JP5563269B2 - Glass polishing composition - Google Patents

Description

  The present invention relates to a glass polishing composition. In particular, the present invention relates to a polishing composition that improves the grindability of a glass substrate and reduces scratches and fine deposits on the substrate surface, and further relates to the provision of a processing composition suitable for polishing such as a glass substrate for a magnetic disk. .

  For glass polishing, various technologies have been used to polish and flatten the substrate surface with a polishing slurry containing abrasive grains and water, surfactants, solvents, amines, alkalis and other additives. Has been proposed.

In particular, memory hard disks used in magnetic disk drives, which are a major and important application for glass substrates, are in the direction of higher capacity and higher density in recent years. Magnetic media can be plated from conventional coated media. Method, and further to a thin film medium by sputtering. As the density increases, the distance between the memory hard disk and the magnetic head, that is, the flying height of the head is becoming smaller, and recently it has become 0.01 μm or less.
In this memory hard disk, surface processing that gives fine irregularities called texturing processing for the purpose of controlling the magnetic anisotropy of the magnetic layer provided on the nonmagnetic substrate and preventing sticking (adsorption) of the recording / reproducing head Is often performed. Further, since the flying height of the head is extremely small, if there is a protrusion on the disk, a head crash may occur and the magnetic medium or magnetic head on the disk surface may be damaged. Even a minute protrusion that does not lead to a head crash is likely to cause various errors in reading and writing information due to disturbance of the magnetic characteristics of the protrusion. Also, the presence of deep grooves increases the distance between the head disks, weakens the signal output and causes an error. Therefore, in recent years, it has been emphasized to prevent the generation of large irregularities in the memory hard disk substrate grinding process before forming the magnetic medium.

JP2008-105168 Special table 2005-515646

(Japanese Patent Laid-Open No. 2008-105168)
In this patent document, the height of the main surface of a glass hard disk substrate using a slurry containing cerium oxide abrasive grains having a specific composition obtained by a specific manufacturing method including melt cooling, heat treatment, acid treatment, and separation and extraction is described. A precision polishing method has been proposed. In addition, use of polyamidoamines, polyetheramines and aliphatic polyamines as water-soluble polymers containing amino groups contained in the slurry during polishing has also been proposed. However, the purpose of the use is merely to provide step selectivity at the time of polishing, and the effect of use is not specifically described. Rather, high-accuracy polishing regardless of the abrasive grains is required.

(Special Table 2005-515646)
This patent document proposes a chemical-mechanical polishing (CMP) system for semiconductor materials in which an abrasive and an amine-containing polymer such as polyaminoamide are blended. However, the present invention is expected and intended for amine-containing polymers to be formulated, a stop compound that allows selective polishing that slows the removal of the substrate layer but does not affect the removal of the metal layer. This effect has been confirmed to be achieved for specific polyaminoamides. However, when this system is applied to a polishing process of a glass substrate not having a metal layer, what kind of polishing effect is exhibited is not clearly described.

In glass polishing processing, it is possible to increase the polishing rate of the surface, reduce scratches and scratches, reduce the surface roughness and flatten the substrate surface, and reduce deposits on the substrate surface. A composition was sought.
Furthermore, the above-mentioned memory hard disk has recently been required to have a larger capacity and higher density, and since the head flying height is further reduced, scratches and microscopicities that do not pose a problem in the past are required. Yield reduction and signal loss due to deposits (grinding debris) have also become problems. Since the conventional composition cannot reduce scratches and increase the grinding speed, it is possible to provide a balanced polishing composition that has a low scratch and a high grinding speed while maintaining the necessary evaluation as a magnetic recording medium. It is desired.

  The present inventors have studied a glass polishing composition for the purpose of solving such problems, and contain an alkylene oxide adduct of a polycondensate of a polyalkylene polyamine and a C2-C12 alkylene or arylene dicarboxylic acid. It was found that a balanced polishing composition with less scratches and higher grinding speed can be obtained by using the composition.

The effect of the present invention is as described in detail later, but mainly lies in the following points:
1) Improvement of grindability of glass substrate: Grindability is improved and surface roughness is lowered, and electromagnetic conversion characteristics are improved.
2) Reduction of scratches: Reduces scratches on the hard disk surface and improves yield.
3) Improved removal of grinding scraps (fine deposits): Reduces the amount of grinding scraps adhering to the hard disk surface and improves the yield.

Improvement of hard disk properties Polishing composition containing alkylene oxide adduct of polycondensate of dicarboxylic acid and polyalkylene polyamine is smooth, has a small surface roughness, and is a good glass substrate for hard disk with little scratches and deposits. Can be manufactured (see Tables 1 to 12 below). The mechanism of action is not clear, but is estimated as follows. The amide group and amino group of the alkylene oxide adduct of the polycondensate of dicarboxylic acid and polyalkylene polyamine are adsorbed on the glass substrate surface during polishing, so that the glass surface is softened and polishing is promoted (a metal polishing revider Effects and effects).
Further, by forming an adsorption film on the surface, moderate lubricity can be obtained and scratches can be reduced. Furthermore, the adsorption film suppresses adhesion of grinding scraps and abrasive grains to the substrate surface.

  Hereinafter, embodiments of the present invention will be described in detail.

A. Alkylene oxide adduct of polycondensate of dicarboxylic acid and polyalkylene polyamine The hard disk polishing composition of the present invention is practically a composition containing various components as described later. To achieve the object of the invention, the most important component is (c) a C2-8 alkylene of a polycondensate of (a) a polyalkylene polyamine and (b) a C2-C12 alkylene or arylene dicarboxylic acid. An oxide adduct,
The following repeating units:
^{[NR 1 - (R 4 -NR} 2) n-R 5 -NR 3 -CO-R 6 -CO]
Wherein R ¹ and R ³ are a hydrogen atom or a C1-C8 lower alkyl group, R ⁴ and R ⁵ are alkylene groups, and R ² is a hydrogen atom or the following formula — (RO) mH
(Here, R is an alkylene group of C2-8, m is an integer of 1 to 30) a group represented by at least one formula of the n ^{R 2} - (RO) mH N is an integer of 1 to 30, and R ⁶ is a C2 to C12 alkylene or arylene group. )
It is a high molecular compound (A) which has this. The constituent molar ratio of the polymer compound is preferably (a) :( b) = 1: 0.5 to 1.5. More preferably, (a) :( b) = 1: 0.9 to 1.1. Particularly preferably, (a) :( b) = 1: 0.95 to 1.05. In the polymer compound, the average number of added moles of alkylene oxide (RO) per nitrogen atom in the middle of the polyalkylene polyamine chain is 0.1 to 30, preferably 0.2 to 20, More preferably, it is 0.5-20.

(A) The polyalkylene polyamine has dialkylene triamines such as diethylenetriamine, dipropylenetriamine, diisopropylenetriamine, dibutylenetriamine and diisobutylenetriamine, amino groups such as triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. It is at least one compound selected from the group consisting of 3 or more polyalkylene polyamines. Among these, diethylenetriamine and triethylenetetramine are particularly preferable. When the alkylene groups R ⁴ and R ⁵ in the polyalkylene polyamine chain are C5 or more, the solubility in water becomes low, and the resulting solution becomes a non-uniform solution, so that the grinding performance is not sufficiently exhibited.

  (B) C2-C12 alkylene or arylene dicarboxylic acid is succinic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, 1,10-decanedicarboxylic acid, 1,1-dimethyl-1,3- It is at least one compound selected from the group consisting of alkylenedicarboxylic acids such as propanedicarboxylic acid and 1-methyl-1-ethyl-1,3-propanedicarboxylic acid, and arylenedicarboxylic acids such as terephthalic acid and isophthalic acid. Of these, the use of adipic acid is particularly desirable. Use of a dicarboxylic acid exceeding C12 is not preferable because the solubility in water becomes low and the resulting solution becomes a non-uniform solution and the grinding performance is not sufficiently exhibited.

  (C) Examples of the C2-8 alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like, and one or more of these may be used. When adding 2 or more types, the compound obtained may be random or block. C2-4 alkylene oxide is preferable, and ethylene oxide, propylene oxide, and butylene oxide are more preferable.

The polymer compound (A) can be produced using a known method.
Preferably, since molecular design is easy, (c) C2-8 alkylene oxide is added to (a) polyalkylene polyamine and (b) polyalkylene polyamide obtained by reacting C2 to C12 alkylene or arylene dicarboxylic acid. Manufacture by the method.

