the molecule as the agent composition Things are disclosed.

  Patent Document 2 discloses a cleaning composition having a low foaming property, which is effective for removing fine organic or inorganic foreign matters and oils, which is used when a semiconductor element is formed on a semiconductor substrate such as a silicon wafer. Polyacrylic acid having a weight average molecular weight of 500 to 150,000 obtained by using at least one selected from acrylic acid, methacrylic acid and maleic acid as a monomer component and using the monomer component in an amount of 20 mol% or more of the total monomer component usage amount Disclosed is a cleaning composition for a semiconductor substrate or a semiconductor element, which contains a carboxylic acid compound.

  In Patent Document 3, there is little environmental load, and before and after chemical mechanical polishing (CMP), CMP abrasive grains such as silica and alumina remaining on a semiconductor component such as a semiconductor substrate, during CMP, As a cleaning agent having a high cleaning effect against impurities such as Fe, Mn, Al, Ce, Cu, W, and Ti based on contained metal impurities or metal wiring, a monomer component containing at least itaconic acid (salt) is used. Disclosed is a cleaning agent for semiconductor parts, the main component of which is a (co) polymerized (co) polymer.

JP 2000-309796 A Japanese Patent Laid-Open No. 11-181494 JP 2001-64680 A

  Generally, a manufacturing process of a hard disk substrate includes a polishing process using a polishing liquid composition. If particles such as polishing scraps and abrasive grains remain on the surface of the substrate that has undergone the polishing process, the performance and yield of the magnetic disk are adversely affected. In particular, even if fine particles are once peeled off from the substrate, they tend to reattach to the substrate surface, and the cleaning composition is also required to have high particle dispersibility.

  Therefore, the present disclosure provides a cleaning composition that is excellent in cleaning properties of particles remaining on the substrate surface, a substrate cleaning method using the same, and a hard disk substrate manufacturing method.

〔式（Ｉ）中、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立に、水素原子、メチル基、又は−(ＣＨ₂)_pＣＯＯＭ²を示し、Ｍ¹及びＭ²はそれぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）、有機アンモニウム基、又はアンモニウム基を示し、ｐは０以上２以下の整数を示す。〕

〔式（ＩＩ）中、Ｒ⁴及びＲ⁵はそれぞれ独立に、水素原子又はメチル基を示し、ｑは０以上２以下の整数を示し、ＡＯは炭素数２又は３のアルキレンオキシ基を示し、ｎはＡＯの平均付加モル数であって、４以上３００以下の数を示し、Ｘは水素原子又は炭素数１以上３以下のアルキル基を示す。〕

〔式（ＩＩＩ）中、Ｒ⁶及びＲ⁷はそれぞれ独立に、水素原子又はメチル基を示し、ｒは０以上２以下の整数を示し、ＡＯは炭素数２又は３のアルキレンオキシ基を示し、ｍはＡＯの平均付加モル数であって、４以上３００以下の数を示し、Ｙは水素原子又は炭素数１以上３以下のアルキル基を示す。〕 In one aspect, the present disclosure provides a structural unit (a1) derived from a monomer a1 represented by the following general formula (I) or an anhydride thereof, a monomer represented by the following general formula (II), and the following general formula ( III) containing a polymer (component A) containing a structural unit (a2) derived from at least one monomer a2 selected from the monomers represented by formula (III), the weight average molecular weight of component A being 15000 or more and 200000 or less, pH The present invention relates to a cleaning composition for a hard disk substrate, wherein is 8 or more.

[In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ² , and M ¹ and M ² each independently represent a hydrogen atom , An alkali metal, an alkaline earth metal (1/2 atom), an organic ammonium group, or an ammonium group, and p represents an integer of 0 or more and 2 or less. ]

[In Formula (II), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, q represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, n is the average number of added moles of AO and represents a number of 4 to 300, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[In the formula (III), R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, r represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, m is the average number of added moles of AO and represents a number of 4 to 300, and Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

  In another aspect, the present disclosure includes a cleaning step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure, and the substrate to be cleaned is a substrate polished with a polishing liquid composition. This relates to the cleaning method.

  In another aspect, the present disclosure includes a cleaning step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure, wherein the substrate to be cleaned is a substrate polished with a polishing composition. The present invention relates to a method for manufacturing an industrial substrate.

  According to the present disclosure, it is possible to provide a cleaning composition having excellent cleaning properties for particles remaining on the substrate surface. And according to the washing | cleaning method and manufacturing method using the cleaning composition of this indication, the board | substrate for hard disks excellent in the cleanliness of the board | substrate surface after washing | cleaning can be obtained. Furthermore, according to the cleaning method and the manufacturing method using the cleaning composition of the present disclosure, a high recording density hard disk recording apparatus can be obtained.

  The present disclosure can improve the removability of particles remaining on a substrate surface when a substrate polished with a polishing composition is washed with a cleaning composition containing a predetermined polymer (component A) and having a pH of 8 or higher. Based on this knowledge.

  That is, in one aspect, the present disclosure provides the structural unit (a1) derived from the monomer a1 represented by the general formula (I) or an anhydride thereof, the monomer represented by the general formula (II), and the following general formula It contains a polymer (component A) containing a structural unit (a2) derived from at least one monomer a2 selected from the monomers represented by formula (III), and the weight average molecular weight of component A is 15000 or more and 200000 or less The present invention relates to a cleaning composition for hard disk substrates having a pH of 8 or more (hereinafter, also referred to as “cleaning composition according to the present disclosure”).

Although the details of the mechanism by which the effects of the present disclosure are manifested are not clear, they are estimated as follows.
By adsorbing the carboxyl group of the polymer (component A) in the cleaning composition to the substrate surface and the particle surface, a three-dimensional barrier due to the polyalkyleneoxy group is formed on the substrate surface and the particle surface. Three-dimensional repulsion occurs between particles or between particles, and as a result, the removal of particles from the substrate surface is promoted, and the reattachment of particles to the substrate surface and the aggregation of particles are suppressed. It is presumed that can be efficiently removed and the cleaning property can be improved.
Furthermore, since the polymer (component A) has a predetermined weight average molecular weight, the action of the above-described steric repulsion occurs more effectively, and the reattachment of particles to the substrate surface and the aggregation of particles are more effectively suppressed. It is considered possible. Usually, particles derived from abrasive scraps are smaller in particle size and difficult to remove than particles derived from abrasive grains. However, the cleaning composition of the present disclosure can be removed by containing a predetermined polymer (component A). It is considered that particles derived from difficult polishing waste can be efficiently removed.
However, the present disclosure need not be construed as limited to these mechanisms.

  Therefore, according to the cleaning composition according to the present disclosure, in one or a plurality of embodiments, the particles in the cleaning composition are excellent in dispersibility, and the particles remaining on the substrate surface can be effectively removed. And according to the washing | cleaning method and manufacturing method using the cleaning composition concerning this indication, the board | substrate for hard disks which is excellent in the cleanliness in one or some embodiment can be obtained. Furthermore, a hard disk recording device having a high recording density can be realized by using a hard disk substrate that has been cleaned using the cleaning composition according to the present disclosure.

  In the present disclosure, “particle” refers to a foreign matter remaining on or adhering to the substrate surface. “Particle” in the present disclosure includes foreign matters derived from polishing scraps such as nickel oxide and silicon oxide; foreign matters derived from abrasive grains such as silicon oxide (silica), aluminum oxide (alumina), and cerium oxide (ceria); .

  Hereinafter, each component contained in the cleaning composition according to the present disclosure will be described.

[Component A: Polymer]
Component A contained in the cleaning composition according to the present disclosure is represented by the structural unit (a1) derived from the monomer a1 represented by the following general formula (I) or its anhydride, and the following general formula (II). And a polymer containing a structural unit (a2) derived from at least one monomer a2 selected from monomers represented by the following general formula (III).

(Monomer a1)

In formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ² , and M ¹ and M ² each independently represent a hydrogen atom, An alkali metal, an alkaline earth metal (1/2 atom), an organic ammonium group, or an ammonium group is represented, and p represents an integer of 0 or more and 2 or less.

In formula (I), R ¹ , R ² and R ³ are at least one selected from a hydrogen atom, a methyl group and — (CH ₂ ) _p COOM ² , and R ¹ and R R ³ is a hydrogen atom, R ² is preferably a hydrogen atom or a methyl group, R ¹ and R ³ is a hydrogen atom, R ² is more preferably a methyl group.

In formula (I), M ¹ and M ² are at least one selected from a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an organic ammonium group, and an ammonium group, and have improved detergency. In view of the above, alkali metals are preferable, and sodium and potassium are more preferable.

In the formula (I), p is an integer of 0 or more and 2 or less, and 0 or 1 is preferable from the viewpoint of improving the cleaning property.
Is more preferable.

  The monomer a1 represented by the formula (I) may be an anhydride.

  Examples of the monomer a1 include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and their anhydrides and salts thereof, and acrylic acid, methacrylic acid, maleic acid from the viewpoint of improving detergency. And at least one selected from maleic anhydride is preferred, at least one of acrylic acid and methacrylic acid is more preferred, and methacrylic acid is even more preferred. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and the like. From the viewpoint of improving detergency, alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.

