CN106661428A

CN106661428A - Method for producing polishing slurry, polishing abrasive grains, polishing slurry, and method for producing glass substrate

Info

Publication number: CN106661428A
Application number: CN201580040539.2A
Authority: CN
Inventors: 田村健; 玉置将德; 饭泉京介
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2014-07-31
Filing date: 2015-07-31
Publication date: 2017-05-10
Anticipated expiration: 2035-07-31
Also published as: SG10202102010YA; MY182259A; JP6357536B2; SG11201610743PA; WO2016017819A1; JPWO2016017819A1; CN106661428B

Abstract

Provided are a method for producing a polishing slurry, polishing abrasive grains, and a polishing slurry with which polishing rate can be improved and the occurrence of damage to a glass substrate can be suppressed. Further provided is a method for producing a glass substrate using such a polishing slurry and polishing abrasive grains. This method for producing a polishing slurry including polishing abrasive grains is used in the polishing treatment of a glass substrate and is characterized by comprising: an addition process in which a binder is added to a raw material slurry that includes raw material abrasive grains which constitute the raw material for the polishing abrasive grains; a drying process in which the raw material slurry which includes the binder is dried to produce a mass of raw material abrasive grains containing the binder; and a sintering process in which the mass of raw material abrasive grains is sintered to produce an aggregate of raw material abrasive grains containing the binder.

Description

The manufacture method of ground slurry, grinding abrasive particle, ground slurry and glass substrate Manufacture method

Technical field

The present invention relates to the manufacturer of the manufacture method of ground slurry, grinding abrasive particle, ground slurry and glass substrate Method.

Background technology

Glass substrate used in mask substrate for disk, photomask or as its substrate etc., generally using with After cerium oxide (ceria) is ground for the grinding abrasive particle (hereinafter referred to cerium based abrasive material) of main component, using glue State silicon dioxide is polished grinding.Wherein, cerium based abrasive material is due to the oxide comprising expensive rare earth element, thus Reclaimed after use and recycled.

With regard to the renovation process for cerium based abrasive material to be recycled, for example, by from used ground slurry Solid-liquid separation is carried out after middle removal foreign body, and its solid constituent is dried, is fired, is crushed, and then carry out filtration carrying out. As the renovation process of existing grinding-material, it is known that：In order that the grinding rate of lowered used grinding-material connects The grinding rate of nearly untapped grinding-material, such as implement acid treatment before solid-liquid separation is carried out to used ground slurry (for example, patent documentation 1).

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 2007-276055 publications

The content of the invention

Invent problem to be solved

With regard to cerium based abrasive material, it is known that：Combined in crystal boundary by firing, in actual grinding as granule The particle diameter for playing a role becomes big, so as to grinding rate raising.But, carry out again even with the method using patent documentation 1 Give birth to and grinding rate is recovered to the grinding-material of the level Jie Jin untapped grinding-material, the adhesion of grain boundaries is not also filled Point, thus be easily broken when reusing and diameter diminishes, grinding rate is reduced sometimes.In addition we know, if grinding material in use Material is broken and granules are decomposed in a large number in generation, then the particle size distribution of grinding-material becomes uneven, suffered by the big grinding-material of particle diameter The load for arriving becomes big, and the load local for thus applying to glass substrate becomes big, and glass substrate easily produces grinding flaw.

It is an object of the invention to provide a kind of improved in grinding rate while glass substrate can also be suppressed The manufacture method of the ground slurry of the generation of damage, grinding abrasive particle and ground slurry.In addition, it is an object of the invention to provide making With such ground slurry, the manufacture method of the glass substrate of grinding abrasive particle.

Means for solving the problems

The present invention the 1st mode be a kind of manufacture method of ground slurry, its be comprising for glass substrate grinding at The manufacture method of the ground slurry of the grinding abrasive particle of reason, it is characterised in that the manufacture method possesses：

Add in the raw material slurry of the raw material abrasive particle comprising the raw material as above-mentioned grinding abrasive particle at the addition of binding agent Reason；

It is dried the raw material slurry comprising above-mentioned binding agent and makes the dry of the block of the raw material abrasive particle containing above-mentioned binding agent Dry process；With

The block of above-mentioned raw materials abrasive particle is fired and the burning of the aggregation of the raw material abrasive particle containing above-mentioned binding agent is made System process.

Above-mentioned binding agent preferably comprises silica dioxide granule.

The mean diameter of above-mentioned binding agent is preferably 3nm～20nm.

The mean diameter of above-mentioned raw materials abrasive particle is preferably 0.3 μm～2 μm.

Preferably, it is further equipped with the aggregation of above-mentioned raw materials abrasive particle is broken and makes the broken of above-mentioned grinding abrasive particle Process,

The mean diameter of the grinding abrasive particle made by above-mentioned break process is 0.5 μm～10 μm.

Preferably, in above-mentioned addition process, further add for suppressing the viscous of the mutual coagulation of above-mentioned binding agent Knot agent aggregation inhibitor,

In above-mentioned dried, above-mentioned binding agent is distributed in above-mentioned by above-mentioned binding agent aggregation inhibitor In the block of raw material abrasive particle.

Preferably, in above-mentioned firing process, it is fired by the block to above-mentioned raw materials abrasive particle and makes above-mentioned bonding At least a portion of agent aggregation inhibitor disappears.

Above-mentioned binding agent aggregation inhibitor is preferably polysaccharide, water is more preferably dissolved in by heating or gelation occurs Polysaccharide.

It is preferred that the temperature below 800 DEG C carries out above-mentioned firing.

In above-mentioned dried, preferably by being spray-dried the raw material slurry drying for making to include above-mentioned binding agent.

Above-mentioned raw materials slurry preferably is contained in the cerium oxide particles used in the milled processed of glass substrate.

The another way of above-mentioned 1st mode is a kind of grinding abrasive particle, and it is used in the milled processed of glass substrate Grinding abrasive particle, it is characterised in that

In the grinding abrasive particle, silica dioxide granule as binding agent be present in ceria or zirconic granule it Between.

The meansigma methodss of the comprcssive strength that above-mentioned grinding abrasive particle is preferably determined according to JIS R1639-5 are 0.1MPa～20MPa.

The another way of above-mentioned 1st mode is a kind of ground slurry, it is characterised in that

It includes the grinding abrasive particle of above-mentioned another way.

The another way of above-mentioned 1st mode is a kind of manufacture method of glass substrate, it is characterised in that

The ground slurry that made using the manufacture method by above-mentioned ground slurry, above-mentioned grinding abrasive particle or above-mentioned grind Defibrination material and the surface of glass substrate is ground.

The present invention the 2nd mode be a kind of manufacture method of ground slurry, its be comprising for glass substrate grinding at The manufacture method of the ground slurry of the grinding abrasive particle of reason, it is characterised in that the manufacture method possesses：

Add in the raw material slurry of the raw material abrasive particle comprising the raw material as above-mentioned grinding abrasive particle at the addition of pore creating material Reason；

It is dried the raw material slurry comprising above-mentioned pore creating material and makes the dry of the block of the raw material abrasive particle containing above-mentioned pore creating material Dry process；With

The block of above-mentioned raw materials abrasive particle is fired and makes at least a portion of above-mentioned pore creating material disappear, so as to make above-mentioned The interstitial firing in part of the block of the above-mentioned raw materials abrasive particle that hole agent is located at is processed.

Above-mentioned pore creating material is preferably polysaccharide, water is more preferably dissolved in by heating or the polysaccharide of gelation occurs.

In the block of above-mentioned raw materials abrasive particle, the mean diameter of above-mentioned pore creating material is preferably 3 μm～20 μm.

In above-mentioned dried, preferably by being spray-dried the raw material slurry drying for making to include above-mentioned pore creating material.

Preferably, in above-mentioned addition process, further addition is configured at the binding agent on the surface of above-mentioned raw materials abrasive particle,

In above-mentioned dried, above-mentioned binding agent is distributed in above-mentioned raw materials abrasive particle by above-mentioned pore creating material In block.

The another way of above-mentioned 2nd mode is a kind of manufacture method of glass substrate, it is characterised in that

The surface of glass substrate is ground using the ground slurry of the manufacture method making by above-mentioned ground slurry Mill.