Specifically, the polymer compound (A) first undergoes a step of producing a polyalkylene polyamide by reacting (a) a polyalkylene polyamine with (b) a C2 to C12 alkylene or arylene dicarboxylic acid. This step can be performed by a known method, and in particular, can be performed by dehydration polycondensation without using a polymerization initiator or the like. The polycondensation method may be a block or a solution. For the polycondensation in the solution, aliphatic hydrocarbons such as n-hexane, 2-ethylhexane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene can be used, but aromatic hydrocarbons such as toluene and xylene are used. It is preferable to use it.
Next, (c) C2-8 alkylene oxide is added to the obtained polyalkylene polyamide. This addition step can be performed by a known method, and can be performed without using a catalyst or the like, but also by using an alkali catalyst such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Can be reacted. Further, when the number of added moles (m) of alkylene oxide is 2 moles or more, it is preferable to use a catalyst, and it is particularly preferable to use an alkali catalyst.
Further, before adding the alkylene oxide (c) to the polyalkylene polyamide obtained by reacting (a) and (b), the polyalkylene polyamide (a) and (b) is dissolved in water. It is preferable. This is because the polyalkylene polyamides (a) and (b) have high viscosity, so that they are dissolved in water in advance to reduce the viscosity as an aqueous polyalkylene polyamide solution. This is to facilitate the addition of oxide. The amount of water is not particularly limited, but it is preferably 50 to 500% by weight based on the polyalkylene polyamide because the viscosity can be reduced. Moreover, when making it melt | dissolve in water, the addition reaction temperature of alkylene oxide has preferable 40-80 degreeC.

Even if the polycondensate itself of dicarboxylic acid and polyamine is blended in the glass polishing composition, the polishing state, the surface roughness, the scratch generation rate, and the number of particles on the substrate surface are completely improved. Even in the recording medium formed on the surface of the obtained substrate, no improvement is observed in any of SNR, glide yield, error yield, and missing count. The remarkable effect of the present invention is achieved for the first time by the alkylene oxide adduct of the polycondensate.
In the present invention, the blending amount of the alkylene oxide adduct of the polycondensate of dicarboxylic acid and polyalkylene polyamine is 1 to 10 parts by weight, preferably 1 to 8 parts per 100 parts by weight of the total weight of the glass polishing composition. Parts by weight, particularly preferably 2 to 6 parts by weight. If the amount is less than this range, the ability to remove scratches and fine deposits is insufficient, and if it exceeds, the blending stability becomes unstable (in some cases, other components may precipitate), which is not preferable.
The molecular weight of the alkylene oxide adduct of the polycondensate of dicarboxylic acid and polyamine is preferably in the range of 500 to 200,000, more preferably in the range of 1000 to 100,000 in terms of achieving the remarkable effects of the present invention. More preferably.

Specific Composition of Polishing Composition The polishing composition for a hard disk of the present invention preferably contains an alkali etching agent, an amine, a surfactant, and an acrylic acid-based water-soluble polymer. Specifically, what has the following composition with respect to 100 weight part of the total weight of the composition for glass polishing processing is mentioned.
A. Alkylene oxide adduct of polycondensate of dicarboxylic acid and polyalkylene polyamine: 1 to 10 parts by weight Alkali etching agent: 0 to 30 parts by weight Amines: 1 to 30 parts by weight C.I. Surfactant: 0.01 to 30 parts by weight Acrylic acid-based water-soluble polymer: 0 to 10 parts by weight Water: 20 to 97 parts by weight Preferably
A. Alkylene oxide adduct of polycondensate of dicarboxylic acid and polyalkylene polyamine: 1 to 8 parts by weight Alkali etching agent: 2 to 20 parts by weight Amines: 2 to 20 parts by weight C.I. Surfactant: 0.05 to 20 parts by weight Acrylic acid-based water-soluble polymer: 0.2 to 5 parts by weight Water: 29-93 parts by weight

B. Alkaline Etching Agent and Amines The composition of the present invention preferably contains an alkali etching agent or amines for the purpose of improving the polishing rate and surface roughness.
In the present invention, the alkaline etchant is at least one compound selected from ammonia, alkali metal hydroxides, alkali metal or alkaline earth metal carbonates, and quaternary ammonium compounds. Is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetraoctylammonium hydroxide, triethylphenylammonium hydroxide, trimethyl Benzylammonium hydroxide, triethylbenzylammonium hydroxide, tribenzylmethylammonium hydroxide, tetrabenzylammonium hydroxide, trimethyl Cyclohexylammonium hydroxide, tributylcyclohexylammonium hydroxide, monohydroxyethyltrimethylammonium hydroxide, dihydroxyethyldimethylammonium hydroxide (dimethylbis (hydroxyethyl) ammonium hydroxide), trihydroxyethylmonomethylammonium hydroxide, monohydroxyethyltriethylammonium Hydroxide, dihydroxyethyl diethylammonium hydroxide, trihydroxyethyl monoethylammonium hydroxide, monohydroxypropyltrimethylammonium hydroxide, dihydroxypropyldimethylammonium hydroxide, trihydroxypropylmonomethylammonium hydroxide, monohydroxyl Pills triethylammonium hydroxide, dihydroxypropyl diethylammonium hydroxide, tri-hydroxypropyl monoethyl ammonium hydroxide or the like is selected. Preferred are tetramethylammonium hydroxide, tetraethylammonium hydroxide, monohydroxyethyltrimethylammonium hydroxide, dimethylbis (hydroxyethyl) ammonium hydroxide, and trihydroxyethylmonomethylammonium hydroxide.
The amines are at least one compound selected from primary amines, secondary amines, and tertiary amines. Specifically, monoethanolamine, diethanolamine, triethanolamine, monoisopropanol Examples include amine, diisopropanolamine, triisopropanolamine, aminoethylethanolamine, piperazine, aminoethylpiperazine and the like. Preferred are amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

The blending amount of the alkali etching agent or amine is 0 to 30 parts by weight, preferably 2 to 20 parts by weight, with respect to 100 parts by weight of the glass polishing processing composition. If the amount is insufficient, the blending stability becomes unstable. On the other hand, it is preferable that the compounding quantity of amines is 1-30 weight part, Most preferably, it is 2-20 weight part. If the amount is less than 1 part by weight, the polishing rate and surface roughness of the glass material are not sufficient, and if it exceeds 30 parts by weight, the surface condition is deteriorated and the surface roughness, scratches and deposits are not sufficient.
Thus, among the B components, the alkaline etchants are all strongly alkaline compounds, which are combined with an alkylene oxide adduct of a polycondensate of carboxylic acid and polyalkylene polyamine as the A component for a long time. If left in contact, there is a risk that the amide group in component A will hydrolyze. Therefore, in order to avoid this danger, the A component and the alkaline etching agent are mixed with other components as necessary to make a so-called two-component product that is a separate solution, and both are mixed immediately before use. It is good to do.

C. Surfactant If abrasives remain on the surface of the hard disk, it will adversely affect the recordability of the finished product. Therefore, nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants are used for cleaning and removing abrasives. It is important to use a compound having surface activity such as an agent. Of these, the use of amphoteric surfactants or anionic surfactants is preferred. Specifically, as the amphoteric surfactant, an alkyl betaine type surfactant, an amidopropyl betaine type surfactant, an imidazolinium betaine type surfactant, or the like can be used. In particular, the use of amphoteric surfactants such as 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl betaine, coconut oil sodium alkylaminopropionate, sodium laurylaminodipropionate is preferred. . As anionic surfactants, alkyl sulfate ester salts, alkyl ether sulfate ester salts, α-olefin sulfonates, alkyl sulfonates, alkyl naphthalene sulfonates, taurine surfactants, sarcosinate surfactants, isethionates Surfactants, N-acyl acidic amino acid surfactants, monoalkyl phosphate salts, higher fatty acid salts, acylated polypeptides, and the like, especially sodium dodecylbenzenesulfonate, laureth sulfate triethanolamine salt (lauryl) Ether sulfate (TEA salt), α-olefin sulfonate Na, lauroyl N-methylalanine triethanolamine salt, p-toluene sulfonate Na, xylene sulfonate Na, cumene sulfonate Na and the like are preferably used.
The practical surfactant content is preferably 0.01 to 30 parts by weight, particularly preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the glass polishing composition. If the amount is less than 0.01 parts by weight, the ability to remove scratches and fine deposits is insufficient, and if it exceeds, blending stability becomes unstable (in some cases, other components may precipitate), which is not preferable.