(Monomer a2)
The monomer a2 is selected from a monomer represented by the following general formula (II) (hereinafter also referred to as “monomer a21”) and a monomer represented by the following general formula (III) (hereinafter also referred to as “monomer a22”). At least one monomer.

<Monomer a21>

In formula (II), R ⁴ and R ⁵ each independently represents a hydrogen atom or a methyl group, q represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, n Is the average number of moles of AO added and represents a number from 4 to 300, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  In the formula (II), AO represents an alkyleneoxy group having 2 or 3 carbon atoms, and the alkyleneoxy group may be in a linear or branched form. AO may be one type or two or more types. When there are two or more types of AO, the addition format may be random or block. Examples of AO include an oxyethylene (EO) group and an oxypropylene (PO) group, and an oxyethylene (EO) group is preferable from the viewpoint of detergency.

  In formula (II), n is a number of 4 or more and 300 or less, preferably 6 or more, more preferably 9 or more, still more preferably 20 or more, and still more preferably 40 or more, from the viewpoint of improving the cleaning property. 80 or more is more preferable, and from the same viewpoint, 200 or less is preferable, 150 or less is more preferable, and 130 or less is more preferable.

  In the formula (II), X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of improving detergency. The alkyl group may be in any of linear and branched forms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  As the monomer a21, when q in the formula (II) is 0, for example, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, propoxypolyethyleneglycol (meth) acrylate, methoxy Examples include polypropylene glycol (meth) acrylic acid ester, ethoxypolypropylene glycol (meth) acrylic acid ester, and propoxypolypropylene glycol (meth) acrylic acid ester. From the viewpoint of improving detergency, methoxypolyethylene glycol (meth) acrylic acid ester , Ethoxypolyethylene glycol (meth) acrylic acid ester, and propoxypolyethylene glycol (meth) acrylic acid ester are preferred. Ku, methoxy polyethylene glycol (meth) acrylate are more preferred, even more preferably from methoxy polyethylene glycol methacrylate. “(Meth) acrylic acid ester” means at least one of acrylic acid ester and methacrylic acid ester.

  As the monomer a21, when q in the formula (II) is 1, for example, methoxypolyethyleneglycol-3-butenoate, ethoxypolyethyleneglycol-3-butenoate, propoxypolyethyleneglycol-3-butenoate, methoxy Examples thereof include polypropylene glycol-3-butenoic acid ester, ethoxy polypropylene glycol-3-butenoic acid ester, and propoxypolypropylene glycol-3-butenoic acid ester.

  As the monomer a21, when q in the formula (II) is 2, for example, methoxypolyethyleneglycol-4-pentenoate, ethoxypolyethyleneglycol-4-pentenoate, propoxypolyethyleneglycol-4-pentenoate, methoxy Examples thereof include polypropylene glycol-4-pentenoic acid ester, ethoxy polypropylene glycol-4-pentenoic acid ester, and propoxypolypropylene glycol-4-pentenoic acid ester.

<Monomer a22>

In formula (III), R ⁶ and R ⁷ each independently represents a hydrogen atom or a methyl group, r represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, m Is the average number of moles of AO added and represents a number of 4 to 300, and Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  In the formula (III), AO represents an alkyleneoxy group having 2 or 3 carbon atoms, and the alkyleneoxy group may be in a linear or branched form. AO may be one type or two or more types. When there are two or more types of AO, the addition format may be random or block. Examples of AO include an oxyethylene (EO) group and an oxypropylene (PO) group, and an oxyethylene (EO) group is preferable from the viewpoint of detergency.

  In the formula (III), m is a number of 4 or more and 300 or less, preferably 6 or more, more preferably 9 or more, still more preferably 20 or more, and still more preferably 40 or more, from the viewpoint of improving the cleaning property. 80 or more is more preferable, and from the same viewpoint, 200 or less is preferable, 150 or less is more preferable, and 130 or less is more preferable.

  In formula (III), Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of improving detergency. The alkyl group may be in any of linear and branched forms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  As the monomer a22, when r in the formula (III) is 0, for example, polyethylene glycol vinyl ether, methoxy polyethylene glycol vinyl ether, ethoxy polyethylene glycol vinyl ether, propoxy polyethylene glycol vinyl ether, polypropylene glycol vinyl ether, methoxy polypropylene glycol vinyl ether, ethoxy polypropylene glycol Examples include vinyl ether, propoxy polypropylene glycol vinyl ether, polyethylene glycol isopropenyl ether, and polyprolene glycol isopropenyl ether.

  As the monomer a22, when r in the formula (III) is 1, for example, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, ethoxy polyethylene glycol allyl ether, propoxy polyethylene glycol allyl ether, polypropylene glycol allyl ether, methoxy polypropylene glycol Allyl ether, ethoxypolypropylene glycol allyl ether, propoxypolypropylene glycol allyl ether, polyethylene glycol-2-methylallyl ether, polyprolene glycol-2-methylallyl ether, polyethylene glycol-2-butenyl ether, polyprolene glycol-2-butyl ether Examples include tenenyl ether.

  As the monomer a22, when r in the formula (III) is 2, for example, polyethylene glycol-3-butenyl ether, methoxypolyethylene glycol-3-butenyl ether, ethoxypolyethylene glycol-3-butenyl ether, propoxypolyethylene Glycol-3-butenyl ether, polypropylene glycol-3-butenyl ether, methoxypolypropylene glycol-3-butenyl ether, ethoxypolypropylene glycol-3-butenyl ether, propoxypolypropylene glycol-3-butenyl ether, polyethylene glycol- 3-methyl-3-butenyl ether, methoxypolyethylene glycol-3-methyl-3-butenyl ether, ethoxypolyethylene glycol-3-methyl-3-butene Ether, propoxypolyethylene glycol-3-methyl-3-butenyl ether, polyprolene glycol-3-methyl-3-butenyl ether, methoxypolyprolene glycol-3-methyl-3-butenyl ether, ethoxypolyprolene glycol- Examples include 3-methyl-3-butenyl ether and propoxypolyprolene glycol-3-methyl-3-butenyl ether.

  In the present disclosure, the molar ratio a1 / a2 of the structural unit (a1) to the structural unit (a2) in all the structural units of the component A is preferably 0.1 or more, more preferably 0.5 or more, from the viewpoint of improving detergency. Preferably, 1 or more is more preferable, 2 or more is more preferable, and from the same viewpoint, 100 or less is preferable, 50 or less is more preferable, 30 or less is further preferable, and 20 or less is more preferable. The molar ratio a1 / a2 in all the structural units of component A is preferably from 0.1 to 100, more preferably from 0.5 to 50, even more preferably from 1 to 30 from the viewpoint of improving the cleaning properties. More preferably, it is 20 or less.

  The component A in this indication can further contain other structural units other than a structural unit (a1) and a structural unit (a2). Examples of other structural units include (meth) acrylic acid alkyl ester, hydroxyethyl (meth) acrylate, acrylamides, vinyl acetate, styrene, olefin, vinyl alcohol, allyl alcohol, and polyalkylene oxide adducts of allyl alcohol. Examples include structural units derived from at least one selected compound. From the viewpoint of expressing the effects of the present disclosure, the content of the other structural units in all the structural units of Component A in the present disclosure is preferably 10% by mass or less, more preferably 3% by mass or less, and 1% by mass or less. Is more preferable.

  Component A in the present disclosure can be obtained by a known method such as polymerizing a monomer mixture containing monomer a1 and monomer a2 by a solution polymerization method. Examples of the solvent used for the solution polymerization include water; aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; . As the polymerization initiator used for the polymerization, a known radical initiator can be used, and examples thereof include ammonium peroxodisulfate (ammonium persulfate salt), hydrogen peroxide solution, sodium peroxodisulfate and the like. In the polymerization, a chain transfer agent can be further used. Examples thereof include thiol chain transfer agents such as 2-mercaptoethanol and β-mercaptopropionic acid; and chain transfer agents and solvents such as 1,2-propanediol. . In the present disclosure, the content of each structural unit in all the structural units of Component A can be regarded as a ratio of the amount of each monomer used to the total amount of monomers used for polymerization.

  The arrangement of each structural unit constituting Component A may be any of random, block, or graft.

When Component A has a salt-forming group (—COOH, — (CH ₂ ) _p COOH) derived from monomer a1, it can be used after neutralizing with a neutralizing agent. Examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, ammonia and the like.

  From the viewpoint of detergency, the weight average molecular weight of component A is 15000 or more, preferably 20000 or more, more preferably 25000 or more, further preferably 30000 or more, still more preferably 50000 or more, and from the same viewpoint. 200000 or less, preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 80000 or less. The weight average molecular weight of component A is 15000 or more and 200000 or less from the viewpoint of detergency, preferably 20000 or more and 150,000 or less, more preferably 20000 or more and 100,000 or less, further preferably 20000 or more and 80000 or less, and 25000 or more and 80000 or less. Even more preferred. In the present disclosure, the weight average molecular weight is based on a gel permeation chromatography method (in terms of polyethylene glycol), and can be specifically measured by the method described in Examples.