The effect of invention

The manufacture method of ground slurry of the invention, the raw material abrasive particle of the aggregation of raw material abrasive particle is each other by bonding Agent is combined, and the intensity of crystal boundary is improved, thus the grinding abrasive particle made by the aggregation of the raw material abrasive particle is difficult to crush in use. Therefore, it is suppressed that make glass substrate produce damage because crushing the decomposition granule for generating.In addition, grinding abrasive particle is by raw material abrasive particle By binding agent engages, particle diameter becomes made by big material, and thus grinding rate is improved, simultaneously because be difficult to it is broken and can be with Maintain high grinding rate.

The grinding abrasive particle of the present invention and ground slurry are included in surface configuration and have the ceria of binding agent or zirconic Granule, compared with the grinding abrasive particle without binding agent, grinding abrasive particle is difficult to crush, it is suppressed that the reduction of grinding rate.

The manufacture method of glass substrate of the invention, can be ground, together with high grinding rate to glass substrate When can obtain damaging few glass substrate.

Description of the drawings

In Fig. 1, (a) of Fig. 1 is the figure of the block of the raw material abrasive particle for illustrating the 1st and the 2nd embodiment.(b) of Fig. 1 is to illustrate The figure of the aggregation of the raw material abrasive particle of the 1st and the 2nd embodiment.

Fig. 2 is to conceptually illustrate the grinding made by the manufacture method by the ground slurry of the 1st and the 2nd embodiment The figure of abrasive particle.

Specific embodiment

Below, to the ground slurry of the present invention manufacture method, grinding abrasive particle, the manufacture of ground slurry and glass substrate Method is described in detail.

<1st embodiment>

(manufacture method of ground slurry)

1st embodiment of the present invention is illustrated.

The manufacture method of the ground slurry of the 1st embodiment is the grinding abrasive particle comprising the milled processed for glass substrate Ground slurry manufacture method, the manufacture method possess addition process, dried, fire process each process.In addition In process, in the raw material slurry of the raw material abrasive particle comprising the raw material as grinding abrasive particle binding agent is added.In dried, It is dried the raw material slurry comprising binding agent and makes the block of the raw material abrasive particle containing binding agent.In firing is processed, to raw material The block of abrasive particle is fired and makes the aggregation of the raw material abrasive particle containing binding agent.

Raw material slurry is as disperse medium and obtained from making raw material abrasive particle scatter using water.

The block of raw material abrasive particle refers to the raw material agglomeration of abrasive particles of more than 2 and the block that formed, and the block of raw material abrasive particle has The binding agent aggregation inhibitor of raw material abrasive particle, binding agent and optional mixture.The block of raw material abrasive particle for example has following forms：In a large number Raw material abrasive particle be attached to the binding agent aggregation inhibitor comprising moisture to cover its surface, be distributed between raw material abrasive particle There is binding agent.

The aggregation of raw material abrasive particle is referred to and (for example, passed through by least one of binding agent in the block of raw material abrasive particle Binding agent melts and solidifies) and make the material that raw material abrasive particle is engaged with each other.The aggregation of raw material abrasive particle has raw material abrasive particle And binding agent.The aggregation of raw material abrasive particle preferably has hole (space), and the hole (space) is included in block by raw material abrasive particle At least one of binding agent aggregation inhibitor disappear and formed.

Furthermore it is possible to by after dried, the state of firing before processing be referred to as the block of raw material abrasive particle, firing can be processed Afterwards, the state before break process is referred to as the aggregation of raw material abrasive particle.

It should be noted that being not particularly limited to the purposes of glass substrate, for example, liquid crystal indicator etc. is various aobvious The panel of showing device；Photomask or the mask substrate as its substrate；The disk of HDD device.At the grinding of glass substrate Reason for example used in the manufacture method of glass substrate described later double-side polishing apparatus carrying out.

It is not particularly limited to grinding abrasive particle, also glass substrate is carried out using chemical action from addition to mechanism Set out in terms of grinding, preferably use cerium based abrasive material or the zirconium oxide system with zirconium oxide (zirconia) as main component Grinding-material.Ground slurry is that, as disperse medium and obtained from making grinding abrasive particle scatter, grinding abrasive particle is in grinding using water Use as free abrasive in process.Ground slurry can also for example include phosphate in addition to comprising grinding abrasive particle, water Other compositions such as dispersant.The concentration of the grinding abrasive particle in ground slurry is not particularly limited, for example, 1 mass %～30 matter Amount %, preferably 3 mass %～20 mass %.

A () addition is processed

Raw material abrasive particle is the original of the grinding abrasive particle included in ground slurry made by the method by the 1st embodiment Material, in the case of the grinding abrasive particle included in used ground slurry is stated after use as raw material abrasive particle, raw material abrasive particle is Refer to the used grinding abrasive particle.The mean diameter of raw material abrasive particle is preferably 0.3 μm～2 μm.By using this mean diameter Raw material abrasive particle, the grinding abrasive particle of the size of the milled processed for being adapted for glass substrate can be made.It is known that being in The raw material abrasive particle of mean diameter smaller (such as 0.3 μm～be less than 0.5 μm) in the raw material abrasive particle of 0.3 μm～2.0 μm of scope Be difficult to be recovered in solid-liquid separation, even and if can reclaim, the raw material abrasive particle regenerated using existing method is at grinding Particle diameter also can diminish in reason, and grinding rate is reduced, or glass substrate can produce damage.According to the making side of the 1st embodiment Method, makes as described later the grinding abrasive particle of appropriate hardness (comprcssive strength), is thus suitable for the smaller material of mean diameter Ground slurry is made as raw material abrasive particle.It should be noted that raw material abrasive particle be several to tens primary particle coagulations and Into second particle, the mean diameter of raw material abrasive particle refers to the mean diameter of second particle.It should be noted that grinding in actual What granule during mill as 1 grinding abrasive particle played a role is second particle.In addition, in this specification, during mean diameter is referred to Value particle diameter (d50).D50 be for example based on Measurement of particle size distribution by laser diffraction accumulation particle diameter from microgranule side with tire out 50% corresponding particle diameter of product.

Raw material slurry can be untapped material, or used ground slurry.In this specification, used Refer to situation about at least having used in the milled processed of glass substrate once.Grind being made using used ground slurry In the case of slurry, used grinding abrasive particle recirculation can be suppressed the cost of ground slurry.Need explanation It is, in this specification, by the use of used ground slurry as in the case of raw material slurry, can grinding present embodiment The manufacture method of defibrination material is referred to as the renovation process of used ground slurry, includes with cerium oxide particles in the ground slurry In the case of cerium based abrasive material for main component, the renovation process of used ceria sizing agent is properly termed as.

In addition, the used ground slurry for being used as raw material abrasive particle can also be by using cross ground slurry again The ground slurry that generation method is regenerated.In this case, by the way that used ground slurry repeated regeneration is used, will can grind The cost of slurry suppresses lower.

Binding agent is engaged with each other raw material abrasive particle by melting when firing and processing, such that it is able to improve the strong of crystal boundary Degree.It should be noted that crystal boundary refers to the border between adjacent raw material abrasive particle.Thus, the aggregate particle size (grinding of abrasive particle is ground The particle diameter of the granule that the granule of 1 grinding abrasive particle of Shi Zuowei plays a role) become big, so as to the grinding rate for grinding abrasive particle is improved, It is difficult to crush in milled processed simultaneously, high grinding rate can be maintained.On the other hand, it is joined directly to each other with raw material abrasive particle Situation is compared, in raw material abrasive particle each other by binding agent engages in the case of, the intensity of crystal boundary will not be too strong, thus can suppress to grind Glass substrate produces damage in mill process.

If in addition, being easily broken in milled processed, short grained ratio increases, and grinding load is significantly applied to phase To the bulky grain for reducing, therefore easily produce grinding flaw.Thus, abrasive particle is made to be engaged with each other by binding agent, such that it is able to press down The generation of system grinding flaw.

On the other hand, the aggregation of the raw material abrasive particle comprising binding agent due to the intensity of crystal boundary will not be too strong, thus pass through Ultrasonic irradiation etc. can be crushed easily, the grinding mill that can obtain even particle size distribution with the size for being suitable for milled processed Grain.Therefore, there is no need to crushing by high cost etc. to be crushed, nor need classification, can be with low cost easily Make grinding abrasive particle.