D. Acrylic acid-based water-soluble polymer The composition of the present invention contains a water-soluble polymer having a carboxylic acid group, a carboxylic acid group and / or a carboxylic acid amide compound group for the purpose of adjusting surface tension, adjusting viscosity or improving dispersion stability. You may mix | blend.
In particular, blending of the water-soluble polymer with acrylic acid, that is, the carboxylic acid is acrylic acid or methacrylic acid (hereinafter sometimes collectively referred to as “(meth) acrylic acid”) It is preferable because it acts on grains and is effective in reducing scratches.
Specific examples of monomers constituting the acrylic acid-based water-soluble polymer include (meth) acrylic acid, (meth) acrylic acid sodium salt, (meth) acrylic acid potassium salt, (meth) acrylic acid ammonium salt, (meta ) Acrylamide, (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide-2,2-dimethylpropanesulfonic acid, and sodium, potassium and ammonium salts thereof. At least one monomer selected from these groups is copolymerized with each other or with an equimolar or less other monomer such as itaconic acid, polyoxyethylene monomethacrylate, hydroxyethyl methacrylate, etc. An acrylic acid-based water-soluble polymer can also be used. In the present invention, the acrylic acid-based water-soluble polymer includes poly (meth) acrylic acid, poly (meth) acrylic acid ammonium salt, poly (meth) acrylic acid sodium salt, poly (meth) acrylic acid potassium salt, poly (meth) It is preferable to use at least one selected from the group consisting of) acrylamide, a copolymer of (meth) acrylic acid and (meth) acrylamide-2-methylpropanesulfonic acid, and salts thereof.
The molecular weight of the water-soluble polymer is not particularly limited as long as it is within the range having water solubility, but is preferably in the range of 500 to 1,000,000, more preferably in the range of 1,000 to 500,000. preferable.
The practical amount of the water-soluble polymer is preferably 0 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the glass polishing composition. If the amount is less than 0.1 parts by weight, the scratch of the glass material increases, and the polishing rate and the surface roughness are insufficient. If the amount exceeds 10 parts by weight, the polishing rate tends to decrease and the scratches tend to increase.

In addition to the compounds exemplified above, various compounds can be added as further auxiliary additives to the composition of the present invention such as fatty acids, other water-soluble polymers, fatty acid amides, glycols, chelating agents and the like. is there. For example, various compounds such as fatty acids, other water-soluble polymers, fatty acid amides, glycols, and chelating agents may be blended for the purpose of dispersing, agglomerating or improving boundary lubricity.
In the present invention, as the fatty acids to be blended, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid and the like are selected.
Examples of fatty acid amides include diethanolamide, monoethanolamide, and ethylene oxide adducts, propylene oxide adducts of fatty acids such as oleic acid, lauric acid, stearic acid, ricinoleic acid, coconut oil fatty acid, and beef tallow fatty acid. Ethylene-propylene) oxide adducts are selected.
Specific examples of other water-soluble polymers include ethers such as polyethylene glycol, polypropylene glycol, and polyethylene glycol alkyl ether. Vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrolein. Polysaccharides such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, cellulose acetate, cellulose nitrate, cellulose sulfate, pectin, gelatin, starch, albumin, polyglycerin, polystyrene sulfonate, alkyl naphthalene sulfonate Na formal condensate At least one compound selected from the group consisting of, and the like.
As glycols, ethylene glycol, propylene glycol, 1,4-butanediol, methylpropanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, alkylene glycol derivatives, glycol esters And glycol ethers.
Chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, α-alanine diacetic acid, aspartic acid diacetic acid, ethylenediamine disuccinic acid, hydroxyethyliminodiacetic acid, 1,3-propanediaminetetraacetic acid, cyclohexane Diaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, L-glutamic acid diacetic acid, aminotri, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta Chelating agents such as (methylenephosphonic acid) and iminodiacetic acid and their alkali metal salts, ammonium salts, amine salts and the like are selected.
Fatty acids and other water-soluble polymers act as abrasive flocculants and are adsorbed by the abrasive grains to aggregate the abrasive grains. The aggregates are cushioned between the polishing tape and the glass substrate surface during polishing. It is presumed that there is an effect in reducing scratches by suppressing the strong biting of abrasive grains.
Fatty acid amides, glycols and chelating agents are adsorbed on the surface of the glass substrate and when they act strongly, a lubricating film is formed at the interface between the substrate surface and the polishing liquid. It acts as a lubricant and both are presumed to be effective in reducing scratches.

Polishing Slurry The composition for glass polishing processing of the present invention is a polishing composition on the surface of a glass material. In addition, the polishing composition shown as the above specific composition is further dispersed with abrasive grains and water or water in advance. Is used as a slurry-like polishing liquid in which abrasive grains are stably dispersed in water. Therefore, the concentration of the abrasive grains in the slurry-like polishing liquid is selected from the range of 0.01 to 50 parts by weight with respect to 100 parts by weight of the slurry-like polishing liquid.
In the present invention, as the abrasive particles dispersed in the polishing liquid, fine particles or powders having a maximum particle size of 15 μm or less measured according to the electrical resistance test method of JIS R6002 are usually selected. According to JIS R6001-1987, the seed abrasive grains belong to the fine powder category and have a particle size distribution (electrical resistance test method) having a maximum particle size of 15 μm or less, specifically, # 3000. , # 4000, # 6000, # 8000 or a similar material is selected.
The material of the abrasive grains is not particularly limited, and specifically, diamond (eg, nanocluster diamond, polycrystalline diamond), garnet, glass, carborundum, metal oxide (eg, alumina, silica, colloidal silica, TiO ₂ , ZrO ₂ , cerium oxide, Ge ₂ O ₃ , MgO), nitride (eg, silicon nitride), carbide (eg, silicon carbide, boron carbide, titanium carbide, tungsten carbide) and the like.

Of these materials, diamond is preferably selected for the memory hard disk substrate because of its good dispersibility and small amount and good polishing. As long as the maximum particle diameter is 15 μm or less, diamond may be a natural product or an industrial synthetic product. Alumina and silicon carbide are artificial abrasives specified in JIS R6111-1987 or equivalent, and those having a maximum particle size of 15 μm or less are selected. According to the provisions of JIS R6111-1987, among the various types belonging to the classification of alumina abrasives or silicon carbide abrasives, such as white alumina abrasives, green silicon carbide abrasives, etc. For this, those having a particle size of # 3000, # 4000, # 6000, # 8000 or the like are selected.
Cerium oxide particles have a lower hardness than silica particles and alumina particles, and therefore are less likely to scratch the polished surface, and are useful for finish mirror polishing. In addition, there is an advantage that the polishing rate is higher than that of the silica abrasive. However, when selecting cerium oxide, it should be noted that the dispersibility is poor, the abrasiveness is not improved unless it is added in a large amount, and the price is high. Of the silica-based polishing dispersions, colloidal silica slurry also has an advantage of excellent dispersion stability. However, there is a problem that the polishing rate is low unless the silica concentration is increased. That is, the colloidal silica slurry requires a high silica concentration in order to obtain a sufficient polishing rate. In selecting colloidal silica, it is necessary to pay attention to the fact that the drying property is high, the slurry introduction nozzle is easily clogged, and it is difficult to use it.
As the dispersing agent for these abrasive grains, at least one kind is selected from the group consisting of polyethylene glycol, polypropylene glycol, poly (ethylene-propylene) glycol and the like. Polypropylene glycol is preferred.

Water plays a very important role as a cooling medium during grinding. The amount of use is 40 to 99% by weight, preferably 50 to 98% by weight, based on the total weight of all components in the slurry-like polishing liquid that is actually used during grinding and in which the abrasive grains are stably dispersed in water. It is. The water preferably used in the present invention is secondary ion-exchanged water having an electric conductivity of 10 μS / cm or less. If tap water is used, chlorine may remain on the hard disk surface, causing corrosion, and metal components such as calcium may remain on the hard disk surface, adversely affecting the recordability of the finished product. It is not preferable.

Glass type :
In the present invention, the material of the glass to be polished is not particularly limited, specifically, blue plate glass, white plate glass, aluminosilicate glass, aluminoborosilicate glass, soda aluminosilicate glass, chemically tempered glass, Examples thereof include crystallized glass, soda lime glass substrate, borosilicate glass, and alkali-free glass.
The glass used for manufacturing the glass substrate for the magnetic disk can be either amorphous glass or crystallized glass, but the former is more tough and durable for applications where flatter and more workability is required. In the case of use, the latter is used.

Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is not limited at all by this Example.
Moreover, in the following examples, the following were used as a compounding component of a polishing liquid composition.

Surfactant <amphoteric surfactant>
(1) 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (CNS) Product name Enacol CNS manufactured by Lion Corporation
(2) Coconut oil fatty acid amidopropyl betaine made by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name Amorgen CB-C
(3) Palm oil sodium alkylaminopropionate, manufactured by Lion, trade name Lipomin LA
(4) Sodium laurylaminodipropionate, manufactured by Lion Co., Ltd., trade name Enadicol DP-30
<Anionic surfactant>
(1) Dodecylbenzenesulfonic acid Na (soft type) manufactured by Kao Corporation, trade name Neopelex G-15
(2) Laureth sulfate triethanolamine salt (lauryl ether sulfate TEA salt) manufactured by Kao Corporation, trade name EMAL 20T
(3) α-olefin sulfonic acid Na manufactured by Lion, trade name Lipolane LB440
(4) Lauroyl N-methylalanine triethanolamine salt manufactured by Lion Co., Ltd., trade name ENADICOL L30-ANT
(5) Na-p-toluenesulfonate, manufactured by Kishida Chemical Co., Ltd., trade name: sodium p-toluenesulfonate (6) Naxylene sulfonate, manufactured by Teika Co., Ltd. Trade name: Tacatox N1140
(7) Sodium cumene sulfonate manufactured by Teika Co., Ltd. Trade name: Teikatox N5040

Amines (1) Monoethanolamine (MEA) Kishida Chemical Co., Ltd., trade name 2-aminoethanol (2) Diethanolamine (DEA) Kishida Kagaku Co., Ltd., trade name 2,2′-iminodiethanol (3) Triethanolamine ( TEA) Product name 2,2 ', 2 "-nitrilotriethanol, manufactured by Kishida Chemical Co., Ltd.
Alkali etching agent (1) NaOH Kishida Chemical Co., Ltd., trade name Sodium hydroxide (2) Tetramethylammonium hydroxide (TMAH) Kishida Chemical Co., trade name Tetramethylammonium hydroxide (25% aqueous solution)
(3) Dimethylbis (hydroxyethyl) ammonium hydroxide (AH212) manufactured by Yokkaichi Gosei Co., Ltd., trade name AH212

Acrylic acid-based water-soluble polymer (1) Polyacrylic acid Na Toagosei Co., Ltd., trade name A30SL Molecular weight 6000
(2) Polyacrylic acid ammonium salt, manufactured by Toagosei Co., Ltd., trade name T540, molecular weight 6000
(3) Copolymer of acrylic acid Na and acrylamido-2-methylpropane sulfonic acid Na Yokkaichi Gosei Co., Ltd. Molecular weight 10000 Copolymer monomer ratio (Na acrylate / acrylamido-2-methylpropane sulfonic acid Na = 1/1 )
Fatty acids (1) Ricinoleic acid, manufactured by Kishida Chemical Co., Ltd., trade name: Ricinoleic acid (2) Decanoic acid, manufactured by Kishida Chemical Co., Ltd., trade name: Decanoic acid
Fatty acid amides, glycols (1) oleic acid amide / 5EO manufactured by Lion Akzo Co., Ltd., trade name Esomide / O15
(2) Propylene glycol (PG) Product name Propylene glycol manufactured by Kishida Chemical Co., Ltd.

Alkylene oxide adduct of polycondensate of dicarboxylic acid and polyamine (1) Diethylenetriamine / adipic acid / 1.0EO Yokkaichi Gosei Co., Ltd., molecular weight 2700
(2) Diethylenetriamine / Adipic acid / 1.0PO Yokkaichi Gosei Co., Ltd. Molecular weight 4100
(3) Diethylenetriamine / Adipic acid / 1.0BO Yokkaichi Gosei Co., Ltd. Molecular weight 7000
(4) Diethylenetriamine / suberic acid / 2.5EO Yokkaichi Gosei Co., Ltd. Molecular weight 12000
(5) Diethylenetriamine / Sebacic acid / 3.5EO, Yokkaichi Gosei Co., Ltd. molecular weight 5000
(6) Diethylenetriamine / terephthalic acid / 1.5PO Yokkaichi Gosei Co., Ltd. Molecular weight 3000
(7) Triethylenetetramine / Adipic acid / 0.5EO Yokkaichi Gosei Co., Ltd. Molecular weight 20000
(8) Triethylenetetramine / suberic acid / 15EO, Yokkaichi Gosei Co., Ltd. molecular weight 50000
(9) Triethylenetetramine / suberic acid / 10PO Yokkaichi Gosei Co., Ltd. molecular weight 45000

[Application Example 1] Production of glass substrate for magnetic disk <Examples 1 to 64 and Comparative Examples 1 to 9>

Polishing :
Polishing was performed on the surface of a disc-shaped glass substrate having a diameter of 2.5 inches as a nonmagnetic substrate. As the glass substrate, crystallized glass and amorphous glass substrate manufactured by KMG were used. The substrate has an outer diameter of 65 mm, an inner diameter of 20 mm, and a plate thickness of 0.635 mm.
The conditions for the polishing process are as follows. That is, for the abrasive grains contained in the polishing liquid, a cluster diamond having primary particles of 5 nm and secondary particles of 30 nm was used. As a polishing liquid, 0.02 part by weight of a cluster diamond, 30 parts by weight of a polishing liquid composition having a composition described in each of Examples and Comparative Examples in Tables 1 to 12, and 69.98 parts by weight of ion-exchanged water as a solvent, An aqueous diamond slurry blended with was used. The polishing liquid was dropped for 2 seconds before processing was started at 50 ml / min. A polyester woven fabric was used as the polishing tape. The polishing conditions were a nonmagnetic substrate rotation speed of 600 rpm, a polishing tape feed of 75 mm / min, and a nonmagnetic substrate swing of 120 times / min. The pressing force of the tape was 2.0 kgf (19.6 N), and the processing time was 10 seconds. After polishing, the surface was washed with ion exchange water. In this way, a glass substrate whose surface was polished was obtained.

Preparation of magnetic recording media :
After polishing, the glass substrate is accommodated in a film forming chamber of a DC magnetron sputtering apparatus (C-3040 manufactured by Anelva), and the film forming chamber is evacuated until the ultimate vacuum is 1 × 10 ⁻⁵ Pa. A 100 nm soft magnetic layer is formed on a substrate at a substrate temperature of 100 ° C. or lower using a target of Co-4Zr-7Nb (Zr content 4 at%, Nb content 7 at%, balance Co) on the substrate, and a Ru layer is formed thereon After that, a Co-4Zr-7Nb soft magnetic layer was further formed to a thickness of 100 nm to form a soft magnetic underlayer 2. On the soft magnetic underlayer, a Ni-6W (W content 6 at%, remaining Ni) target and a Ru target were sequentially formed to a thickness of 10 nm and 20 nm, respectively, to form an orientation control layer.
On the orientation control _{layer, (Co-13Cr-16Pt)} 90- (SiO 2) 4- (Cr 2 O 3) 3- (TiO 2) 3 {Cr content 13 atomic%, Pt content of 16 atomic%, the remainder Co A magnetic layer having a composition of 90 mol%, 4 mol% of an oxide composed of SiO ₂ , 3 mol% of an oxide composed of Cr ₂ O ₃ , and 3 mol% of an oxide composed of TiO _{2 in} a thickness of 60 nm. Formed. This on the magnetic layer was formed by _{(Co-20Cr) 88- (TiO} 2) of 10nm nonmagnetic layer composed of 12 thickness. This on the non-magnetic layer was formed by _{(Co-9.5Cr-16Pt-7Ru} ) 92- (SiO 2) 5- (Cr 2 O 3) thickness of 30nm magnetic layer consisting of 3. A nonmagnetic layer made of Ru was formed to a thickness of 10 nm on this magnetic layer. On this nonmagnetic layer, using a target made of Co-16Cr-16Pt-8B (Cr content: 16 at%, Pt content: 16 at%, B content: 8 at%, balance Co: remainder) The layer was formed to a thickness of 10 nm. Subsequently, a protective layer having a thickness of 4 nm was formed by a CVD method. Next, a lubricating layer made of perfluoropolyether was formed by a dipping method to obtain a magnetic recording medium.