  The content of Component A with respect to the total mass of components other than water in the cleaning composition according to the present disclosure is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass from the viewpoint of improving detergency. The above is more preferable, 20% by mass or more is more preferable, and from the same viewpoint, 99.9% by mass or less is preferable, 99% by mass or less is more preferable, and 98% by mass or less is more preferable. Furthermore, the content of the component A with respect to the total mass of components other than water in the cleaning composition is preferably 1% by mass or more and 99.9% by mass or less from the viewpoint of improving detergency, and is 10% by mass or more and 99.9% by mass. More preferably, it is 15 mass% or less, More preferably, it is 15 mass% or more and 99 mass% or less, More preferably, it is 20 mass% or more and 98 mass% or less.

  The content of Component A during the cleaning of the cleaning composition according to the present disclosure is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and 0.01% by mass or more from the viewpoint of detergency. Further, from the same viewpoint, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less, and 0.5% by mass or less. More preferably, 0.2 mass% or less is still more preferable. Furthermore, the content of component A at the time of cleaning in the cleaning composition is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, from the same viewpoint, 0.01 mass% or more and 2 mass% or less are more preferable, 0.01 mass% or more and 1 mass% or less are more preferable, 0.01 mass% or more and 0.5 mass% or less are more preferable, 0.01 mass% % To 0.2% by mass is even more preferable.

  As described later, the cleaning composition according to the present disclosure is manufactured as a concentrate, and may be used after being diluted. Therefore, in the present disclosure, “each component at the time of cleaning the cleaning composition” The “content of” in one or more embodiments refers to the content of each component of the cleaning composition used in the cleaning step. Therefore, in the present disclosure, the cleaning composition at the time of cleaning, that is, the cleaning composition used in the cleaning process refers to a cleaning composition in a diluted state in one or a plurality of embodiments.

[Component B: Alkaline agent]
The cleaning composition according to the present disclosure may further contain an alkaline agent (component B). Examples of the alkaline agent include compounds that can impart alkalinity to the cleaning composition, and compounds that can adjust the pH of the cleaning composition within the range described below, and examples include inorganic alkaline agents and organic alkaline agents. Examples of the inorganic alkali agent include ammonia; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; and the like. Examples of the organic alkali agent include hydroxyalkylamines and quaternary ammonium salts. Examples of hydroxyalkylamines include monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylpropanolamine, methyldipropanolamine, and aminoethylethanol. An amine etc. are mentioned. Examples of the quaternary ammonium salt include tetramethylammonium hydroxide and choline. These alkaline agents may be used alone or in combination of two or more.

  Component B is preferably at least one selected from alkali metal hydroxides, hydroxyalkylamines and quaternary ammonium salts from the viewpoint of improving detergency, and alkali metal hydroxides from the viewpoint of reducing wastewater treatment load. More preferred is at least one of potassium hydroxide and sodium hydroxide.

  The content of Component B with respect to the total mass of components other than water in the cleaning composition according to the present disclosure is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more from the viewpoint of improving detergency. 0.5 mass% or more is more preferable, and from the same viewpoint, 99 mass% or less is preferable, 90 mass% or less is more preferable, 80 mass% or less is further preferable, and 75 mass% or less is more preferable. Furthermore, the content of Component B with respect to the total mass of components other than water in the cleaning composition according to the present disclosure is preferably 0.1% by mass or more and 99% by mass or less from the viewpoint of improving detergency. The mass is more preferably 90% by mass or less, further preferably 0.3% by mass or more and 80% by mass or less, and further preferably 0.5% by mass or more and 75% by mass or less.

  The content of Component B during cleaning of the cleaning composition according to the present disclosure is preferably 0.00005% by mass or more, more preferably 0.0001% by mass or more, and 0.001% by mass or more from the viewpoint of detergency. From the same viewpoint, it is preferably 2.0% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less, and even more preferably 0.07% by mass or less. 0.05 mass% or less is more preferable. Further, the content of Component B during cleaning of the cleaning composition is preferably 0.00005% by mass to 2.0% by mass, and 0.00005% by mass to 0.3% by mass from the same viewpoint. More preferably, 0.00005% by mass or more and 0.1% by mass or less is more preferable, 0.0001% by mass or more and 0.07% by mass or less is more preferable, and 0.001% by mass or more and 0.05% by mass or less is more preferable. Further preferred.

  The ratio A / B of the content of the component A to the content of the component B in the cleaning composition according to the present disclosure is preferably 0.01 or more, more preferably 0.1 or more, from the viewpoint of improving the detergency. 0.3 or more is more preferable, and from the same viewpoint, 20000 or less is preferable, 1000 or less is more preferable, and 100 or less is more preferable. The ratio A / B of the content in the cleaning composition is preferably 0.01 or more and 20000 or less, more preferably 0.1 or more and 1000 or less, and further preferably 0.3 or more and 100 or less, from the viewpoint of improving cleaning properties. .

[Component C: Water]
The cleaning composition according to the present disclosure may further contain water (component C). The water is not particularly limited as long as it can serve as a solvent, and examples thereof include ultrapure water, pure water, ion-exchanged water, or distilled water. Pure water or ion exchange water is preferable, and ultrapure water is more preferable. Pure water and ultrapure water can be obtained, for example, by passing tap water through activated carbon, subjecting it to ion exchange treatment, and further distilling it, irradiating a predetermined ultraviolet germicidal lamp as necessary, or passing it through a filter. .

  The content of Component C during cleaning of the cleaning composition according to the present disclosure is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of improving the cleaning property and stabilizing the cleaning composition. From the same viewpoint, 99.99% by mass or less is preferable, 99.98% by mass or less is more preferable, and 99.97% by mass or less is more preferable.

[Optional ingredients]
In addition to the components A to C, the cleaning composition according to the present disclosure includes any of chelating agents, anionic polymers, nonionic surfactants, solubilizers, antioxidants, antiseptics, antifoaming agents, antibacterial agents, and the like. Ingredients can be included. The optional component is preferably contained in the cleaning composition within a range not impairing the effects of the present disclosure, and the content of the optional component at the time of cleaning the cleaning composition is 0% by mass or more and 2.0% by mass. The following is preferable, 0% by mass to 1.5% by mass is more preferable, 0% by mass to 1.3% by mass is further preferable, and 0% by mass to 1.0% by mass is further more preferable.

(Chelating agent)
The cleaning composition according to the present disclosure may contain a chelating agent from the viewpoint of improving cleaning properties. Examples of the chelating agent include aldonic acids such as gluconic acid and glucoheptonic acid; aminocarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; hydroxycarboxylic acids such as citric acid and malic acid; 1-hydroxyethylidene-1,1- And at least one selected from the group consisting of phosphonic acids such as diphosphonic acid; and salts thereof.

(Anionic polymer)
The cleaning composition according to the present disclosure may contain an anionic polymer such as a carboxylic acid polymer from the viewpoint of improving the cleaning property. Examples of the carboxylic acid polymer include acrylic acid polymer, methacrylic acid polymer, maleic acid polymer, acrylic acid / methacrylic acid copolymer, acrylic acid / maleic acid copolymer, methacrylic acid / acrylic acid. An anionic polymer containing methacrylic acid or acrylic acid as a structural unit, such as a copolymer of methyl ester.

(Nonionic surfactant)
The cleaning composition according to the present disclosure may contain a nonionic surfactant from the viewpoint of improving the cleaning performance. Examples of nonionic surfactants include polyalkylene glycol alkyl ethers.

(Solubilizer)
The cleaning composition according to the present disclosure may contain a solubilizer from the viewpoint of improving storage stability. Examples of the solubilizer include at least one selected from p-toluenesulfonic acid, dimethylbenzenesulfonic acid, 2-ethylhexanoic acid, and salts thereof.

  The cleaning composition according to the present disclosure may further contain an aqueous solvent (for example, alcohol such as ethanol) in addition to the water as a solvent, but the solvent included in the cleaning composition according to the present disclosure is water. It is preferable that it consists only of.

[PH of cleaning composition]
The cleaning composition according to the present disclosure has a pH of 8 or more, preferably 9 or more, more preferably 9.5 or more, still more preferably 10 or more, and 10.5 or more from the viewpoint of detergency. Is more preferable, and from the same viewpoint, 14 or less is preferable, 13 or less is more preferable, 12.5 or less is more preferable, 12 or less is more preferable, and 11.5 or less is more preferable. The pH of the cleaning composition according to the present disclosure can be adjusted using, for example, an acid or an alkaline agent of Component B from the viewpoint of improving cleaning properties. Examples of the acid include inorganic acids such as nitric acid, sulfuric acid, and hydrochloric acid; organic acids such as oxycarboxylic acid and amino acids; and the like. In the present disclosure, the “pH at the time of cleaning” is the pH at the time of use (after dilution) of the cleaning composition at 25 ° C., and can be measured using a pH meter, and preferably the electrode of the pH meter is used as the cleaning composition. It is a numerical value after 3 minutes of immersion.