Specifically, binding agent uses the material that will not be disappeared in ablating work procedure.From this viewpoint, binding agent point Solution temperature is preferably more than the temperature of the firing temperature in ablating work procedure.It is therefore preferable that not being Organic substance.This is because, it is organic The binding agent of thing can disappear in ablating work procedure.Binding agent is preferably the granule being made up of inorganic compound, wherein, from raw material The excellent aspect of dispersibility in slurry is set out, and is preferably aoxidized by silicon dioxide (silica), titanium dioxide (titania) etc. The hydroxide such as the glass such as thing or their hydrate, aluminosilicate, cerium hydroxide, silicon hydroxide, zirconium hydroxide constitute Grain.Wherein, silicon dioxide is engaged with each other raw material abrasive particle due to melting at than relatively low temperature (such as less than 800 DEG C), So even it is such low temperature to fire firing temperature when processing, it is also possible to improve the intensity of the crystal boundary of raw material abrasive particle.With regard to Silicon dioxide, it is believed that it in the form of hydrate, occurs dehydration and form silicon dioxide when firing and processing in the slurry Without hydrate, thus raw material abrasive particle is engaged with each other.It should be noted that crystal boundary refers to the side between adjacent raw material abrasive particle Boundary.As silicon dioxide, for example, can enumerate colloidal silica, fumed silica, from dispersibility it is more excellent in terms of Set out, preferably use colloidal silica.It should be noted that raw material abrasive particle is connect each other in silicon dioxide or glass melting In the case of conjunction, it is additionally considered that a part defines vitrified combination.

The mean diameter of binding agent is preferably 3nm～20nm.The binder phase of this mean diameter is for raw material abrasive particle foot It is enough little, it is easily dispersed in dried, firing are processed and is configured between raw material abrasive particle, as raw material abrasive particle is engaged with each other Binding agent can function well.Less than in the case of 3nm, raw material abrasive particle is mutual to be bonded to the mean diameter of binding agent When become insufficient, during more than 20nm, binding agent is engaged with each other and forms big particle, and grinding flaw is caused sometimes.Bonding The mean diameter of agent can be determined using laser diffraction granularity distribution measurement device.

Binding agent is preferably the used grinding used in the 2nd milled processed of the manufacture method of aftermentioned glass substrate Abrasive particle.Used as used grinding abrasive particle, such as colloidal silica generally goes out of use after use, thus by as Binding agent is used, without cost of material, can be with low-cost production's ground slurry.Alternatively, it is also possible to be reclaimed Used ground slurry is directly appended in raw material slurry, thus workability is excellent.

Relative to the mass parts of raw material abrasive particle 100, the addition of binding agent is preferably 1 mass parts～10 mass parts, more preferably For 1 mass parts～5 mass parts.If being less than 1 mass parts, the effect of binding agent cannot be fully obtained, grinding abrasive particle is easily broken, Grinding rate is reduced sometimes.If in addition, being more than 10 mass parts, there is each other coagulation in binding agent, generates cause glass sometimes Glass substrate produces the big particle for damaging.If in addition, being more than 10 mass parts, excessive binding agent is attached to grinding for ceria The surface of mill abrasive particle, so as to the grinding function produced by grain surface is reduced, grinding rate is likely to reduce.Particularly, exist In the case that grinding abrasive particle is cerium based abrasive material, it is said that chemical action has been given play to glass substrate and high grinding rate is formed, If therefore the material beyond ceria excessively covers surface, reduce with the contact area for being ground substrate, grinding rate Reduce.

In addition is processed, preferably further add for suppressing the binding agent coagulation of the mutual coagulation of binding agent to suppress Agent.If binding agent aggregation inhibitor is present in raw material slurry, the mutual coagulation of binding agent is suppressed, and binding agent is easily divided Dissipate and be configured between raw material abrasive particle.Particularly, the more little then easier coagulation in water of the particle diameter of silicon dioxide, forms draw sometimes Play glass substrate and produce the thick silica dioxide granule for damaging, therefore by adding binding agent aggregation inhibitor, can suppress The coagulation of such silica dioxide granule.Particularly in the case where the mean diameter of silicon dioxide is 3nm～20nm, preferably add Adding additives aggregation inhibitor.

Binding agent aggregation inhibitor is preferably the material high with the affinity of binding agent, as such material, for example may be used To enumerate the material that surface has hydroxyl.Specifically, polysaccharide can be enumerated.Water is more preferably dissolved in by heating or is sent out The polysaccharide (below, also referred to as above-mentioned polysaccharide in the present embodiment) of raw gelation.Such polysaccharide is in dried The middle state that the easy attachment of binding agent is formed during drying, therefore with suppressing the same of the mutual coagulation of binding agent When, help the effect that is distributed between raw material abrasive particle of binding agent.With regard to the effect, it is believed that entered by following manner OK：Binding agent is caught by the polysaccharide comprising water, so as to position binding agent relative to raw material abrasive particle.

The temperature for water being dissolved in above-mentioned polysaccharide or gelation occurring is not particularly limited, it is preferred that be for example dried Under baking temperature in process, above-mentioned polysaccharide is dissolved in water or gelation occurs.Above-mentioned polysaccharide in dried by wrapping It is aqueous, so as to raw material abrasive particle is easily adhered on its surface.In addition, above-mentioned polysaccharide is by being fired at relatively low temperatures, Can easily disappear.From this viewpoint, the decomposition temperature of binding agent aggregation inhibitor be preferably less than 600 DEG C, more preferably For less than 500 DEG C.In addition, above-mentioned polysaccharide by processing in firing at least partly disappear, so as in the block of raw material abrasive particle The part of presence forms hole (space) in the aggregation of raw material abrasive particle, thus the aggregation of raw material abrasive particle can be made to form many The material of hole matter.From this viewpoint, binding agent aggregation inhibitor is properly termed as pore creating material.

Specifically, above-mentioned polysaccharide preferably uses starch, glycogen, agarose, pectin or combinations thereof.As shallow lake Powder, for example, can enumerate corn starch, wheat flour, Pseudobulbus cremastrae seu pleiones powder, rice starch etc., and its raw material is not particularly limited, for example, make With corn such as Caulis Sacchari sinensis, Semen Tritici aestivi, rice, Rhizoma Solani tuber osi, Ipomoea batatas Lam..

Relative to the mass parts of raw material abrasive particle 100, the addition of binding agent aggregation inhibitor is preferably 10 mass parts～100 matter Amount part, more preferably 10 mass parts～50 mass parts.When less than 10 mass parts, cannot abundant shape in the aggregation of raw material abrasive particle Into hole, it is difficult to crush sometimes.If in addition, being more than 100 mass parts, the effect of binding agent is hindered, grinds abrasive particle (raw material Abrasive particle) cannot fully become big, cannot obtain improving the effect of grinding rate by pelletize sometimes.

Binding agent aggregation inhibitor for example to be scattered in water equal solvent in state be added in raw material slurry.

It should be noted that by the use of used ground slurry as in the case of raw material abrasive particle, preferably at addition Reason before used ground slurry is filtered in advance, solid-liquid separation, crush.In filtration, by (such as 15 μm of coarse size More than) foreign body remove.In solid-liquid separation, by the glass such as the glass dregs included in the used ground slurry for being reclaimed into Divide and remove.In broken, the solid constituent generated in solid-liquid separation is broken by using the ultrasonic irradiation of homogenizer It is broken.Crush to easily carry out this, can in advance add in used ground slurry before solid-liquid separation prevents solid Composition becomes hard cake (hard cake) preventing agent (for example, water-fast polysaccharide) really up to the mark.

In addition, after solid-liquid separation, can be using as the further solid-liquid separation of the residual liquid of supernatant, by resulting solid Composition is crushed, and resulting material is used for into raw material slurry.Thus, it is possible to reclaim what is be not recovered in initial solid-liquid separation The used grinding abrasive particle of mean diameter little (such as 0.3 μm～2 μm), is used as raw material abrasive particle, regenerates grinding abrasive particle. In the case of so carrying out the solid-liquid separation of more than 2 times, grinding mill expensive as particularly cerium based abrasive material can be improved The response rate of grain, therefore suppress the effect of the cost of ground slurry to improve.It should be noted that in this case, for initial Solid-liquid separation in big (such as 0.5 μm～5 μm) solid constituent of the mean diameter that obtains, separately can be broken after charging It is broken, and then filtered, recycle during the milled processed of glass substrate is carried out afterwards, it is also possible to be stored in storage and grind In the tank of defibrination material, the manufacture method it can in addition contain the ground slurry using present embodiment is regenerated.