Evaluation of polished glass substrate :
For the polished substrate obtained as described above (5 processed sheets for each example or comparative example), the surface polishing state was evaluated for the following four items, and the procedure was as follows: The following was followed.
(1) Polishing rate:
The polishing rate was expressed as a rate (μm / min) obtained by converting the weight difference of the substrate measured before and after the above polishing process into a change in thickness and dividing by the processing time.
(2) Surface roughness Ra:
It was measured with a laser light reflection / scattering measuring instrument. The number of measurement points was 10 points / surface, and the average value (Å) of those measurement values was displayed.
(3) Scratch rate:
The surface was observed using a MicroMAX measuring apparatus. Count the scratches generated during polishing as scratches, and calculate the scratch rate using the following formula:
Scratch occurrence rate (%) = (number of substrate surfaces with scratches / total number of evaluation surfaces) × 100
It was displayed in four levels according to the following criteria, divided by the magnitude of the value represented by the scratch occurrence rate (%).
0% ◎
0% to 5% ○
5% -14% △
15% or more ×
(4) Number of particles:
The number of particles adhering to the glass surface was measured using an optical microscope. From the photograph taken with the microscope, the number of particles having a diameter of 0.1 μm or more and 2.0 μm or less was counted using image analysis software. The number of particles (number) for each field of view (7 × 10 ⁻⁴ cm ² ) is totaled for 10 fields of view per surface, and the value is represented by the number per unit area (number / cm ² ). Classified and displayed in 4 levels according to the following criteria.
0-10 pieces / cm ² ◎
10-100 pieces / cm ² ○
100-300 pieces / cm ² △
300 / cm ² or more ×

Evaluation of perpendicular magnetic recording media :
Evaluation on the perpendicular magnetic recording medium (recording medium 10 surface for each example or comparative example) obtained as described above was performed on the following three items, and the procedure was as follows.
(1) SNR:
The measurement was performed using a read / write analyzer (machine name RWA1632) manufactured by GUZIK and a spin stand S1701MP. As the head, a head using a single pole magnetic pole for writing and a GMR element for the reproducing portion was used. The S / N ratio was measured at a recording density of 700 kFCI. The numerical value of SNR is compared with the SNRo of the reference comparative example in each table (indicated by “-” in the SNR column), and is divided into four levels according to the following criteria, which are divided by the difference (ΔSNR = SNR−SNRo). displayed.
+0.2 dB or more ◎
+0.1 dB to +0.2 dB ○
0 dB to +0.1 dB (no difference)
Less than 0 dB (minus) ×
(2) Product acceptance rate:
The percentage of products that passed as the final product was calculated as a pass rate (%) and displayed in three stages according to the following criteria.
100% ~ 90% ○
89% -80% △
Less than 80% ×
(3) Missing count:
For the missing count, substrate inspection was performed at a bit size of a recording density of 700 kFCI, an average value per one surface of the number of bits with an output of 80% or less was calculated, and displayed in three stages according to the following criteria.
2.1 (pieces / face) or less ○
2.1-2.5 (pieces / surface)
2.5 (pieces / plane) or more ×

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Tables 1 and 2 above.
(1) Polishing processing of amorphous glass and crystallized glass using aqueous diamond slurry having the composition described in Comparative Examples 2 and 4 not containing diethylenetriamine / adipic acid / 1.0EO in the production of a glass substrate for magnetic disk The polishing state of the substrate surface achieved by using an aqueous diamond slurry having the composition described in Comparative Examples 1 and 3 that does not contain not only diethylenetriamine / adipic acid / 1.0EO but also an alkaline etchant (TMAH or AH212) The polishing rate (μm / min) and the surface roughness Ra (Å) have been improved compared to the polishing state in the case of polishing, but the scratch generation rate (%) per polishing surface and the number of particles adhering to the glass surface ( Piece / cm ² ) is not improved at all, and cannot be used practically.
(2) On the other hand, substrate surface achieved by polishing of amorphous glass and crystallized glass using aqueous diamond slurry having the formulation of Examples 1-8 containing diethylenetriamine / adipic acid / 1.0EO As compared with the polishing state in the case of using an aqueous diamond slurry having the composition described in Comparative Examples 2 and 4 that does not contain the above-mentioned diethylenetriamine / adipic acid / 1.0EO, scratching per polished surface occurs. The rate (%) and the number of particles adhering to the glass surface (pieces / cm ² ) are not only sufficiently improved, but also the polishing rate (μm / min) and the surface roughness Ra (Å) are diethylenetriamine / adipic acid By adjusting the amount of /1.0 EO, it is further improved and is sufficiently practical.
(3) Moreover, in Example 4, it is completely the same except having used the condensate of the diethylenetriamine / adipic acid which is not performing EO addition instead of diethylenetriamine / adipic acid / 1.0EO, The description of the comparative example A description The polishing state of the substrate surface achieved by the polishing process of the amorphous glass using the aqueous diamond slurry having the composition is the above-mentioned Example 4 in which the EO adduct diethylenetriamine / adipic acid / 1.0EO is blended Completely different, no improvement in polishing state was observed in any of polishing speed, surface roughness, scratch generation rate, and number of particles, rather, this kind of polyalkylene polyamide compound was not blended at all. The polishing state is almost the same as in Example 2 and cannot be used practically.

Further, the following facts are found from the evaluation results of the perpendicular magnetic recording media shown in Tables 1 and 2 above.
(1) Polishing processing of amorphous glass and crystallized glass using aqueous diamond slurry having the composition described in Comparative Examples 2 and 4 not containing diethylenetriamine / adipic acid / 1.0EO in the production of a glass substrate for magnetic disk In the recording medium formed on the surface of the substrate obtained by the above, the water-based diamond having the composition described in Comparative Examples 1 and 3 not containing not only diethylenetriamine / adipic acid / 1.0EO but also an alkaline etchant (TMAH or AH212) Compared with the recording medium formed on the substrate surface when slurry is used, the SNR (dB) and the product pass rate can be improved, but the missing count (pieces / surface) has not been improved at all. Unusable.
(2) On the other hand, on the substrate surface obtained by polishing of amorphous glass and crystallized glass using an aqueous diamond slurry having the composition of Examples 1 to 8 containing diethylenetriamine / adipic acid / 1.0EO. In the formed recording medium,
Compared to the recording medium formed on the surface of the substrate using the aqueous diamond slurry having the composition described in Comparative Examples 2 and 4 that does not contain diethylenetriamine / adipic acid / 1.0EO, the missing count (pieces / piece In addition, the SNR (dB) and product acceptance rate have been further improved by adjusting the blending amount of diethylenetriamine / adipic acid / 1.0EO, which is sufficiently practical. is there.
(3) Moreover, in Example 4, it is completely the same except having used the condensate of the diethylenetriamine / adipic acid which is not performing EO addition instead of diethylenetriamine / adipic acid / 1.0EO, The description of the comparative example A description In the recording medium formed on the surface of the substrate obtained by polishing the amorphous glass using the aqueous diamond slurry having the composition, the aqueous diamond slurry containing the EO adduct diethylenetriamine / adipic acid / 1.0EO Unlike the recording medium of Example 4 formed on the surface of the substrate obtained using the above, no improvement was observed in any of SNR, product pass rate, and missing count. Formed when no such polyalkylene polyamide compound is blended, Be substantially equal to that of the recording medium Comparative Examples 2, it is practically unusable.

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Tables 3 to 5 above.
(1) In manufacturing a glass substrate for magnetic disk, it is achieved by polishing amorphous glass using an aqueous diamond slurry having the composition described in Comparative Examples 2, 5, and 6 not containing diethylenetriamine / adipic acid / 1.0EO. In the case of using an aqueous diamond slurry having a composition described in Comparative Example 1 that does not contain not only diethylenetriamine / adipic acid / 1.0EO but also an alkaline etching agent (NaOH, TMAH or AH212). Compared to the polished state of
Although the polishing rate (μm / min) and the surface roughness Ra (Å) can be improved, the scratch generation rate (%) per polished surface and the number of particles adhering to the glass surface (pieces / cm ² ) are completely improved. It is not available for practical use.
(2) On the other hand, the polished state of the substrate surface achieved by polishing amorphous glass using an aqueous diamond slurry having the formulation described in Examples 11 to 18 containing diethylenetriamine / adipic acid / 1.0EO is Compared with the polishing state when using an aqueous diamond slurry having the composition described in Comparative Examples 2, 5, and 6 that does not contain diethylenetriamine / adipic acid / 1.0EO, scratch generation rate per polished surface ( %) And the number of particles adhering to the glass surface (pieces / cm ² ) are sufficiently improved, the polishing rate (μm / min) and the surface roughness Ra (Å) are also included in the amount of the alkaline etching agent. By adjusting the value, it is further improved and is sufficiently practical.