[Production method of cleaning composition]
The cleaning composition according to the present disclosure can be produced by blending Component A and, if necessary, Component B, Component C and an optional component by a known method. For example, the cleaning composition according to the present disclosure can be formed by blending at least Component A. Therefore, this indication is related with the manufacturing method of the detergent constituent including the process of blending at least ingredient A. In the present disclosure, “compounding” includes mixing component A and optionally component B, component C and optional components simultaneously or in any order. In the manufacturing method of the cleaning composition according to the present disclosure, the blending amount of each component may be the same as the content of each component of the cleaning composition according to the present disclosure described above.

  The cleaning composition according to the present disclosure may be manufactured as a concentrate and diluted at the time of use from the viewpoint of storage and transportation. The concentrate of the cleaning composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of storage and transportation, and is preferably a concentrate having a dilution ratio of 200 times or less from the viewpoint of storage stability. . The concentrate of the cleaning composition can be used after being diluted with water so that the content of each component at the time of use becomes the above-described content (that is, the content at the time of cleaning). Furthermore, the concentrate of a cleaning composition can also be used by adding each component separately at the time of use. In the present disclosure, “when using” or “when cleaning” the concentrate of the cleaning composition refers to a state in which the concentrate of the cleaning composition is diluted.

  The pH of the concentrate of the cleaning composition according to the present disclosure is preferably 8 or more, more preferably 9.0 or more, still more preferably 9.5 or more, and 10.0 or more from the viewpoint of improving the washability after dilution. Is more preferable, and from the same viewpoint, 14.0 or less is preferable, 13.0 or less is more preferable, and 12.0 or less is more preferable. The pH of the concentrate of the cleaning composition according to the present disclosure can be measured by the same method as the pH of the cleaning composition according to the present disclosure.

[Substrate to be cleaned]
In one or a plurality of embodiments, the cleaning composition according to the present disclosure may be used for cleaning a substrate polished with a polishing composition or a substrate on which particles remain or adhere.

  Examples of the substrate to be cleaned include a Ni-P plated aluminum alloy substrate and a glass substrate. The glass substrate may be a crystallized glass substrate or a non-crystallized glass substrate.

  Examples of the particles remaining or adhering to the substrate to be cleaned include particles derived from polishing waste such as nickel oxide and silica; particles derived from abrasive grains such as silica, alumina and ceria; and the like in one or a plurality of embodiments. .

  In one or a plurality of embodiments, the cleaning composition according to the present disclosure is a substrate on which particles derived from polishing scraps such as nickel oxide and silica, preferably particles derived from polishing scraps of nickel oxide, are attached in terms of cleaning effect. It can be suitably used for washing. Furthermore, in one or a plurality of embodiments, the cleaning composition according to the present disclosure includes a Ni—P plated aluminum alloy substrate, preferably Ni— after being polished with a polishing liquid composition in terms of cleaning effect. It can be suitably used for cleaning a P-plated aluminum alloy substrate, more preferably for cleaning a Ni-P plated aluminum alloy substrate after being polished with a polishing liquid composition containing silica abrasive grains.

[Substrate cleaning method]
In one aspect, the present disclosure includes a cleaning step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure, and the substrate to be cleaned is a substrate polished with a polishing liquid composition. The cleaning method (hereinafter, also referred to as “cleaning method according to the present disclosure”). The cleaning method according to the present disclosure may further include a dilution step of diluting the concentrate of the cleaning composition according to the present disclosure. The substrate described above can be used as the substrate to be cleaned. In one or a plurality of embodiments, the cleaning step may include a step of bringing the cleaning composition according to the present disclosure into contact with the substrate to be cleaned. In one or more embodiments, the cleaning step may include performing immersion cleaning and / or scrub cleaning. With the cleaning method according to the present disclosure, particles adhering to the substrate surface, preferably particles derived from polishing waste such as nickel oxide and silicon oxide, more preferably particles derived from polishing waste of nickel oxide can be efficiently removed.

(Immersion cleaning)
There are no particular limitations on the conditions for immersing the substrate to be cleaned in the cleaning composition. For example, the temperature of the cleaning composition is preferably 20 to 100 ° C. from the viewpoints of workability and operability. For example, the immersion time is preferably 5 seconds or more, more preferably 10 seconds or more, and even more preferably 100 seconds or more, from the viewpoint of improving the cleanability by the cleaning composition, and improvement of the production efficiency of the cleaned substrate In view of the above, 30 minutes or less is preferable, 10 minutes or less is more preferable, and 5 minutes or less is more preferable. From the viewpoint of improving the removability of the residue and the dispersibility of the residue, it is preferable that ultrasonic vibration is applied to the cleaning composition. As a frequency of an ultrasonic wave, 20-2000 kHz is preferable, for example, 40-2000 kHz is more preferable, and 40-1500 kHz is further more preferable.

(Scrub cleaning)
As a scrub cleaning method, from the viewpoint of promoting the cleaning properties of residues such as abrasive particles and the solubility of oil, a cleaning agent composition to which ultrasonic vibration is applied is injected to the surface of the substrate to be cleaned. The cleaning composition is brought into contact with the surface to be cleaned, or the cleaning composition is supplied onto the surface of the substrate to be cleaned by injection, and the surface to which the cleaning composition is supplied is applied with a cleaning brush. It is preferable to perform washing. Furthermore, from the same viewpoint, the scrub cleaning method supplies the cleaning composition to which the ultrasonic vibration is applied to the surface to be cleaned by injection, and cleans the surface to which the cleaning composition is supplied. It is preferable to wash by rubbing with a brush.

  As means for supplying the cleaning composition onto the surface of the substrate to be cleaned, for example, means such as a spray nozzle can be used. There is no restriction | limiting in particular as a brush for washing | cleaning, For example, a nylon brush, a PVA (polyvinyl alcohol) sponge brush, etc. can be used. As the frequency of the ultrasonic wave, for example, the same value as that preferably employed in the above-described immersion cleaning can be used.

  The cleaning method according to the present disclosure may include one or more steps using known cleaning such as rocking cleaning, cleaning using rotation of a spinner, paddle cleaning, in addition to the immersion cleaning and / or the scrub cleaning. Good.

  In the cleaning method according to the present disclosure, the substrates to be cleaned may be cleaned one by one, but a plurality of substrates to be cleaned may be cleaned at once. The number of cleaning tanks used for cleaning may be one or more.

[Method of manufacturing hard disk substrate]
In one aspect, the present disclosure is a method for manufacturing a substrate for a hard disk (hereinafter, also referred to as “manufacturing method according to the present disclosure”) including a step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure. About. The substrate described above can be used as the substrate to be cleaned.

  Generally, a hard disk substrate can be manufactured by a base material that is a base of a hard disk substrate being subjected to a shape processing step, a rough grinding step, a fine grinding step, a rough polishing step, a final polishing step, and the like. A cleaning process may be included between the processes. The hard disk substrate can be a magnetic hard disk, for example, through a recording section forming process after the final cleaning process.

  The recording part forming step can be performed, for example, by forming a magnetic layer having a magnetic recording region and including a metal thin film on a hard disk substrate by a method such as sputtering. Examples of the metal material constituting the metal thin film include an alloy of chromium, tantalum, platinum and the like and cobalt, an alloy of iron and platinum, and the like. The magnetic layer may be formed on both main surfaces of the hard disk substrate, or may be formed only on one main surface.

  The rough polishing step and the finish polishing step are performed in this order, for example. As the inorganic fine particles contained in the abrasive composition used in the rough polishing step, for example, cerium oxide particles or alumina particles are preferable because high-speed polishing is possible. Silica particles are preferable because the inorganic fine particles contained in the abrasive composition used in the final polishing step improve surface smoothness (surface roughness).

  In one or a plurality of embodiments, after the rough polishing step, a cleaning step using the cleaning composition (first cleaning step), a rinsing step (first rinsing step), a drying step (first drying step), and finish polishing The step, the cleaning step using the cleaning composition (second cleaning step), the rinsing step (second rinsing step), and the drying step (second drying step) can be performed in this order. The cleaning method according to the present disclosure can be applied to the first cleaning step and / or the second cleaning step. The cleaning method according to the present disclosure is preferably used in the second cleaning step from the viewpoint of improving the cleaning performance.

Therefore, this indication is related with a manufacturing method of a substrate for hard disks including the following processes (1) and (2) in one mode.
(1) A polishing step of polishing a substrate to be polished using a polishing liquid composition.
(2) A cleaning step of cleaning the substrate (substrate to be cleaned) obtained in step (1) using the cleaning composition according to the present disclosure.

  The substrate to be polished in the step (1) is generally a substrate after undergoing a fine grinding step, and is preferably a substrate after undergoing a rough polishing step. As the substrate to be polished, a substrate similar to the substrate to be cleaned can be used. In the step (1), a polishing liquid composition 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 a predetermined pressure (load) is applied to the polishing pad and the substrate to be polished. It can be done by moving it. The step (1) is preferably a final polishing step using a polishing liquid composition containing silica particles from the viewpoint of improving the quality of the final substrate. In the final polishing step, it is preferable to repeatedly use the polishing composition.