(b) dried

In dried, preferably it is dried the raw material slurry comprising binding agent by spray drying method.By being sprayed Mist is dried, and can control the size of the block of raw material abrasive particle.Compared with other methods, spray drying method can reduce mean diameter, And then can reduce the deviation of particle diameter, thus it is preferred that.With regard to being spray-dried, specifically, it is possible to use rotary disc-type, biliquid Sprayer unit known to nozzle-type, drive nozzle formula etc. is sprayed, and being supplied to the interior that is dried of spray dryer is dried it, So as to carry out.The condition such as the species of sprayer unit and the aperture of nozzle, the supply pressure of raw material slurry is according to target material abrasive particle Block size and suitably set.For example it is preferably by being spray-dried the size (mean diameter) of the block of the raw material abrasive particle for obtaining 5 μm～10 μm or so of size.If being more than 10 μm, big particle residual, causes sometimes grinding flaw after crushing.The opposing party Face, if being less than 5 μm, short grained increasing proportion, grinding rate is reduced sometimes.It should be noted that average grain herein Footpath refers to that the block to randomly selected 100 above-mentioned raw materials abrasive particles in SEM observations obtains respectively major diameter and carries out average and obtain Value.

In addition, in the case of adding pore creating material in raw material slurry before spray drying, the size of pore creating material be (pore creating material Mean diameter) it is preferably 3 μm～20 μm.By the scope for making pore creating material be this size, the raw material abrasive particle after firing can be made The size in hole of aggregation be appropriate size, can make it is broken after the size of grinding abrasive particle be that appropriate size (for example, is put down Equal 0.5 μm～10 μm of particle diameter).With regard to baking temperature (being dried indoor atmosphere temperature), for example, the inlet temperature of hothouse is 150 DEG C～250 DEG C.It should be noted that dried can not also be heated and carried out.

Herein, the block of the raw material abrasive particle made in dried is shown in (a) of Fig. 1.Herein, illustrate to send as an envoy to and include The spherical block of the raw material abrasive particle that the raw material slurry of binding agent aggregation inhibitor is dried and makes.The block 10 of raw material abrasive particle is being included On the binding agent aggregation inhibitor 7 of moisture to cover its surface in the way of be attached with substantial amounts of raw material abrasive particle 3, in raw material abrasive particle 3 Between be distributed binding agent (not shown).It should be noted that the block 10 of raw material abrasive particle includes substantial amounts of raw material abrasive particle 3, But in (a) of Fig. 1, for convenience, eliminate the diagram on the border of substantial amounts of raw material abrasive particle 3.

C () firing is processed

Device to being fired process is not particularly limited, for example, can enumerate muffle furnace.Firing in firing process Temperature is preferably less than 800 DEG C.Firing temperature refers to the atmosphere temperature in the space being fired.By making firing temperature be Less than 800 degree, can reduce making the energy cost of ground slurry.If firing temperature is more than 800 degree, in raw material abrasive particle each other Grain boundaries combine, grind the intensity of crystal boundary of abrasive particle becomes too high sometimes.In addition, binding agent each other sometimes combine and Form big particle.In the case of these, the damage of glass substrate is easily produced.If former in addition, firing temperature is more than 800 DEG C The composition of material abrasive particle changes, hardness increases, and glass substrate produces sometimes damage.In addition, the firing temperature in firing process Degree is preferably more than 500 DEG C, more preferably more than 600 DEG C.In the case of less than 500 DEG C, raw material abrasive particle is mutual to be combined with When it is insufficient.

In firing is processed, in the case of binding agent aggregation inhibitor is added with raw material slurry, preferably made by firing At least a portion of binding agent aggregation inhibitor disappears.Thus, binding agent aggregation inhibitor is configured with the block of raw material abrasive particle Part become hole, the aggregation of the raw material abrasive particle of Porous can be produced.

Herein, the aggregation of made raw material abrasive particle in firing is processed is shown in (b) of Fig. 1.Herein, exemplify The aggregation of the raw material abrasive particle raw material slurry comprising binding agent aggregation inhibitor is dried, fired and make.Raw material abrasive particle Aggregation 20 has the hole 9 for being disappeared and being formed by binding agent aggregation inhibitor.It should be noted that the set of raw material abrasive particle Body except with diagram hole 9 in addition to, also with by be configured at surround hole 9 raw material abrasive particle between binding agent Aggregation inhibitor also disappears and is formed, the substantial amounts of slight void between raw material abrasive particle, so as to define Porous.It is former The size (mean diameter) of the aggregation 20 of material abrasive particle is for example preferably 5 μm～10 μm or so of size.If being more than 10 μm, break Broken rear big particle residual, causes sometimes grinding flaw.On the other hand, if being less than 5 μm, short grained increasing proportion is ground Mill speed is reduced sometimes.It should be noted that mean diameter herein is referred on randomly selected 100 in observing SEM State raw material abrasive particle block obtain respectively major diameter and carry out it is average obtained from value.With regard to the aggregation 20 of raw material abrasive particle, firing Binding agent (not shown) is melted in process, is solidified afterwards, and now raw material abrasive particle 3 is engaged with each other, and thus form raw material The size (for example, the meansigma methodss of aftermentioned comprcssive strength are 0.1MPa～20MPa) of the intensity appropriateness of the crystal boundary of abrasive particle 3.Need It is bright, substantial amounts of raw material abrasive particle 3 is included in the aggregation 20 of raw material abrasive particle, but in (b) of Fig. 1, for convenience, save The diagram on the border of substantial amounts of raw material abrasive particle 3 is omited.For example, by based on EDX (Energy Dispersive X-ray Microanalyzer, energy dispersion X-ray differential analyzer) distribution diagram of element can confirm that between raw material abrasive particle 3 press from both sides It is miscellaneous to have binding agent.

(d) break process

The manufacture method of the ground slurry of the 1st embodiment preferably further possess by the aggregation of raw material abrasive particle it is broken and Make the break process of grinding abrasive particle.Thus, it is possible to obtain being suitable for the grinding abrasive particle of the size of milled processed.In raw material abrasive particle Aggregation in be formed with hole in the case of, it is easier to it is broken.

It is broken to carry out ultrasonic irradiation to carry out for example by using homogenizer, to the aggregation of raw material abrasive particle.Ultrasound wave Frequency be preferably 16kHz～120kHz.It is broken to be carried out using the unit beyond homogenizer.The broken time is not had Especially limit, for example, 1 minute～20 minutes.

The broken mode for preferably reaching 0.5 μm～10 μm according to the mean diameter of grinding abrasive particle is carried out.More preferably 0.5 μm ～5 μm, 0.7 μm～3 μm.If being ground process using the grinding abrasive particle of this mean diameter, can be with high grinding rate It is ground, while the surface that can suppress glass substrate produces damage.

Break process can also be to grind method, but above-mentioned supercritical ultrasonics technology using what ball mill etc. was destroyed for physically It is excellent in terms of simplicity.

After break process, it is dispersed in water grinding abrasive particle, it is possible thereby to make ground slurry.Now, preferably in water filling Before filtered, in advance remove coarse size (such as more than 15 μm) granule.The granule of coarse size herein is by broken A part for the broken aggregation for processing the unbroken raw material abrasive particle into given size.

According to the manufacture method of the ground slurry of the 1st embodiment, binding agent is added in raw material slurry, and it is carried out It is dried, fires, it is possible thereby to make the aggregation of the raw material abrasive particle containing binding agent.The aggregation of the raw material abrasive particle has raw material Abrasive particle each other by the part of binding agent engages, therefore compared with the situation that raw material abrasive particle is joined directly to each other crystal boundary it is strong Degree will not be too strong.Therefore, can easily be crushed by ultrasonic irradiation etc., can be obtained with the size for being suitable for milled processed The grinding abrasive particle of even particle size distribution.So, according to the method for the 1st embodiment, it is not necessary to carry out crushing of high cost etc., and And also without classification, therefore, it is possible to easily make grinding abrasive particle with low cost.Grinding abrasive particle is become by raw material Abrasive Particle Size Greatly, so as to grinding rate raising.In addition, for by the grinding abrasive particle made by the method for the 1st embodiment, by mat Raw material abrasive particle is engaged with each other by binding agent, so as to the intensity of crystal boundary will not be too strong, thus glass substrate can be suppressed to produce damage. On the other hand, for by the grinding abrasive particle made by the method for the 1st embodiment, by raw material abrasive particle each other by viscous Knot agent and engage, so as to aggregate particle size becomes big, thus while grinding rate is improved crystal boundary intensity enhancing, so as to grind It is difficult to crush in process, high grinding rate can be maintained.