Further, the following facts are found from the evaluation results of the perpendicular magnetic recording media shown in Tables 3 to 5 above.
(1) In manufacturing a glass substrate for a magnetic disk, obtained by polishing amorphous glass using an aqueous diamond slurry having the composition described in Comparative Examples 2, 5, and 6 containing no diethylenetriamine / adipic acid / 1.0EO. In the recording medium formed on the surface of the obtained substrate, an aqueous diamond slurry having a composition described in Comparative Example 1 not containing not only diethylenetriamine / adipic acid / 1.0EO but also an alkaline etching agent (NaOH, TMAH or AH212) is used. Compared with the recording medium formed on the surface of the substrate when used, the SNR (dB) and the product pass rate can be improved, but the missing count (pieces / surface) has not been improved at all, and is not practically used. Is possible.
(2) On the other hand, a record formed on the surface of a substrate obtained by polishing an amorphous glass using an aqueous diamond slurry having the composition described in Examples 11 to 18 containing diethylenetriamine / adipic acid / 1.0EO. In the medium
Compared to the recording medium formed on the surface of the substrate using the aqueous diamond slurry having the composition described in Comparative Examples 2, 5, and 6 that does not contain diethylenetriamine / adipic acid / 1.0EO, the missing count ( (Piece / surface) is not only sufficiently improved, but also the SNR (dB) and product pass rate are further improved by adjusting the blending amount of the alkaline etchant, and can be sufficiently practically used.

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Tables 6 to 8 above.
(1) When manufacturing a glass substrate for a magnetic disk, by polishing a crystallized glass using an aqueous diamond slurry having the composition described in Comparative Examples 7, 4 and 8 not containing diethylenetriamine / adipic acid / 1.0EO. The achieved polishing state of the substrate surface was obtained using an aqueous diamond slurry having the composition described in Comparative Example 3 not containing not only diethylenetriamine / adipic acid / 1.0EO but also an alkaline etchant (NaOH, TMAH or AH212). The polishing rate (μm / min) and the surface roughness Ra (Å) were improved compared to the polishing state in the case, but the scratch generation rate (%) per polishing surface and the number of particles adhering to the glass surface (number / Cm ² ) is not improved at all and cannot be used practically.
(2) On the other hand, the polished state of the substrate surface achieved by polishing of crystallized glass using an aqueous diamond slurry having the formulation of Examples 21 to 28 containing diethylenetriamine / adipic acid / 1.0EO Is a scratch generation rate per polished surface as compared with the polished state when using an aqueous diamond slurry having the composition described in Comparative Examples 7, 4 and 8, which does not contain diethylenetriamine / adipic acid / 1.0EO. (%) And the number of particles adhering to the glass surface (pieces / cm ² ) are not only sufficiently improved, but also the polishing rate (μm / min) and surface roughness Ra (Å) are blended with an alkali etching agent. By adjusting the amount, it is further improved and is sufficiently practical.

Further, the following facts are found from the evaluation results of the perpendicular magnetic recording media shown in Tables 6 to 8 above.
(1) When manufacturing a glass substrate for a magnetic disk, by polishing a crystallized glass using an aqueous diamond slurry having the composition described in Comparative Examples 7, 4 and 8 not containing diethylenetriamine / adipic acid / 1.0EO. In the recording medium formed on the surface of the obtained substrate, an aqueous diamond slurry having the composition described in Comparative Example 3 which does not contain not only diethylenetriamine / adipic acid / 1.0EO but also an alkaline etching agent (NaOH, TMAH or AH212) Compared with the recording medium formed on the surface of the substrate when using SNR, the SNR (dB) and the product acceptance rate have been improved, but the missing count (pieces / surface) has not been improved at all. Impossible.
(2) On the other hand, formed on the surface of a substrate obtained by polishing of crystallized glass using an aqueous diamond slurry having the composition described in Examples 21 to 28 containing diethylenetriamine / adipic acid / 1.0EO. The recording medium does not contain the above-mentioned diethylenetriamine / adipic acid / 1.0EO, and has the composition described in Comparative Examples 7, 4 and 8, compared with the recording medium formed on the substrate surface when an aqueous diamond slurry is used. And
Not only the missing count (pieces / surface) has been sufficiently improved, but also the SNR (dB) and product acceptance rate have been further improved by adjusting the blending amount of the alkaline etchant, which is sufficiently practical. is there.

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Table-9 above.
When producing a glass substrate for a magnetic disk, instead of diethylenetriamine / adipic acid / 1.0EO in Example 3 of Table-1, alkylene oxides of polycondensates of various dicarboxylic acids and polyamines shown in Table-9 above The polishing state of the substrate surface achieved by polishing an amorphous glass with an aqueous diamond slurry having the formulation of Examples 31-39 containing an adduct is diethylenetriamine / adipic acid / 1.0 EO. Compared to the polished state when using an aqueous diamond slurry having the composition described in Comparative Example 2 not contained, the scratch generation rate (%) per polished surface and the number of particles adhering to the glass surface (pieces / cm ² ) Is sufficiently improved, the polishing rate (μm / min) and the surface roughness Ra (粗) Is also improved and sufficiently practical, as in the case of Example 3 in Table-1.

  Further, the following facts are found from the evaluation results of the perpendicular magnetic recording medium shown in Table 9 above. When producing a glass substrate for a magnetic disk, instead of diethylenetriamine / adipic acid / 1.0EO in Example 3 of Table-1, alkylene oxides of polycondensates of various dicarboxylic acids and polyamines shown in Table-9 above In a recording medium formed on the surface of a substrate obtained by polishing an amorphous glass using an aqueous diamond slurry having the formulation described in Examples 31 to 39 containing an adduct, diethylenetriamine / adipic acid / 1 Compared with the recording medium formed on the surface of the substrate in the case of using the aqueous diamond slurry having the composition described in Comparative Example 2 that does not contain 0.0EO, the missing count (pieces / surface) is sufficiently improved. In addition, SNR (dB) and product acceptance rate are also improved and practical enough And are the same as in Example 3 of Table 1.

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Table-10 above.
In the production of the glass substrate for magnetic disk, the formulation described in Examples 41 to 47 containing various amphoteric or anionic surfactants shown in Table 10 above instead of CNS in Example 3 of Table 1 was used. An aqueous diamond slurry having a composition according to Comparative Example 2, wherein the polishing state of the substrate surface is achieved by polishing the amorphous glass using the aqueous diamond slurry, and the polishing state of the substrate surface does not contain diethylenetriamine / adipic acid / 1.0EO Compared with the polishing state when using, the scratch generation rate (%) per polished surface and the number of particles adhering to the glass surface (pieces / cm ² ) are not only sufficiently improved, but also the polishing rate (μm / Min) and surface roughness Ra (Å) are also improved and sufficiently practical, as in the case of Example 3 in Table 1. It is the same.

  Further, the following facts are found from the evaluation results of the perpendicular magnetic recording medium shown in Table-10. In the production of the glass substrate for magnetic disk, the formulation described in Examples 41 to 47 containing various amphoteric or anionic surfactants shown in Table 10 above instead of CNS in Example 3 of Table 1 was used. The recording medium formed on the surface of the substrate obtained by polishing an amorphous glass using an aqueous diamond slurry has a formulation described in Comparative Example 2 that does not contain diethylenetriamine / adipic acid / 1.0EO. Compared to the recording medium formed on the substrate surface using an aqueous diamond slurry, not only the missing count (pieces / surface) is sufficiently improved, but also the SNR (dB) and product pass rate are improved. Therefore, the fact that it is sufficiently practical is the same as in the case of Example 3 in Table-1.

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Table-11 above.
When manufacturing the glass substrate for magnetic disk, instead of DEA (5 parts by weight) + TEA (10 parts by weight) in Example 3 of Table-1, various alkaline polishing agents (MEA, DEA and The polishing state of the substrate surface achieved by polishing amorphous glass with an aqueous diamond slurry having the formulation of Examples 51-55, containing TEA) in varying amounts, is diethylenetriamine / adipic acid Compared to the polished state when using an aqueous diamond slurry having a composition described in Comparative Example 2 that does not contain /1.0 EO, the scratch generation rate (%) per polished surface and the number of particles attached to the glass surface ( pieces / cm ²⁾ is not only sufficiently improved, the polishing rate ([mu] m / min) and the surface roughness Ra (Å) As in the case of Example 3 in Table 1, it is improved and sufficiently practical.