  The cleaning step (2) can be performed in the same manner as the cleaning method according to the present disclosure described above.

[kit]
In one aspect, the present disclosure is a kit for producing a cleaning composition, the kit containing a component A solution in a container in which a solution containing the component A is contained in a container (hereinafter referred to as “the present disclosure”). Kit)). The kit which concerns on this indication can further contain at least 1 sort (s) chosen from the component B, the component C, and arbitrary components accommodated in the container different from the said component A solution in a container. For example, as a kit according to the present disclosure, a solution containing the component A (first liquid) and a solution containing the component B (second liquid) are stored in a state where they are not mixed with each other. A kit to be mixed (two-component detergent composition) can be mentioned. In each of the first liquid and the second liquid, the above-described component C and optional components may be mixed as necessary. At the time of mixing the first liquid and the second liquid, for example, the concentration of each component in the cleaning composition can be adjusted by adjusting the amount of the second liquid used.
According to the present disclosure, it is possible to provide a kit capable of obtaining a cleaning composition for a substrate for a hard disk that is excellent in cleaning properties of particles remaining on the substrate surface.

[Hard disk recorder]
In one aspect, the present disclosure relates to a hard disk recording apparatus (hereinafter, also referred to as “hard disk recording apparatus according to the present disclosure”) using a hard disk substrate that has been cleaned using the cleaning composition according to the present disclosure. By using a hard disk substrate that has been cleaned using the cleaning composition according to the present disclosure, a hard disk recording device having a high recording density can be provided.

〔式（Ｉ）中、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立に、水素原子、メチル基、又は−(ＣＨ₂)_pＣＯＯＭ²を示し、Ｍ¹及びＭ²はそれぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）、有機アンモニウム基、又はアンモニウム基を示し、ｐは０以上２以下の整数を示す。〕

〔式（ＩＩ）中、Ｒ⁴及びＲ⁵はそれぞれ独立に、水素原子又はメチル基を示し、ｑは０以上２以下の整数を示し、ＡＯは炭素数２又は３のアルキレンオキシ基を示し、ｎはＡＯの平均付加モル数であって、４以上３００以下の数を示し、Ｘは水素原子又は炭素数１以上３以下のアルキル基を示す。〕

〔式（ＩＩＩ）中、Ｒ⁶及びＲ⁷はそれぞれ独立に、水素原子又はメチル基を示し、ｒは０以上２以下の整数を示し、ＡＯは炭素数２又は３のアルキレンオキシ基を示し、ｍはＡＯの平均付加モル数であって、４以上３００以下の数を示し、Ｙは水素原子又は炭素数１以上３以下のアルキル基を示す。〕 The present disclosure further relates to one or more of the following embodiments.
<1> The structural unit (a1) derived from the monomer a1 represented by the following general formula (I) or its anhydride, the monomer represented by the following general formula (II), and the following general formula (III) A polymer (component A) containing a structural unit (a2) derived from at least one monomer a2 selected from the following monomers:
The weight average molecular weight of component A is 15000 or more and 200000 or less,
A cleaning composition for hard disk substrates having a pH of 8 or more.

[In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ² , and M ¹ and M ² each independently represent a hydrogen atom , An alkali metal, an alkaline earth metal (1/2 atom), an organic ammonium group, or an ammonium group, and p represents an integer of 0 or more and 2 or less. ]

[In Formula (II), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, q represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, n is the average number of added moles of AO and represents a number of 4 to 300, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[In the formula (III), R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, r represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, m is the average number of added moles of AO and represents a number of 4 to 300, and Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

<2> In the formula (I), R ¹ , R ² and R ³ are at least one selected from a hydrogen atom, a methyl group and — (CH ₂ ) _p COOM ² , and R ¹ and R ³ are hydrogen. atoms, R ² is preferably a hydrogen atom or a methyl group, R ¹ and R ³ is a hydrogen atom, R ² is more preferably a methyl group, the cleaning composition according to <1>.
<3> In formula (I), M ¹ and M ² are a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom)
The cleaning composition according to <1> or <2>, wherein at least one selected from organic ammonium groups and ammonium groups, alkali metals are preferable, and sodium and potassium are more preferable.
<4> In the formula (I), p is an integer of 0 or more and 2 or less, preferably 0 or 1, more preferably 0.
The cleaning composition according to any one of <1> to <3>.
<5> In the formula (II), n is 4 or more, preferably 6 or more, more preferably 9 or more, further preferably 20 or more, still more preferably 40 or more, and still more preferably 80 or more, < The cleaning composition according to any one of <1> to <4>.
<6> In the formula (II), n is 300 or less, preferably 200 or less, more preferably 150 or less, and further preferably 130 or less, the cleaning composition according to any one of <1> to <5> object.
<7> In the formula (II), X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, any one of <1> to <6> The cleaning composition described in 1.
<8> The molar ratio a1 / a2 of the structural unit (a1) to the structural unit (a2) in all structural units of the component A is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more. The cleaning composition according to any one of <1> to <7>, wherein 2 or more is more preferable.
<9> The molar ratio a1 / a2 of the structural unit (a1) to the structural unit (a2) in all structural units of the component A is preferably 100 or less, more preferably 50 or less, further preferably 30 or less, and 20 or less. The cleaning composition according to any one of <1> to <8>, which is still more preferable.
<10> The molar ratio a1 / a2 of the structural unit (a1) to the structural unit (a2) in all structural units of the component A is preferably 0.1 or more and 100 or less, more preferably 0.5 or more and 50 or less. The cleaning composition according to any one of <1> to <9>, preferably 30 or less and more preferably 2 or more and 20 or less.
<11> The weight average molecular weight of component A is 15000 or more, preferably 20000 or more, more preferably 25000 or more, further preferably 30000 or more, and even more preferably 50000 or more, any one of <1> to <10> A cleaning composition according to claim 1.
<12> The cleaning composition according to any one of <1> to <11>, wherein the weight average molecular weight of component A is 200000 or less, preferably 150,000 or less, more preferably 100000 or less, and further preferably 80000 or less. object.
<13> The weight average molecular weight of Component A is 15000 or more and 200000 or less, preferably 20000 or more and 150,000 or less, more preferably 20000 or more and 100000 or less, further preferably 20000 or more and 80000 or less, and further preferably 25000 or more and 80000 or less. <1> to <12> The cleaning composition in any one of <12>.
<14> The content of Component A with respect to the total mass of components other than water in the cleaning composition is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and 20% by mass. The cleaning composition according to any one of <1> to <13>, wherein the above is more preferable.
<15> The content of Component A with respect to the total mass of components other than water in the cleaning composition is preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. The cleaning composition according to any one of <1> to <14>.
<16> The content of Component A relative to the total mass of components other than water in the cleaning composition is preferably 1% by mass or more and 99.9% by mass or less, and more preferably 10% by mass or more and 99.9% by mass or less. The cleaning composition according to any one of <1> to <15>, wherein 15% by mass to 99% by mass is more preferable, and 20% by mass to 98% by mass is more preferable.
<17> The content of component A during cleaning of the cleaning composition is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.01% by mass or more. <1> To <16>.
<18> The content of the component A at the time of cleaning the cleaning composition is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, and still more preferably 1% by mass or less, The cleaning composition according to any one of <1> to <17>, further preferably 0.5% by mass or less, and further preferably 0.2% by mass or less.
<19> The content of Component A during cleaning in the cleaning composition is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.005% by mass or more and 5% by mass or less, and 0.01% by mass. % To 2% by weight is more preferable, 0.01% to 1% by weight is more preferable, 0.01% to 0.5% by weight is further more preferable, 0.01% to 0. The cleaning composition according to any one of <1> to <18>, further preferably 2% by mass or less.
<20> The cleaning composition according to any one of <1> to <19>, further including an alkaline agent (component B).
<21> Component B is preferably at least one selected from alkali metal hydroxides, hydroxyalkylamines and quaternary ammonium salts, more preferably alkali metal hydroxides, and at least one of potassium hydroxide and sodium hydroxide. The cleaning composition according to <20>, wherein the seed is more preferable.
<22> The content of Component B with respect to the total mass of components other than water in the cleaning composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. More preferably, the cleaning composition according to any one of <20> or <21>.
<23> The content of Component B with respect to the total mass of components other than water in the cleaning composition is preferably 99% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and 75% by mass. The cleaning composition according to any one of <20> to <22>, wherein the following is more preferable.
<24> The content of Component B with respect to the total mass of components other than water in the cleaning composition is preferably 0.1% by mass or more and 90% by mass or less, and more preferably 0.3% by mass or more and 80% by mass or less. The cleaning composition according to any one of <20> to <23>, further preferably 0.5% by mass to 75% by mass.
<25> The content of Component B at the time of cleaning the cleaning composition is preferably 0.00005% by mass or more, more preferably 0.0001% by mass or more, and further preferably 0.001% by mass or more. <20> To <24>.
<26> The content of Component B during cleaning of the cleaning composition is preferably 2.0% by mass or less, more preferably 0.3% by mass or less, further preferably 0.1% by mass or less, and 0.07. The cleaning composition according to any one of <20> to <25>, more preferably not more than mass%, and still more preferably not more than 0.05 mass%.
<27> The content of Component B during the cleaning of the cleaning composition is preferably 0.00005% by mass or more and 2.0% by mass or less, more preferably 0.00005% by mass or more and 0.3% by mass or less. 0.0005 mass% or more and 0.1 mass% or less is more preferable, 0.0001 mass% or more and 0.07 mass% or less is more preferable, 0.001 mass% or more and 0.05 mass% or less is more preferable, < The cleaning composition according to any one of 20> to <26>.
<28> The ratio A / B of the content of component A to the content of component B in the cleaning composition is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.3 or more. The cleaning composition according to any one of <20> to <27>.
<29> The ratio A / B of the content of component A to the content of component B in the cleaning composition is preferably 20000 or less, more preferably 1000 or less, and even more preferably 100 or less, from <20> to <28 > The cleaning composition in any one of>.
<30> The ratio A / B of the content of component A to the content of component B in the cleaning composition is preferably 0.01 or more and 20000 or less, more preferably 0.1 or more and 1000 or less, and 0.3 or more. The cleaning composition according to any one of <20> to <29>, further preferably 100 or less.
<31> The cleaning composition according to any one of <1> to <30>, further containing water (component C).
<32> The cleaning composition according to <31>, wherein the content of Component C during cleaning of the cleaning composition is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more. object.
<33> The content of component C at the time of cleaning the cleaning composition is preferably 99.99% by mass or less, more preferably 99.98% by mass or less, and further preferably 99.97% by mass or less, <31> Or the cleaning composition as described in <32>.
<34> Further containing at least one optional component selected from a chelating agent, an anionic polymer, a nonionic surfactant, a solubilizer, an antioxidant, an antiseptic, an antifoaming agent and an antibacterial agent, from <1> The cleaning composition according to any one of <33>.
<35> The content of the optional component during cleaning of the cleaning composition is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and more preferably 0% by mass or more and 1% by mass. The cleaning composition according to <34>, more preferably 3% by mass or less, and still more preferably 0% by mass or more and 1.0% by mass or less.
<36> The pH at the time of washing is 8 or more, preferably 9 or more, more preferably 9.5 or more, further preferably 10 or more, and still more preferably 10.5 or more, <1> to <35> The cleaning composition according to any one of the above.
<37> The pH during washing is preferably 14 or less, more preferably 13 or less, still more preferably 12.5 or less, still more preferably 12 or less, even more preferably 11.5 or less, <1> to <36 > The cleaning composition in any one of>.
<38> Use of the cleaning composition according to any one of <1> to <37> for cleaning a substrate polished with a polishing liquid composition or a substrate on which particles remain or adhere.
<39> A cleaning step of cleaning a substrate to be cleaned using the cleaning composition according to any one of <1> to <37>, wherein the substrate to be cleaned is a substrate polished with a polishing liquid composition. There is a method for cleaning a substrate.
<40> The cleaning method according to <39>, wherein the substrate is an aluminum alloy substrate plated with Ni—P.
<41> The cleaning method according to <39> or <40>, wherein the polishing liquid composition is a polishing liquid composition containing silica abrasive grains.
<42> A cleaning step of cleaning a substrate to be cleaned using the cleaning composition according to any one of <1> to <37>, wherein the substrate to be cleaned is a substrate polished with a polishing composition. A manufacturing method for a hard disk substrate.
<43> A kit for producing the cleaning composition according to any one of <1> to <37>, comprising a component A solution in a container in which a solution containing component A is contained in a container .
<44> A hard disk recording apparatus using a hard disk substrate cleaned with the cleaning composition according to any one of <1> to <37>.
<45> Use of the cleaning composition according to any one of <1> to <37> for cleaning a substrate for a hard disk.