In addition, for by the grinding abrasive particle made by the method for the 1st embodiment, by raw material abrasive particle mat each other Engaged by binding agent, particle diameter becomes big, so as to grinding rate raising, and with the grain-boundary strength of appropriateness, thus in use It is difficult to crush, high grinding rate can be maintained.

(grinding abrasive particle and ground slurry)

The grinding abrasive particle 1 of the 1st embodiment is conceptually illustrated in fig. 2.

Grinding abrasive particle 1 possesses：For the original comprising ceria or zirconic granule of the milled processed of glass substrate Material abrasive particle 3；With the binding agent 5 on the surface for being configured at raw material abrasive particle 3.More specifically, it is for glass substrate to grind abrasive particle 1 The grinding abrasive particle of milled processed, silica dioxide granule is present between ceria or zirconic granule as binding agent 5.

It should be noted that as shown in figure 1, a large amount of respectively in the block 10 of raw material abrasive particle and the aggregation 20 of raw material abrasive particle Comprising raw material abrasive particle 3.

Raw material abrasive particle 3 is identical with cerium based abrasive material or zirconium oxide based abrasive material in the raw material abrasive particle of described above. For cerium based abrasive material, in addition to ceria, in order to suppress glass substrate while high grinding rate is realized Produce at least one in damage, oxide, their fluoride preferably comprising other rare earth elements such as lanthanum, praseodymium, neodymiums etc. Mixture.Can be that silica containing mixture is also wrapped in addition to zirconium oxide for zirconium oxide based abrasive material.

The mean diameter of raw material abrasive particle 3 is, for example, 0.3 μm～2 μm, and e.g. primary particle size is 80nm～150nm's or so Particle agglutination.

Binding agent 5 is same with the binder phase of described above.It should be noted that in Fig. 2, binding agent 5 is configured at as two The surface of the raw material abrasive particle 3 of secondary granule, but it is also possible to be configured at the surface of the primary particle for constituting raw material abrasive particle 3.Binding agent 5 is excellent Choosing covers the surface area on the surface of the raw material abrasive particle 3 less than 50%.For more than 50% when, grind abrasive particle surface and be ground base The contact surface of plate reduces, and grinding rate is easily reduced.

The meansigma methodss of the comprcssive strength that grinding abrasive particle 1 is preferably determined according to JIS R1639-5 are 0.1MPa～20MPa.It is logical Crossing makes the meansigma methodss of comprcssive strength be more than 0.1MPa, can suppress to grind abrasive particle in milled processed and is susceptible to broken and makes grain Footpath diminishes, and thus can suppress the reduction of grinding rate.It should be noted that due to deviation greatly, thus comprcssive strength is preferably determined More than 20 points.From from the aspect of the reduction for more reliably suppressing grinding rate, the meansigma methodss of comprcssive strength are more preferably 3MPa More than.In addition, being below 20MPa by the meansigma methodss for making comprcssive strength, the glass baseplate surface in milled processed can be suppressed Produce damage.

The mean diameter of grinding abrasive particle 1 is, for example, 0.5 μm～10 μm.The number of the raw material abrasive particle 3 included in grinding abrasive particle 1 Amount is not particularly limited, for example, several～more than ten.

The ground slurry of the 1st embodiment possesses the disperse medium such as the water of above-mentioned grinding abrasive particle 1 and dispersion grinding abrasive particle 1.

The grinding abrasive particle of the 1st embodiment and ground slurry are for example entered by the manufacture method of the ground slurry of described above Row makes.

<2nd embodiment>

(manufacture method of ground slurry)

Then, the 2nd embodiment of the present invention is illustrated.

The manufacture method of the ground slurry of the 2nd embodiment is the grinding abrasive particle comprising the milled processed for glass substrate Ground slurry manufacture method, the manufacture method possesses addition process, dried, fire and process each process.At addition In reason, in the raw material slurry of the raw material abrasive particle comprising the raw material as grinding abrasive particle pore creating material is added.In dried, make Raw material slurry comprising pore creating material is dried and the block of raw material abrasive particle of the making containing pore creating material.In firing is processed, to abrasive particle Block is fired and makes at least a portion of pore creating material disappear, so as to the part shape of the block of raw material abrasive particle being located in pore creating material Pore-forming.

The block of raw material abrasive particle refers to the raw material agglomeration of abrasive particles of more than 2 and the block that formed, and the block of raw material abrasive particle has The binding agent of raw material abrasive particle, pore creating material and optional mixture.The block of raw material abrasive particle for example has following forms：Substantial amounts of raw material abrasive particle It is attached to the pore creating material comprising moisture to cover its surface.Between raw material abrasive particle, binding agent has preferably been distributed.

The aggregation of raw material abrasive particle is referred to and is disappeared by least one of pore creating material and formed in the block of raw material abrasive particle The material in hole (space).The aggregation of raw material abrasive particle has the binding agent of raw material abrasive particle and optional mixture.In raw material abrasive particle In aggregation, preferred feedstock abrasive particle is engaged each other by binding agent (for example, melted by binding agent and solidified).

With regard to cerium based abrasive material, combined in crystal boundary by firing, played as granule in actual grinding The particle diameter of effect becomes big, so as to grinding rate raising.But, for making particle diameter become big grinding-material by firing, It is generally crushed in order to be adjusted to the size for being suitable to milled processed.But, the crushing of grinding-material needs cost and time.Separately Outward, if being crushed, the particle size distribution of grinding-material easily becomes uneven, therefore needs to be classified after crushing, thus Also Expenses Cost and time.Therefore, the purpose of the 2nd embodiment is easily to provide grinding rate with low cost to be improved Ground slurry manufacture method.In addition, the purpose of the 2nd embodiment is to provide the glass for having used such ground slurry The manufacture method of substrate.

According to the manufacture method of the ground slurry of the 2nd embodiment, by using pore creating material, can make and be formed with hole (sky Gap), the aggregation of raw material abrasive particle that is easily broken.Accordingly, it is capable to enough simple methods break the aggregation of raw material abrasive particle It is broken, ground slurry can easily be made with low cost.In addition, grinding abrasive particle is because raw material abrasive particle is through being dried, firing and grain Footpath becomes big, so as to grinding rate raising.In addition, the manufacture method of the glass substrate according to the 2nd embodiment, can be with high grinding Speed is ground to glass substrate.

It should be noted that being not particularly limited to the purposes of glass substrate, for example, liquid crystal indicator etc. is various aobvious The panel of showing device；Photomask or the mask substrate as its substrate；The disk of HDD device.Grinding with regard to glass substrate Mill process, such as double-side polishing apparatus are carrying out used in the manufacture method of aftermentioned glass substrate.

A () addition is processed

Raw material abrasive particle is the original of the grinding abrasive particle included in ground slurry made by the method by the 2nd embodiment Material, in the case of stating used ground slurry after use as raw material abrasive particle, refers to the used grinding abrasive particle.Raw material The mean diameter of abrasive particle is preferably 0.3 μm～2 μm.By using the raw material abrasive particle of this mean diameter, can make be suitable to into The grinding abrasive particle of the size of the milled processed of row glass substrate.It is known that in the raw material of the scope in 0.3 μm～2.0 μm The raw material abrasive particle of mean diameter smaller (such as 0.3 μm～be less than 0.5 μm) is difficult to be recovered in solid-liquid separation in abrasive particle, and Even and if can reclaim, the raw material abrasive particle regenerated using existing method particle diameter in milled processed also can diminish, grinding rate Reduce, or glass substrate can produce damage.According to the manufacture method of the 2nd embodiment, appropriate hardness is made as described later (anti- Compressive Strength) grinding abrasive particle, be thus suitable for for the smaller material of mean diameter making ground slurry as raw material abrasive particle. It should be noted that raw material abrasive particle is several second particles to tens primary particle coagulations, raw material abrasive particle it is average Particle diameter refers to the mean diameter of second particle.It should be noted that sending out as the granule of 1 grinding abrasive particle in actual grinding Wave effect is second particle.In addition, in this specification, mean diameter refers to median particle diameter (d50).D50 is for example based on sharp Optical diffraction scattering formula determination of particle size distribution accumulation particle diameter from microgranule side with accumulation 50% corresponding particle diameter.