  In addition, the following facts are found from the evaluation results of the perpendicular magnetic recording medium shown in Table-11 above. When manufacturing the glass substrate for magnetic disk, instead of DEA (5 parts by weight) + TEA (10 parts by weight) in Example 3 of Table-1, various alkaline polishing agents (MEA, DEA and In a recording medium formed on the surface of a substrate obtained by polishing an amorphous glass using an aqueous diamond slurry having a composition as described in Examples 51 to 55 containing TEA) in a different amount ratio, diethylenetriamine Compared with the recording medium formed on the substrate surface in the case of using the aqueous diamond slurry having the composition described in Comparative Example 2 that does not contain / adipic acid / 1.0EO, the missing count (pieces / surface) is sufficiently high Not only has it been improved, but SNR (dB) and product acceptance rate have also been improved and are fully practical. Is the same as in Example 3 of Table 1.

The following facts are found from the evaluation results of the polishing state of the substrate surface shown in Table-12 above.
Unlike the various aqueous diamond slurries shown in the Examples of Tables 1-11, it does not contain an alkaline etchant but contains diethylenetriamine / adipic acid / 1.0 EO. The polishing state of the substrate surface achieved by polishing an amorphous glass using an aqueous diamond slurry having the formulation described in Examples 61 to 64 specified in Table-12 is diethylenetriamine / adipic acid / 1. Compared with the polished state when using an aqueous diamond slurry having a composition described in Comparative Example 9 and containing no 0.0EO, the scratch generation rate (%) per polished surface and the number of particles adhering to the glass surface (number / piece cm ² ) is sufficiently improved, the polishing rate (μm / min) and the surface roughness Ra (Å) are also improved by adjusting the blending amount of diethylenetriamine / adipic acid / 1.0EO. And is sufficiently practical.

Further, the following facts are found from the evaluation results of the perpendicular magnetic recording medium shown in Table-12 above. Unlike the various aqueous diamond slurries shown in the Examples of Tables 1-11, it does not contain an alkaline etchant but contains diethylenetriamine / adipic acid / 1.0 EO. In a recording medium formed on the surface of a substrate obtained by polishing an amorphous glass using an aqueous diamond slurry having the formulation of Examples 61 to 64 specified in Table-12, diethylenetriamine / adipic acid / Scratch ratio (%) per polished surface and glass surface as compared with the recording medium formed on the substrate surface when using an aqueous diamond slurry having a composition described in Comparative Example 9, which does not contain EO Not only is the number of particles (particles / cm ² ) adhering to the surface sufficiently improved, but also the polishing rate (μm / min) and the surface roughness Ra (Å) are mixed with diethylenetriamine / adipic acid / 1.0EO. By adjusting the value, it is improved and is sufficiently practical.

[Application Example 2] Production of glass substrate for TFT panel <Examples 70 to 79 and Comparative examples 70 to 75>

Polishing :
Polishing was performed on the surface of a 5 cm square (area 25 cm ² ) non-alkali glass substrate (thickness 1 mm).
Polishing was performed using a 4-way double-side polishing machine. At that time, as a polishing liquid, 10 parts by weight of cerium oxide abrasive grains having an average particle diameter of 1.2 μm, 20 parts by weight of a polishing liquid composition having a composition described in each Example or Comparative Example in Table 13, and ion-exchanged water ( An aqueous cerium oxide slurry blended with 70 parts by weight of a specific resistance of 1 MΩ · cm) was used, and a foamed polyurethane pad (Rodes, grade name LP-77) was used as a polishing pad.
The polishing conditions were such that the rotation speed of the surface plate holding the substrate was 60 rpm, and the amount of slurry supplied to the double-side polishing apparatus was 50 ml / min. The processing pressure (pad pressing force) was 150 gf / cm ² and the processing time was 30 minutes. Thus, the glass substrate which gave the polishing process to the surface was obtained.

Cleaning and evaluation :
The polished glass substrate is washed with running water so that no objects touch the polished surface after polishing, and then applied with an ultrasonic cleaner in a Class 1000 clean room. While rinsing with ion-exchanged water (specific resistance 1 MΩ · cm) three times. After rinsing, it was dried by blowing compressed nitrogen.
The thus obtained dried glass substrate for TFT panel (5 processed sheets for each example or comparative example) was evaluated for the polishing state (similar to application example 1). The results are as shown in Table-13.

The following facts are found from the evaluation results shown in Table-13 above.
(1) When producing a glass substrate for a TFT panel, an alkylene oxide adduct of a polycondensate of a dicarboxylic acid such as diethylenetriamine / adipic acid / 1.0EO and a polyamine (hereinafter referred to as “diethylenetriamine / adipic acid / 1.0EO, etc.”) The polishing state of the substrate surface achieved by an alkali-free glass polishing process using an aqueous cerium oxide slurry having the formulation described in Examples 70 to 79, containing diethylenetriamine / adipic acid / 1. Any diethylenetriamine / adipic acid as compared to the polished state when an aqueous cerium oxide slurry is used, which does not contain 0EO or the like, but has the formulation described in Comparative Examples 70 to 75, which has other formulation components and amounts in common /1.0 EO, etc., the scratch rate (%) and the glass surface Wearing the number of particles (number / cm ²⁾ is significantly improved, moreover, this success is possible while maintaining a polishing rate ([mu] m / min) and the surface roughness Ra (Å) in a practical range. Moreover, the polishing rate (μm / min) and the surface roughness Ra (Å) are also improved by adjusting the blending amount of diethylenetriamine / adipic acid / 1.0EO.
(2) On the other hand, the polishing state when using an aqueous cerium oxide slurry having the composition described in Comparative Examples 70 to 75 not containing diethylenetriamine / adipic acid / 1.0 EO, etc. is particularly a scratch occurrence rate (%) and glass. In terms of the number of particles attached to the surface (pieces / cm ² ), it is not suitable for practical use, and as in Comparative Examples 71 and 75, there may be some improvement due to the incorporation of the water-soluble polymer, but still, It is insufficient to make it practically usable.
(3) In Example 74, Comparative Example B is identical except that instead of triethylenetetramine / adipic acid / EO, a condensate of triethylenetetramine / adipic acid without EO addition was used. The implementation described above, wherein the polishing state of the substrate surface achieved by polishing processing of an alkali-free glass using an aqueous cerium oxide slurry having the formulation described above was formulated with triethylenetetramine / adipic acid / EO as an EO adduct Unlike Example 74, no improvement in the polishing state was observed in any of polishing speed, surface roughness, scratch generation rate, and number of particles. Rather, this kind of polyalkylene polyamide compound was blended at all. The polishing state is almost the same as that of Comparative Example 72, and is practically unusable.

Application Example 3 Production of White Plate Glass Substrate for Optical Material <Examples 80 to 89 and Comparative Examples 80 to 85>

Polishing :
Polishing was performed on the surface of a white glass substrate (thickness: 5 mm) having a size of 5 cm square (area: 25 cm ² ).
The polishing process was performed using a single-side polishing apparatus. At that time, as a polishing liquid, 10 parts by weight of colloidal silica abrasive grains having an average particle diameter of 0.006 μm, 20 parts by weight of a polishing liquid composition having a composition described in each Example or Comparative Example in Table 14, and ion-exchanged water ( An aqueous colloidal silica slurry blended with 70 parts by weight of a specific resistance of 1 MΩ · cm) was used, and a urethane resin-impregnated polyester nonwoven fabric (manufactured by Rodel, grade name SUBA400) was used as an abrasive cloth.
The polishing conditions were such that the rotation speed of the surface plate holding the substrate was 150 rpm, and the amount of slurry supplied to the polishing apparatus was 30 ml / min. The processing pressure (non-woven fabric pressing force) was 200 gf / cm ² and the processing time was 10 minutes. Thus, the glass substrate which gave the polishing process to the surface was obtained.

Cleaning and evaluation :
The glass substrate subjected to the polishing process was washed with running water with tap water, rinsed with ion-exchanged water, and sprayed with compressed nitrogen, and dried, as in Application Example 2.
The thus-obtained white plate glass substrate for optical material (5 processed sheets for each example or comparative example) after drying was evaluated for the polishing state (similar to Application Example 2). The results are as shown in Table-14.