Hereinafter, the present disclosure will be specifically described by way of examples. However, the present disclosure is not limited to these examples.

1. Preparation of polymer (component A) The following raw materials were used for the preparation of polymers A1 to A16 shown in Table 1.

<Monomer a1>
(1) MAA: Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) AA: Acrylic acid (Wako Pure Chemical Industries, Ltd.)
(3) MA: maleic anhydride (manufactured by Mitsubishi Chemical Corporation)

<Monomer a2>
(1) Monomer a2-1
1000 parts by mass of polyethylene glycol monomethyl ether (weight average molecular weight 5344) having an ethylene oxide addition mole number of 120 melted at 80 ° C. is charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a cooling condenser. It is. Next, 3 parts by mass of hydroquinone and 32 parts by mass of p-toluenesulfonic acid were added. Here, while introducing air into the reaction liquid at a flow rate of 6 ml / min per kg of the total mass of polyethylene glycol monomethyl ether and methacrylic acid, and further introducing nitrogen at a flow rate of 12 ml / min into the gas phase of the reaction vessel, 483 parts by mass of methacrylic acid (an amount that is 30 mol times with respect to polyethylene glycol monomethyl ether) was added, and heating and pressure reduction in the reaction vessel were started. The pressure is controlled to 26.7 kPa, the reaction start time is the time when the reaction solution temperature reaches 105 ° C., and the reaction is continued by heating to maintain the reaction solution temperature at 110 ° C. while distilling the reaction water and methacrylic acid. Went. The pressure was reduced to 12 to 13.3 kPa 1 hour after the start of the reaction and then maintained as it was. Six hours after the start of the reaction, the pressure was returned to normal pressure, and 1.05 times equivalent of 48% aqueous sodium hydroxide was added to neutralize p-toluenesulfonic acid to complete the reaction. Thereafter, the reaction solution temperature was maintained at 130 ° C. or lower, and unreacted methacrylic acid was recovered by a vacuum distillation method to obtain an esterification reaction product. After cooling to 100 ° C., 200 parts by mass of saturated saline and 1000 parts by mass of toluene were added to the reaction product, and adjusted to 50 ° C. Extraction of the layered lower layer, addition of 200 parts by weight of saturated brine, and layering were repeated 5 times, and then toluene was distilled off to purify the monomer a2-1 methoxypolyethyleneglycol methacrylate (EO average) An additional mole number of 120) was obtained.
(2) Monomer a2-2
Methoxypolyethylene glycol methacrylate (EO average addition mole number 23), M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(3) Monomer a2-3
Methoxypolyethylene glycol methacrylate (EO average addition mole number 9), M-90G (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(4) Monomer a2-4
Monomer a2-4 produced and purified in the same manner as monomer a2-1 except that the number of moles of ethylene oxide added to polyethylene glycol monomethyl ether was changed to 41 (weight average molecular weight 1838) and the amount of methacrylic acid charged was changed to 1405 parts by mass. Of methoxypolyethylene glycol methacrylate (EO average addition mole number 41) was obtained.
(5) EG: ethylene glycol (6) monomer a2-5
Methoxypolyethylene glycol allyl ether (average molecular weight 1500, EO average added mole number 32), UNIOX PKA-5010 (manufactured by NOF Corporation)
(7) Monomer a2-6
Polyethylene glycol-3-methyl-3-butenyl ether (EO average addition mole number 50)
(8) Monomer a2-7
Polyethylene glycol allyl ether (EO average addition mole number 25)
(9) Monomer a2-8
Polyethylene glycol acrylate (EO average addition mole number 5)

<Polymerization chain transfer agent>
・ 2-Mercaptoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Β-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Polymerization chain transfer agent and solvent>
・ 1,2-propanediol (Wako Pure Chemical Industries, Ltd.)
<Polymerization initiator>
・ Ammonium peroxodisulfate (ammonium persulfate) (manufactured by Nacalai Tesque)
・ Hydrogen peroxide solution (30-35.5 mass% aqueous solution, manufactured by Nacalai Tesque)
・ Sodium peroxodisulfate (manufactured by Nacalai Tesque)
<Neutralizing agent>
・ Sodium hydroxide (48% by mass NaOH, manufactured by Asahi Glass Co., Ltd.)

[Production Example of Polymer A1]
Water: 282 g (15.7 mol) was charged into a reaction vessel equipped with a stirrer, and the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. MAA: 20.7 g (0.24 mol), monomer a2-1: 323 g (0.06 mol) (mass ratio = 6/94, molar ratio = 80/20), water: 239 g (13.3 mol) What was mixed and dissolved, 10 mass% ammonium persulfate aqueous solution: 34.7 g, and 2-mercaptoethanol: 1.8 g were simultaneously added dropwise to the reaction system over 2 hours. Next, 10% by mass of ammonium persulfate aqueous solution: 13.9 g was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 1 hour. After completion of aging, 23.9 g of a 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A1 (37% by mass aqueous solution).