Pore creating material is preferably the organic compound that surface has hydroxyl, as such material, for example, can enumerate polysaccharide Class, can preferably enumerate the polysaccharide for water being dissolved in by heating or gelation occurring and (below, be also referred to as in the present embodiment Above-mentioned polysaccharide).Above-mentioned polysaccharide can in dried with comprising water state in surface attachment raw material abrasive particle, and Firing is burned in processing and at least a portion disappears, so as to the part being located in the block of raw material abrasive particle is in raw material abrasive particle Hole is formed in aggregation, thus the aggregation of the raw material abrasive particle of Porous can be made.Water is dissolved in above-mentioned polysaccharide or is sent out The temperature of raw gelation is not particularly limited, it is preferred that under the baking temperature for example in dried, above-mentioned polysaccharide is molten In water or generation gelation.With regard to the decomposition temperature of pore creating material, from by be fired at relatively low temperatures and easily Set out in terms of disappearance, preferably less than 600 DEG C, more preferably less than 500 DEG C.

In addition, for above-mentioned polysaccharide, in the case of aftermentioned binding agent is added with raw material slurry, at drying Formed the state of the easy attachment of binding agent in reason during drying, therefore with suppressing the same of the mutual coagulation of binding agent When, help the effect that is distributed between raw material abrasive particle of binding agent.With regard to the effect, it is believed that entered by following manner OK：Binding agent is caught by the polysaccharide comprising water, so as to position binding agent relative to raw material abrasive particle.From this viewpoint, Pore creating material is properly termed as binding agent aggregation inhibitor.

Relative to the mass parts of raw material abrasive particle 100, the addition of pore creating material is preferably 10 mass parts～100 mass parts, more excellent Elect 10 mass parts～50 mass parts as.When less than 10 mass parts, hole cannot be sufficiently formed in the aggregation of raw material abrasive particle, be had When be difficult to crush.If in addition, being more than 100 mass parts, the effect of binding agent is hindered, and grinding abrasive particle (raw material abrasive particle) cannot Fully become big, cannot obtain improving the effect of grinding rate by pelletize sometimes.

Pore creating material for example to be scattered in water equal solvent in state be added in raw material slurry.

In addition is processed, preferably further addition is configured at the binding agent on the surface of raw material abrasive particle.Binding agent by Fire fusing when processing and raw material abrasive particle is engaged with each other, such that it is able to improve the intensity of crystal boundary.It should be noted that crystal boundary is Refer to the border between adjacent raw material abrasive particle.Thus, grind abrasive particle aggregate particle size (during grinding as 1 grinding abrasive particle The particle diameter of the granule that grain plays a role) become big, so as to the grinding rate for grinding abrasive particle is improved, while being difficult to brokenly in milled processed It is broken, high grinding rate can be maintained.On the other hand, in the case that raw material abrasive particle is engaged each other by binding agent, with raw material The situation that abrasive particle is joined directly to each other is compared, and the intensity of crystal boundary will not be too strong, thus glass substrate in milled processed can be suppressed to produce It is raw to damage.

Specifically, binding agent uses the material that will not be disappeared in ablating work procedure.From this viewpoint, binding agent point Solution temperature is preferably more than the temperature of the firing temperature in ablating work procedure.It is therefore preferable that not being Organic substance.This is because, it is organic The binding agent of thing can disappear in ablating work procedure.Binding agent is preferably the granule being made up of inorganic compound, wherein, from raw material The excellent aspect of dispersibility in slurry is set out, and is preferably aoxidized by silicon dioxide (silica), titanium dioxide (titania) etc. The hydroxide such as the glass such as thing or their hydrate, aluminosilicate, cerium hydroxide, silicon hydroxide, zirconium hydroxide constitute Grain.Wherein, silicon dioxide is engaged with each other raw material abrasive particle due to melting at than relatively low temperature (such as less than 800 DEG C), So even it is such low temperature to fire firing temperature when processing, it is also possible to improve the intensity of the crystal boundary of raw material abrasive particle.With regard to Silicon dioxide, it is believed that it in the form of hydrate, occurs dehydration and form silicon dioxide when firing and processing in the slurry Without hydrate, thus raw material abrasive particle is engaged with each other.As silicon dioxide, for example, can enumerate colloidal silica, vapor phase method Silicon dioxide, from the aspect that dispersibility is more excellent, preferably uses colloidal silica.It should be noted that in titanium dioxide Silicon or glass melting and in the case that raw material abrasive particle is engaged with each other, be additionally considered that a part defines vitrified combination.

Binding agent has and holds agglutinophilic property, but by there is pore creating material in raw material slurry, can suppress binding agent that This coagulation, binding agent is easily dispersed and is configured between raw material abrasive particle.Particularly, silicon dioxide easy coagulation in water, has When can be formed cause glass substrate produce damage thick silica dioxide granule, but by add pore creating material, this can be suppressed The coagulation of the silica dioxide granule of sample.

In addition, after solid-liquid separation, can be using as the further solid-liquid separation of the residual liquid of supernatant, by resulting solid Composition is crushed, and resulting material is used for into raw material slurry.Thus, it is possible to reclaim what is be not recovered in initial solid-liquid separation The used grinding abrasive particle of mean diameter little (such as 0.3 μm～2 μm), is used as raw material abrasive particle, regenerates grinding abrasive particle. When so carrying out the solid-liquid separation of more than 2 times, returning for grinding abrasive particle expensive as particularly cerium based abrasive material can be improved Yield, therefore suppress the effect of the cost of ground slurry to improve.It should be noted that in this case, in initial solid-liquid Big (such as 0.5 μm～5 μm) solid constituent of mean diameter obtained in separation, separately can be crushed after charging, and then Filtered, recycled during the milled processed of glass substrate is carried out afterwards, it is also possible to be stored in storage ground slurry Tank in, the manufacture method it can in addition contain the ground slurry using present embodiment is regenerated.

(b) dried

In dried, preferably it is dried the raw material slurry comprising pore creating material by spray drying method.By being sprayed Mist is dried, and can control the size of the block of raw material abrasive particle.Compared with other methods, spray drying method can reduce mean diameter, And then can reduce the deviation of particle diameter, thus it is preferred that.With regard to being spray-dried, specifically, it is possible to use rotary disc-type, biliquid Sprayer unit known to nozzle-type, drive nozzle formula etc. is sprayed, and being supplied to the interior that is dried of spray dryer is dried it, So as to carry out.The condition such as the species of sprayer unit and the aperture of nozzle, the supply pressure of raw material slurry is according to target material abrasive particle Block size and suitably set.For example it is preferably by being spray-dried the size (mean diameter) of the block of the raw material abrasive particle for obtaining 5 μm～10 μm or so of size.If being more than 10 μm, big particle residual, causes sometimes grinding flaw after crushing.The opposing party Face, if being less than 5 μm, short grained increasing proportion, grinding rate is reduced sometimes.It should be noted that average grain herein Footpath refers to that the block to randomly selected 100 above-mentioned raw materials abrasive particles in SEM observations obtains respectively major diameter and carries out average and obtain Value.

Herein, the block of the raw material abrasive particle made in dried is shown in (a) of Fig. 1.Herein, illustrate to send as an envoy to and include The spherical block of the raw material abrasive particle that the raw material slurry of binding agent is dried and makes.The block 10 of raw material abrasive particle is in the pore-creating comprising moisture In agent 7 to cover its surface in the way of be attached with substantial amounts of raw material abrasive particle 3, be distributed between raw material abrasive particle 3 not shown Binding agent.It should be noted that the block 10 of raw material abrasive particle includes substantial amounts of raw material abrasive particle 3, but in (a) of Fig. 1, for convenience For the sake of, eliminate the diagram on the border of substantial amounts of raw material abrasive particle 3.

C () firing is processed

In firing is processed, in the case of being added with pore creating material in raw material slurry, preferably pore creating material is made extremely by firing A few part disappears.Thus, the part for pore creating material being configured with the block of raw material abrasive particle becomes hole, can produce Porous The aggregation of raw material abrasive particle.