The following facts are found from the evaluation results shown in Table-14 above.
(1) When producing a white glass substrate for an optical material, an alkylene oxide adduct of a polycondensate of a dicarboxylic acid such as diethylenetriamine / adipic acid / 1.0EO and a polyamine (hereinafter referred to as “diethylenetriamine / adipic acid / 1.0EO, etc.) The polishing state of the substrate surface achieved by polishing white glass using an aqueous colloidal silica slurry having the formulation described in Examples 80-89 containing: diethylenetriamine / adipic acid / 1. Compared to the polishing state when an aqueous colloidal silica slurry is used, which does not contain 0EO, etc., but has other blending components and amounts in common, and has the blending described in Comparative Examples 80-85,
In any diethylenetriamine / adipic acid / 1.0EO, etc., the scratch generation rate (%) and the number of particles adhering to the glass surface (number / cm ² ) are remarkably improved, and this achievement is achieved by the polishing rate (μm / min). ) And surface roughness Ra (Å) can be maintained within a practical range. Moreover, the polishing rate (μm / min) and the surface roughness Ra (Å) are also improved by adjusting the blending amount of diethylenetriamine / adipic acid / 1.0EO.
(2) On the other hand, the polishing state when using an aqueous colloidal silica slurry having the formulation of Comparative Examples 80 to 85 which does not contain diethylenetriamine / adipic acid / 1.0 EO, etc. In terms of the number of particles attached to the surface (pieces / cm ² ), it is not suitable for practical use, and as in Comparative Examples 81 and 85, a slight improvement may be observed depending on the formulation of the water-soluble polymer. It is insufficient to make it practically usable.
(3) Also, in Example 84, Comparative Example C was exactly the same except that instead of triethylenetetramine / adipic acid / EO, a condensate of triethylenetetramine / adipic acid without EO addition was used. Example above, where the polishing state of the substrate surface achieved by polishing the white glass using an aqueous colloidal silica slurry having the composition described above was formulated with triethylenetetramine / adipic acid / EO which is an EO adduct Unlike 84, no improvement in the polishing state was observed in any of polishing speed, surface roughness, scratch generation rate, and number of particles. Rather, this kind of polyalkylene polyamide compound was blended at all. The polishing state is almost equivalent to that of Comparative Example 82, and cannot be used practically.

Application Example 4 Production of Soda Lime Glass Substrate for General Purpose Plate Glass <Examples 90 to 99 and Comparative Examples 90 to 95>

Polishing :
Polishing was performed on the surface of a 5 cm square (area 25 cm ² ) soda lime glass substrate (thickness 5 mm).
Polishing was performed using a 4-way double-side polishing machine. At that time, as a polishing liquid, 10 parts by weight of colloidal silica abrasive grains having an average particle diameter of 0.008 μm, 20 parts by weight of a polishing liquid composition having a composition described in each Example or Comparative Example in Table 15, and ion-exchanged water ( An aqueous colloidal silica slurry blended with 70 parts by weight of a specific resistance of 1 MΩ · cm) was used, and a urethane resin-impregnated polyester nonwoven fabric (manufactured by Rodel, grade name SUBA400) was used as an abrasive cloth.
The polishing conditions were such that the rotation speed of the surface plate holding the substrate was 60 rpm, and the amount of slurry supplied to the polishing apparatus was 100 ml / min. The processing pressure (nonwoven fabric pressing force) was 150 gf / cm ² and the processing time was 10 minutes. Thus, the glass substrate which gave the polishing process to the surface was obtained.

Cleaning and evaluation :
The glass substrate subjected to the polishing process was washed with running water with tap water, rinsed with ion-exchanged water, and sprayed with compressed nitrogen, and dried, as in Application Example 2.
The soda-lime glass substrate for general-purpose plate glass after drying thus obtained (5 processed sheets for each example or comparative example) was evaluated for the polishing state (similar to Application Example 2). . The results are as shown in Table-15.

The following facts are found from the evaluation results shown in Table-15 above.
(1) When producing a soda-lime glass substrate for general-purpose flat glass, an alkylene oxide adduct of a polycondensate of a dicarboxylic acid such as diethylenetriamine / adipic acid / 1.0EO and a polyamine (hereinafter referred to as “diethylenetriamine / adipic acid / 1.0EO”). The polishing state of the substrate surface achieved by polishing soda lime glass with an aqueous colloidal silica slurry having the formulation described in Examples 90-99 containing: diethylenetriamine / adipic acid / Compared to the polishing state when using an aqueous colloidal silica slurry, which does not contain 1.0EO or the like, but has other blending components and amounts in common and has the blending of Comparative Examples 90 to 95, any diethylenetriamine / Scratch occurrence rate even in adipic acid / 1.0EO %) And the number of particles adhering to the glass surface (pieces / cm ²⁾ is significantly improved, moreover, possible with this achieved maintaining the polishing rate ([mu] m / min) and the surface roughness Ra (Å) in a practical range is there. Moreover, the polishing rate (μm / min) and the surface roughness Ra (Å) are also improved by adjusting the blending amount of diethylenetriamine / adipic acid / 1.0EO.
(2) On the other hand, the polishing state when using an aqueous colloidal silica slurry having the formulation of Comparative Examples 90 to 95 which does not contain diethylenetriamine / adipic acid / 1.0 EO, etc. In terms of the number of particles attached to the surface (pieces / cm ² ), it is not suitable for practical use, and as in Comparative Examples 91 and 95, a slight improvement may be observed depending on the formulation of the water-soluble polymer. It is insufficient to make it practically usable.
(3) Further, in Example 94, Comparative Example D was identical except that instead of triethylenetetramine / adipic acid / EO, a condensate of triethylenetetramine / adipic acid without EO addition was used. The polished state of the substrate surface, achieved by polishing soda lime glass with an aqueous colloidal silica slurry having the described formulation,
In contrast to Example 94, in which triethylenetetramine / adipic acid / EO, which is an EO adduct, was blended, the polishing state was not affected in any of polishing speed, surface roughness, scratch generation rate, and number of particles. No improvement was observed at all. Rather, the polishing state was almost the same as that of Comparative Example 92, in which this type of polyalkylene polyamide compound was not blended at all, and was not practically usable.

Use:
For manufacturing electronic circuits such as glass substrates for recording media such as magnetic disks and optical disks, glass materials for optical applications such as optical lenses, glass substrates for liquid crystals, color filters for liquid crystal televisions, glass substrates for plasma displays, glass substrates for LSI photomasks, etc. Quartz glass for photomasks, crystal, solar cell panels, various lenses and filters for optical components, optical fibers.

Claims (11)

  A composition for glass polishing processing, comprising an alkylene oxide adduct of a polycondensate of a polyalkylene polyamine and a C2-C12 alkylene or arylene dicarboxylic acid.   The dicarboxylic acid is succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,1-dimethyl-1,3-propanedicarboxylic acid, 1-methyl-1 -At least one selected from ethyl-1,3-propanedicarboxylic acid, terephthalic acid and isophthalic acid, and the polyalkylenepolyamine is diethylenetriamine and triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylenetriamine 2. The glass polishing composition according to claim 1, wherein the composition is at least one selected from propylene triamine, tripropylene tetramine, diisopropylene triamine, dibutylene triamine, and diisobutylene triamine.   The glass polishing composition according to claim 1 or 2, wherein the alkylene oxide is at least one selected from ethylene oxide, propylene oxide, and butylene oxide.   The composition for glass polishing processing according to any one of claims 1 to 3, wherein the composition contains a water-soluble polymer having a carboxylic acid group, a carboxylic acid group, and / or a carboxylic acid amide compound group. object.   The said composition contains surfactant, The composition for glass polishing processing as described in any one of Claims 1-4 characterized by the above-mentioned.   The said composition contains an alkali etching agent and / or amines, The composition for glass polishing processing as described in any one of Claims 1-5 characterized by the above-mentioned.   The said composition contains an abrasive grain and a cooling agent, The composition for glass polishing processing as described in any one of Claims 1-6 characterized by the above-mentioned.   A glass polishing method comprising: polishing a surface of a glass material by pressing a cloth material impregnated with the composition for glass polishing processing according to claim 7 for a predetermined time.   When the composition contains an alkaline substance, the polishing process is performed as soon as possible after obtaining a composition containing an alkylene oxide adduct of a polycondensate of the dicarboxylic acid and the polyalkylene polyamine. The glass polishing method according to claim 8, wherein the glass polishing method is performed.   10. The glass polishing method according to claim 8, wherein the glass material is a glass magnetic disk substrate.   The glass polishing processing method according to claim 10, wherein the abrasive grains in the composition are diamond abrasive grains.