[Production Example of Polymer A2]
A reaction vessel equipped with a stirrer was charged with 367 g (20.4 mol) of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. MAA: 62.9 g (0.73 mol) and monomer a2-2: 300 g (0.27 mol) (mass ratio = 17.3 / 82.7, molar ratio = 73/27), water: 173 g (9. 6 mol), 10 mass% aqueous ammonium persulfate solution: 34.1 g, and 2-mercaptoethanol: 2.9 g were simultaneously added dropwise to the reaction system over 2 hours. Next, 10 mass% ammonium persulfate aqueous solution: 11.4 g was dropped over 30 minutes, and the mixture was aged at the same temperature (75 ° C.) for 1 hour. After completion of the aging, 61 g of 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A2 (36% by mass aqueous solution).

[Production Example of Polymer A3]
A reaction vessel equipped with a stirrer was charged with 317 g (17.6 mol) of water, purged with nitrogen while stirring, and heated to 75 ° C. in a nitrogen atmosphere. MAA: 46.5 g (0.54 mol) and 323 g (0.06 mol) of monomer a2-1 (mass ratio = 12.6 / 87.4, molar ratio = 90/10), water: 239 g (13.3) Mol) were mixed and dissolved, and 10 mass% ammonium persulfate aqueous solution: 41.7 g and 2-mercaptoethanol: 1.9 g were simultaneously added dropwise to the reaction system over 2 hours. Next, 10% by mass of ammonium persulfate aqueous solution: 13.9 g was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 1 hour. After completion of the aging, 49.3 g of 48 mass% NaOH aqueous solution was added to neutralize to obtain polymer A3 (36 mass% aqueous solution).

[Production Example of Polymer A4]
Water: 275 g (15.3 mol) was charged into a reaction vessel equipped with a stirrer, and the atmosphere was purged with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. MAA: 9.5 g (0.11 mol) and monomer a2-1: 323 g (0.06 mol) (mass ratio = 2.9 / 97.1, molar ratio a1 / a2 = 65/35), water: 239 g (13.3 mol) was mixed and dissolved, 10% by mass ammonium persulfate aqueous solution: 3.8 g, and 1.2 g of 2-mercaptoethanol were simultaneously added dropwise to the reaction system over 2 hours. Next, 11.9 g of 10% by mass ammonium persulfate aqueous solution was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 1 hour. After completion of aging, 13.1 g of 48 mass% NaOH aqueous solution was added to neutralize to obtain polymer A4 (38 mass% aqueous solution).

[Production Example of Polymer A5]
A reaction vessel equipped with a stirrer was charged with 449 g (24.9) mol of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. MAA: 55.9 g (0.65 mol) and monomer a2-2: 390 g (0.35 mol) (mass ratio = 12.5 / 87.5, molar ratio = 65/35), water: 220 g (12. 2 mol) were mixed and dissolved, 10% by mass ammonium persulfate aqueous solution: 31.0 g, and 2-mercaptoethanol: 4.2 g were simultaneously added dropwise to the reaction system over 2 hours. Next, 10% by mass of ammonium persulfate aqueous solution: 10.5 g was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 1 hour. After completion of the aging, 54.2 g of a 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A5 (37% by mass aqueous solution).

[Production Example of Polymer A6]
Water: 292 g (16.2 mol) was charged into a reaction vessel equipped with a stirrer, and the atmosphere was purged with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. MAA: 102 g (1.19 mol) and monomer a2-1: 339 g (0.063 mol) (mass ratio = 23.1 / 76.9, molar ratio = 95/5), water: 252 g (14.0 mol) ), 10 mass% ammonium persulfate aqueous solution: 71.5 g, and 2-mercaptoethanol: 10.3 g were simultaneously added dropwise to the reaction system over 2 hours. Next, 107.2% by weight ammonium persulfate aqueous solution: 57.2 g was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 1 hour. After completion of aging, 103.3 g of a 48% by mass NaOH aqueous solution was added for neutralization to obtain polymer A6 (36% by mass aqueous solution).

[Production Example of Polymer A7]
A reaction vessel equipped with a stirrer was charged with 303 g (16.8 mol) of water, purged with nitrogen while stirring, and heated to 75 ° C. in a nitrogen atmosphere. MAA: 40.4 g (0.47 mol) and monomer a2-3: 257 g (0.53 mol) (mass ratio = 13.3 / 86.7, molar ratio = 47/53), water: 152 g (8. 42 mol), 10 mass% ammonium persulfate aqueous solution: 15.5 g, and 2-mercaptoethanol: 2.1 g were simultaneously added dropwise to the reaction system over 2 hours. Next, 10 mass% ammonium persulfate aqueous solution: 5.2g was dripped over 30 minutes, and it age | cure | ripened at the same temperature (75 degreeC) for 1 hour. After completion of aging, 39.2 g of 48 mass% NaOH aqueous solution was added to neutralize to obtain polymer A7 (37 mass% aqueous solution).

[Production Example of Polymer A8]
Water: 22.6 g (1.26 mol) was charged into a reaction vessel equipped with a stirrer, purged with nitrogen while stirring, and heated to 85 ° C. in a nitrogen atmosphere. AA: 8.7 g (0.12 mol) and monomer a2-4: 89.6 g (0.047 mol) (mass ratio = 8.8 / 91.2, molar ratio = 72/28), water: 92. 3 g (5.13 mol) mixed and dissolved, 5 mass% ammonium persulfate aqueous solution: 15.0 g, and 6 mass% β-mercaptopropionic acid aqueous solution: 15.0 g were simultaneously added to the reaction system over 1.5 hours. And dripped. Next, 22 mass% ammonium persulfate aqueous solution: 5.0 g was dripped over 5 minutes, and it matured at the same temperature (85 degreeC) for 0.5 hour. After the completion of aging, 10.1 g of 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A8 (38% by mass aqueous solution).

[Polymer A9]
-Sodium polyacrylate “Aron A-210” (43% by mass aqueous solution, weight average molecular weight 3000, manufactured by Toagosei Co., Ltd.)
[Polymer A10]
-Sodium polyacrylate (35 mass% aqueous solution, weight average molecular weight 60000, manufactured by Polysciences, Inc.)
[Polymer A11]
Polyethylene glycol methyl ether (number average molecular weight 5000, manufactured by Sigma-Aldrich)
[Polymer A12]
・ Sodium dodecylbenzenesulfonate “Neopelex G-25” (25% by mass aqueous solution, manufactured by Kao Corporation)

[Production Example of Polymer A13]
Water: 90.5 g (5.0 mol) was charged into a reaction vessel equipped with a stirrer, and the atmosphere was purged with nitrogen while stirring. MA: 63.7 g (0.65 mol), monomer a2-5: 525 g (0.35 mol) (mass ratio = 11/89, molar ratio = 65/35), water: 161 g (8.9 mol) 37.0 g of 10% by mass ammonium persulfate aqueous solution: 37.0 g of the mixed and dissolved solution were simultaneously added dropwise to the reaction system over 2 hours. Next, 10% by weight of ammonium persulfate aqueous solution: 14.8 g was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 3 hours. After completion of aging, 108 g of 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A13 (60% by mass aqueous solution).

[Production Example of Polymer A14]
A reactor equipped with a stirrer was charged with water: 234 g (13.0 mol) and monomer a2-6: 546 g (0.24 mol), purged with nitrogen while stirring, heated to 65 ° C. in a nitrogen atmosphere, and oxidized. 8.6 g of hydrogen water was added dropwise. Next, AA: 54.4 g (0.76 mol) and water: 45.6 g (2.5 mol) were mixed and dissolved, β-mercaptopropionic acid: 8.0 g, L-ascorbic acid 3.3 g and Water: 38.8 g mixed and dissolved was simultaneously added dropwise to the reaction system over 2 hours. Thereafter, aging was performed at the same temperature (65 ° C.) for 1 hour. After completion of aging, 62.9 g of a 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A14 (60% by mass aqueous solution) (AA / monomer a2-6 mass ratio = 9/91, molar ratio = 76/24). ).

[Production Example of Polymer A15]
In a reaction vessel equipped with a stirrer, water: 193 g (10.7 mol), 1,2-propanediol: 295 g (3.9 mol), AA: 5.0 g (0.069 mol), monomer a2-7: 150 g (0 .13 mol) was charged, and the nitrogen was replaced while stirring, and the temperature was raised to 85 ° C. in a nitrogen atmosphere. AA: 49.7 g (0.69 mol), monomer a2-7: 150 g (0.13 mol) and water: 50.3 g (2.8 mol) mixed and dissolved, sodium peroxodisulfate: 5. 3 g and water: 21.2 g mixed and dissolved were simultaneously added dropwise to the reaction system over 75 minutes. Next, AA: 45.1 g (0.63 mol), sodium peroxodisulfate: 4.8 g, and water: 30.3 g were mixed and dissolved in the reaction system simultaneously over 135 minutes. Thereafter, aging was performed at the same temperature (85 ° C.) for 3 hours. After completion of the aging, 52.2 g of 48% by mass NaOH aqueous solution was added to neutralize to obtain polymer A15 (40% by mass solution) (AA / monomer a2-7 mass ratio = 25/75, molar ratio = 84/16). ).