Herein, the aggregation of made raw material abrasive particle in firing is processed is shown in (b) of Fig. 1.Herein, exemplify The aggregation of the raw material abrasive particle raw material slurry comprising binding agent is dried, fired and make.The aggregation 20 of raw material abrasive particle has There is the hole 9 for disappearing and being formed by pore creating material.It should be noted that the aggregation of raw material abrasive particle is except the hole with diagram Beyond 9, also with by be configured at surround hole 9 raw material abrasive particle between binding agent aggregation inhibitor also disappear and shape Into, substantial amounts of slight void between raw material abrasive particle, so as to define Porous.The chi of the aggregation 20 of raw material abrasive particle Very little (mean diameter) is for example preferably 5 μm～10 μm or so of size.If being more than 10 μm, big particle residual, has after crushing When can cause grinding flaw.On the other hand, if being less than 5 μm, short grained increasing proportion, grinding rate is reduced sometimes.Need It is noted that mean diameter herein is referred to asking respectively the block of randomly selected 100 above-mentioned raw materials abrasive particles in SEM observations Go out major diameter and carry out it is average obtained from value.With regard to the aggregation 20 of raw material abrasive particle, the binding agent (not shown) in firing is processed Melt, solidify afterwards, now raw material abrasive particle 3 is engaged with each other, thus form the intensity appropriateness of the crystal boundary of raw material abrasive particle 3 Size (for example, the meansigma methodss of aftermentioned comprcssive strength be 0.1MPa～20MPa).It should be noted that in the collection of raw material abrasive particle Substantial amounts of raw material abrasive particle 3 is included in fit 20, but in (b) of Fig. 1, for convenience, eliminates substantial amounts of raw material abrasive particle 3 The diagram on border.For example, by the way that based on EDX, (Energy Dispersive X-ray microanalyzer, energy dispersion X are penetrated Line differential analyzer) distribution diagram of element to can confirm that and be mingled with binding agent between raw material abrasive particle 3.

(d) break process

The manufacture method of the ground slurry of present embodiment preferably further possess by the aggregation of raw material abrasive particle it is broken and Make the break process of grinding abrasive particle.Thus, it is possible to obtain being suitable for the grinding abrasive particle of the size of milled processed.In raw material abrasive particle Aggregation in be formed with hole in the case of, it is easier to it is broken.

The broken aggregation for example by using homogenizer and to raw material abrasive particle carries out ultrasonic irradiation to carry out.Ultrasound wave Frequency be preferably 16kHz～120kHz.It is broken to be carried out using the unit beyond homogenizer.The broken time is not had Especially limit, for example, 1 minute～20 minutes.

According to the manufacture method of the ground slurry of present embodiment, pore creating material is added in raw material slurry, and it is carried out It is dried, fires, it is possible thereby to make the aggregation for being formed with hole, Porous raw material abrasive particle.The set of this raw material abrasive particle Body can be crushed easily by ultrasonic irradiation etc., can obtain even particle size distribution with the size for being suitable for milled processed Grinding abrasive particle.So, according to the method for present embodiment, it is not necessary to carry out crushing of high cost etc., nor need classification, Therefore, it is possible to easily make grinding abrasive particle with low cost.Grinding abrasive particle becomes big by raw material Abrasive Particle Size, so as to grinding rate Improve.

(grinding abrasive particle and ground slurry)

The grinding abrasive particle 1 made by said method is conceptually illustrated in fig. 2.

Herein, illustrated as cerium based abrasive material or in case of zirconium oxide based abrasive material with raw material abrasive particle 3.

For the cerium based abrasive material used in raw material abrasive particle 3, in addition to ceria, in order to realize Gao Yan Suppress glass substrate to produce damage while mill speed, oxide preferably comprising other rare earth elements such as lanthanum, praseodymium, neodymiums, it Fluoride etc. at least one mixture.For zirconium oxide based abrasive material, can be except zirconium oxide with Also wrap silica containing mixture outward.

In Fig. 2, binding agent 5 is configured at the surface of the raw material abrasive particle 3 as second particle, but it is also possible to be configured at composition former The surface of the primary particle of material abrasive particle 3.The surface area on the preferred surface for covering the raw material abrasive particle 3 less than 50% of binding agent 5.For When more than 50%, the surface for grinding abrasive particle reduces with the contact surface for being ground substrate, and grinding rate is easily reduced.

The meansigma methodss of the comprcssive strength that grinding abrasive particle 1 is preferably determined according to JIS R1639-5 are 0.1MPa～20MPa.It is logical Crossing makes comprcssive strength be more than 0.1MPa, and the grinding abrasive particle in milled processed can be suppressed to be susceptible to broken and make particle diameter diminish, Thus the reduction of grinding rate can be suppressed.It should be noted that due to deviation it is big, thus comprcssive strength it is preferred determine 20 points with On.From from the aspect of the reduction for more reliably suppressing grinding rate, the meansigma methodss of comprcssive strength are more preferably more than 3MPa.Separately Outward, the meansigma methodss by making comprcssive strength are below 20MPa, and the glass baseplate surface in milled processed can be suppressed to produce damage Wound.

Ground slurry possesses the disperse medium such as the water of above-mentioned grinding abrasive particle 1 and dispersion grinding abrasive particle 1.

(manufacture method of glass substrate)

Then, the manufacture method of the glass substrate of present embodiment is illustrated.

Herein, to manufacture disk in case of glass substrate used illustrating.

The manufacture method of present embodiment is characterised by, using the slurry illustrated in above-mentioned 1st and the 2nd embodiment Expect to be ground the surface of glass substrate.That is, the manufacture method of present embodiment is being capable of general 1st and the 2nd embodiment party The method of the ground slurry illustrated in formula.

The summary of the manufacture method of present embodiment is illustrated, first, the plate with a pair of first type surfaces is formed The forming processes of the glass blank of shape.Glass blank is the raw material of glass substrate for disc.Then, the glass blank is implemented Thick ground.Afterwards, shape processed is implemented to glass blank and forms glass substrate, further implement at end surface grinding Reason.Afterwards, glass substrate is implemented to be processed using the fine ginding of bonded-abrasive.Afterwards, the 1st milled processed is implemented to glass substrate With the 2nd milled processed.It should be noted that in the present embodiment, carried out with above-mentioned flow process, for above-mentioned flow process, process Species is not limited, additionally, above-mentioned process can be omitted suitably as needed.Hereinafter, above-mentioned each process is illustrated.

The forming processes of (a) glass blank

In forming processes, using such as compression molding method molding is carried out.Using compression molding method, can obtain discoideus Glass blank.Can be using glass tube down-drawing, the again known forming method replacement die pressing manufacture gob such as traction therapy, fusion method Material.For the plate glass blank made by these methods, shape processed described later is appropriately carried out, thus obtains plectane The glass substrate of shape, it is the raw material of glass substrate for disc.

(b) thick ground

Then, thick ground is carried out.In thick ground, above-mentioned glass blank is being maintained at into well-known double While on the carrier (not shown) of face grinding attachment, the grinding of the first type surface of the both sides of glass blank is carried out.Specifically, will Glass blank is maintained in the retaining hole being arranged on carrier, while being clamped between upper price fixing and lower price fixing, is contained to its supply While having the grinding fluid of grinding agent, any one or the two moving operation of price fixing or lower price fixing is made, thus make glass substrate With each price fixing relative movement, so as to be ground to two first type surfaces of glass substrate.As grinding agent, it is possible to use for example dissociate Abrasive particle.In thick ground, according to the mode of the glass blank approximately flatness of the thickness of slab size and first type surface of target It is ground.It should be noted that thick ground is entered according to the dimensional accuracy or surface roughness of the glass blank of institute's molding OK, but can suitably omit.

(c) shape processed

Then, shape processed is carried out.In shape processed, using known processing method on glass blank Circular hole is formed, the round-meshed discoideus glass substrate of tool is thus obtained.Afterwards, the chamfering of the end face of glass substrate is carried out.It is right End face in both the inner circumferential side of glass substrate and outer circumferential side carries out chamfering.By carrying out chamfering, in the end face of glass substrate The fillet surface (median surface) of the formation side wall orthogonal with first type surface and connecting side wall and first type surface.

The process of (d) end surface grinding

Then, the end surface grinding for carrying out glass substrate is processed.In end surface grinding process, to abrasive brush and glass substrate The lapping liquid containing free abrasive is supplied between end face, makes abrasive brush relative on the thickness direction of glass substrate with glass substrate It is mobile, thus it is ground.Processed by end surface grinding, the inner circumferential side of glass substrate and the end face of outer circumferential side are ground, become Mirror status.