[Polymer A16]
As the polymer A16, a sodium salt of acrylic acid / polyethylene glycol acrylate ester (EO average addition mole number 5) copolymer (weight average molecular weight 10,000, compound E described in JP 2000-309796 A) was used. In Table 1, the acrylic acid which becomes the structural unit (a1) of the polymer A16 is indicated as AA, and the polyethylene glycol acrylate ester (EO average added mole number 5) which becomes the structural unit (a2) is indicated as the monomer a2-8.

[Measurement of weight average molecular weight]
The weight average molecular weights of the polymers A1 to A11 and A13 to A16 were measured under the following conditions using a gel permeation chromatography (hereinafter also referred to as “GPC”) method. The measurement results are shown in Table 1.
The weight average molecular weight (348.5) of polymer A12 in Table 1 is the value described in the international chemical safety card.
[GPC conditions]
Column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1 (volume ratio)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.5 mg / mL
Reference material: Polyethylene glycol equivalent

2. Preparation of cleaning composition (Examples 1-22 and Comparative Examples 1-8)
The cleaning composition of Examples 1-22 and Comparative Examples 1-8 was prepared by mix | blending and mixing each component of Table 2 by the ratio (mass%, effective part) of Table 2. The pH is the pH of the cleaning composition at 25 ° C., and the value after 3 minutes was measured by immersing the electrode of a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G) in the cleaning composition. Potassium hydroxide and sulfuric acid were used for pH adjustment. The following were used for Component B and Component C.
<Component B: Alkaline agent>
KOH: Potassium hydroxide (manufactured by Kanto Chemical Co., Inc., deer special grade, solid content 48% by mass)
MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
MDA: N-methyldiethanolamine (Nippon Emulsifier Co., Ltd., amino alcohol MDA)
EA: N- (β-aminoethyl) ethanolamine (Nippon Emulsifier Co., Ltd., amino alcohol EA)
<Component C: Water>
Water: Ultrapure water manufactured using Kurita Industries Co., Ltd. continuous pure water production equipment (Pure Conti PC-2000VRL type) and subsystem (Mac Ace KC-05H type) <Other components>
Sulfuric acid: manufactured by Wako Pure Chemical Industries, Ltd., reagent grade, purity 95.0% by mass

3. Evaluation method
[Dispersibility test method]
30.0 g of the cleaning composition is placed in a 50 mL polypropylene bottle, 0.15 g of nickel oxide particles (average particle size less than 50 nm) is added, and an ultrasonic cleaner UT-105HS (manufactured by Sharp Manufacturing System Co., Ltd., 100 W, (35 kHz, 30 minutes), and the absorbance of the supernatant immediately after stirring and after standing for 1 hour is measured with an ultraviolet-visible spectrophotometer UV-2700 (manufactured by Shimadzu Corporation, measurement wavelength 660 nm). The absorbance immediately after stirring is 100, and the relative value is shown in Table 2 as dispersibility. The larger the value, the better the dispersibility.

[Detergency test method]
A Ni-P plated aluminum alloy substrate (outer diameter: 95 mmφ, inner diameter: 25 mmφ, thickness: 1.75 mm) containing a dispersion (concentration) containing nickel oxide particles (average particle size less than 50 nm) corresponding to polishing waste : 0.0025 mass%) for 2 minutes to prepare a contaminated substrate to be cleaned, that is, a substrate to be cleaned to which particles adhered. And the said to-be-cleaned board | substrate was wash | cleaned using each cleaning composition, and the cleaning property of each cleaning composition was evaluated. Washing was performed as follows.

(Washing)
Five substrates to be cleaned were cleaned under the following conditions using a cleaning apparatus. Two sets of rinse tanks were prepared.
(1) Cleaning-1: 4000 g of a cleaning composition used for cleaning was prepared. The prepared cleaning composition was put into the cleaning tank (a), and the temperature of the liquid in the cleaning tank (a) was set to 25 ° C. And the to-be-cleaned board | substrate was immersed in the cleaning composition in the washing tank (a), and it wash | cleaned for 120 second, irradiating an ultrasonic wave (200 kHz).
(2) Rinsing-1: Ultrapure water was placed in the rinsing tank (b), and the liquid temperature in the rinsing tank (b) was set to 25 ° C. The substrate to be cleaned in the cleaning tank (a) was transferred to the rinsing tank (b), immersed in ultrapure water in the rinsing tank (b), and rinsed for 120 seconds while being irradiated with ultrasonic waves (600 kHz).
(3) Using the rinse tank (c) containing ultrapure water prepared under the same conditions as the rinse tank (b), (2) was repeated again.
(4) Cleaning-2: The substrate to be cleaned in the rinsing tank (c) was transferred to a scrub cleaning unit (A) on which a cleaning brush was set. Then, a cleaning composition at 25 ° C. is injected onto the cleaning brush, and cleaning is performed at 25 ° C. at 5 ° C. by pressing the cleaning brush against both surfaces of the substrate to be cleaned while rotating at 400 rpm in the presence of the cleaning composition. For a second. The cleaning composition having the same composition as the cleaning composition used in “(1) Cleaning-1” was used.
(5) Rinsing-2: The substrate to be cleaned is transferred to the scrub cleaning unit (B) prepared under the same conditions as the scrub cleaning unit (A), ultrapure water at 25 ° C. is injected, and the cleaning brush is attached to the substrate to be cleaned. Rinsing was performed at 25 ° C. for 5 seconds by pressing against both sides while rotating at 400 rpm in the same manner as in (4).
(6) Using the scrub cleaning unit (C) prepared under the same conditions as the scrub cleaning unit (A) and the scrub cleaning unit (D) prepared under the same conditions as the scrub cleaning unit (B), again (4) And (5) were repeated.
(7) Rinsing-3: Ultrapure water was placed in the rinsing tank (e), and the liquid temperature in the rinsing tank (e) was set to 25 ° C. Then, the substrate to be cleaned was transferred to the rinsing tank (e), immersed in ultrapure water in the rinsing tank (e), and rinsed for 600 seconds while being irradiated with ultrasonic waves (170 kHz).
(8) Drying: The substrate to be cleaned was transferred to a spin dryer, and the substrate surface was completely dried at a rotation speed of 700 rpm for 60 seconds.

[Evaluation method of detergency]
Measurement of the number of defects (the number of foreign matter on the substrate) is performed by irradiating the cleaned substrate rotating at 10000 rpm with a MODEL Q-scatter of an optical fine defect inspection apparatus (Candela 7100, manufactured by KLA-Tencor). Carried out. The said measurement was performed about 10 board | substrates each about each cleaning composition, and the average value was computed. The relative values are shown in Table 2 with the value of Comparative Example 1 being 100. It can be evaluated that the smaller the value, the smaller the number of defects and the better the cleaning property.

  As shown in Table 2, the detergent compositions of Examples 1 to 22 exhibited superior dispersibility as compared with the detergent compositions of Comparative Examples 1 to 8. Furthermore, the cleaning composition of Examples 1-22 showed the cleaning property outstanding compared with the cleaning composition of Comparative Examples 1-8.

Claims (9)

From the structural unit (a1) derived from the monomer a1 represented by the following general formula (I) or its anhydride, the monomer represented by the following general formula (II), and the monomer represented by the following general formula (III) Containing a polymer (component A) comprising a structural unit (a2) derived from at least one monomer a2 selected;
The weight average molecular weight of component A is 15000 or more and 200000 or less,
A cleaning composition for hard disk substrates having a pH of 8 or more.

[In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ² , and M ¹ and M ² each independently represent a hydrogen atom , An alkali metal, an alkaline earth metal (1/2 atom), an organic ammonium group, or an ammonium group, and p represents an integer of 0 or more and 2 or less. ]

[In Formula (II), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, q represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, n is the average number of added moles of AO and represents a number of 4 to 300, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[In the formula (III), R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, r represents an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, m is the average number of added moles of AO and represents a number of 4 to 300, and Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]   The cleaning composition of Claim 1 whose weight average molecular weights of the component A are 20000 or more and 80000 or less.   The cleaning composition according to claim 1 or 2, further comprising an alkaline agent (component B).   The cleaning composition according to claim 3, wherein Component B is at least one selected from alkali metal hydroxides, hydroxyalkylamines, and quaternary ammonium salts.   The cleaning composition according to any one of claims 1 to 4, wherein the content of component A during cleaning of the cleaning composition is 0.001 mass% or more and 10 mass% or less. A cleaning step of cleaning the substrate to be cleaned using the cleaning composition according to claim 1;
The substrate cleaning method, wherein the substrate to be cleaned is a substrate polished with a polishing composition.   The cleaning method according to claim 6, wherein the substrate is a Ni—P plated aluminum alloy substrate.   The cleaning method according to claim 6 or 7, wherein the polishing composition is a polishing composition containing silica abrasive grains. A cleaning step of cleaning the substrate to be cleaned using the cleaning composition according to claim 1;
The method for producing a substrate for a hard disk, wherein the substrate to be cleaned is a substrate polished with a polishing composition.