The process of (e) fine ginding

Then, implement fine ginding to the first type surface of glass substrate to process.In fine ginding process, preferably use and glued on price fixing The double-sided grinding device of bonded-abrasive is posted, the first type surface of glass substrate is ground.Specifically, using bonded-abrasive generation It is ground for above-mentioned free abrasive, in addition, substantially samely with above-mentioned thick ground to two master meters of glass substrate Face is ground.

(f) the 1st milled processed

Then, the 1st milled processed is implemented to the first type surface of glass substrate.1st milled processed uses known twin grinding Device, makes glass substrate be maintained on carrier, carries out the grinding of the first type surface of the both sides of glass substrate.In the 1st milled processed, Using free abrasive, the grinding pad being pasted onto on price fixing is set to be ground with the major surface contacts of glass substrate.At 1st grinding During reason, the slurry containing free abrasive from the supplying tank (not shown) of double-side polishing apparatus via pipe arrangement (not shown) supply to Between glass substrate and grinding pad.Slurry preferred cycle is used.For the slurry containing free abrasive, using above-mentioned enforcement The ground slurry illustrated in mode.Free abrasive uses such as cerium based abrasive material or zirconium oxide based abrasive material.

As the optimum condition of the 1st milled processed, following conditions can be enumerated.

Grinding wear particle concentration：1 weight %～20 weight %

The load of the upper price fixing of double-side polishing apparatus and lower price fixing to glass substrate：50g/cm²～200g/cm²

Milling time：10 minutes～120 minutes

Generation due to being prevented from slight flaws, thus grinding pad is preferably the grinding pad of suede type.Grind from raising Set out in terms of mill speed and reduction slight flaws, the hardness of grinding pad is preferably 60～90 with ASKER C durometers.

In the 1st milled processed, such as in the case where the grinding using bonded-abrasive is carried out, carry out being remained in first type surface Crackle or strain removal, or the concavo-convex removal of tiny area produced in first type surface because of crystallization process.By appropriate Adjustment allowance, the shape for being prevented from the end of first type surface is excessively sunk or prominent, while first type surface can be reduced Surface roughness, such as arithmetic average roughness Ra.Further, since the ground slurry used in the 1st milled processed has hardly possible With crush grinding abrasive particle, thus particle diameter can be suppressed to diminish, grinding rate reduce.In addition, grinding abrasive particle will not be really up to the mark, thus can The first type surface for suppressing glass substrate produces damage.

It should be noted that ground slurry can be reclaimed after the 1st milled processed, and then grinding using above-mentioned embodiment The manufacture method of defibrination material, the renovation process of i.e. used ground slurry are regenerated, can be by the ground slurry after regeneration It is further used for the milled processed of other glass substrates.

G () the 2nd grinding (mirror ultrafinish) is processed

Then, the 2nd milled processed is implemented.The purpose of the 2nd milled processed is the mirror ultrafinish of first type surface.At 2nd grinding Reason can use double-side polishing apparatus same with the double-side polishing apparatus and Ginding process used in the 1st milled processed and grinding Method, but the size of the grinding abrasive particle being smaller in size than used in the 1st milled processed of preferred grinding abrasive particle.Thereby, it is possible to prevent The shape of the end of first type surface is excessively sunk or prominent, while the roughness of first type surface can be reduced.After 2nd milled processed, Glass substrate is taken out and cleaned together with carrier from double-side polishing apparatus.It is free used in 2nd milled processed Abrasive particle is, for example, colloidal silica.It should be noted that for the used ground slurry used in the 2nd milled processed, Can be recycled, and be added to raw material slurry in the addition of the manufacture method of the ground slurry of above-mentioned embodiment is processed In.

(embodiment)

(1) with regard to the embodiment of the 1st embodiment

In order to confirm the effect of the 1st embodiment of the present invention, following experiments have been carried out.Specifically, for as original The used ground slurry of material abrasive particle, as shown in table 1, makes condition different and is regenerated, and determines the grinding after regeneration The comprcssive strength of abrasive particle (sample 1～5), and then grinding rate when having carried out milled processed is determined, have rated in glass substrate The generation degree of the damage of generation.

Being regenerated by for used ground slurry carry out successively following process 1～7 to carry out.For used grinding For slurry, using following slurries：Using the slurry comprising the untapped cerium based abrasive material that mean diameter D50 is 1.0 μm The 1st milled processed of 1 above-mentioned embodiment is carried out, the slurry obtained by reclaiming.Cerium based abrasive material after recovery it is average Particle diameter D50 is 0.7 μm.1st milled processed uses double-side polishing apparatus, at same with the condition of aftermentioned 1st milled processed article Carry out under part.

Process 1：Foreign body removal is processed

By filtering, grinding pad is considered to be worth doing, material, the glass for being dried the simultaneously granule of coarsening is mixed in milled processed The foreign bodies such as bits are removed from used ground slurry.The size of the granule of removal etc. is more than 15 μm.

Process 2：Solid-liquid separation process

After processing 1, for used ground slurry, 20 minutes solid-liquids point are carried out with 800G using centrifugal separator From recovery supernatant.Then, using centrifugal separator with 800G by supernatant solid-liquid separation 1 hour, reclaim solid constituent.

Process 3：Break process

Concentration according to solid constituent is the mode of 10 weight %～30 weight %, to the 2nd solid-liquid point by process 2 Add water in resulting solid constituent, ultrasonic irradiation is carried out with the frequency of 20kHz using homogenizer, so as to be consolidated Body composition it is broken.It should be noted that the time of break process is not fixed, carry out to by fully crushing.

Process 4：Granulating and drying process

Concentration according to solid constituent is the mode of 10 weight %～30 weight %, is added in the solid constituent to after crushing Water, makes raw material slurry, and according to table 1 binding agent and binding agent aggregation inhibitor are added.The addition of binding agent is included by addition The used ground slurry of used colloidal silica (mean diameter under used state is 3nm～20nm) comes Carry out.Binding agent aggregation inhibitor has used corn starch, wheat flour.

Then, raw material slurry is spray-dried using the spray dryer of parallel flow type, so as to carry out pelletize, is produced The block of raw material abrasive particle.The spray dryer of parallel flow type is following apparatus：By to being dried room spray slurry, and with this concurrently Injection hot blast, so that slurry drying.Sprayer unit has used the sprayer unit of rotary disc-type.Spray condition is：Rotational circle A diameter of 50mm of disk (aerosol apparatus), 20000 revs/min of disc rotation speed, spray volume 30mL/ minutes, the inlet temperature of hothouse 150 degree of (rotating circular disk position temperature), 50 degree of outlet temperature.

Process 5：Firing is processed

The block of raw material abrasive particle is put into into crucible, is fired 2 hours with the temperature shown in table 1 in muffle furnace, make raw material mill The aggregation of grain.

Process 6：Break process

For the aggregation of the raw material abrasive particle fired below 800 DEG C, carried out with frequency 20kHz using homogenizer Ultrasonic irradiation, so as to carry out the broken of solid constituent, produces grinding abrasive particle.On the other hand, in the temperature more than 800 DEG C The aggregation of the raw material abrasive particle that degree is fired, has carried out 4 hours crushing using ball mill.

Process 7：Big particle removal is processed

More than 15 μm that are mixed into grinding abrasive particle of big particle is removed by filtering.

(measure of comprcssive strength)

According to JIS R1639-5, the comprcssive strength of the grinding abrasive particle by processing 7 each sample for obtaining is surveyed It is fixed.As a result it is shown in table 1.In table 1, with the scope and meansigma methodss of measured value illustrate from each sample it is random extract out n (n=20 with On) comprcssive strength of individual sample.

(evaluation of the degree that grinding rate, damage are produced)

The grinding abrasive particle of each sample is dispersed in water, ground slurry is made, using made ground slurry, as tool The double-side polishing apparatus of standby planetary gears, using the 1st milled processed described in Japanese Unexamined Patent Publication 2012-133882 publications In double-side polishing apparatus 400 used, glass substrate is carried out at the 1st grinding of above-mentioned embodiment with following grinding conditions Reason.It should be noted that up and down the surface of price fixing has used the grinding pad of the suede type of polyurathamc.In addition, grinding The slurry discharged from price fixing afterwards is again returned in lapping device, so as to recycle.

Grinding wear particle concentration：10 weight %

The load of upper price fixing and lower price fixing to glass substrate：100g/cm²

Milling time：60 minutes

Glass substrate has used 2.5 inches of alumina silicate glass.The piece of the glass substrate being ground in 1 milled processed Number is 100.

After the 1st milled processed has been carried out, glass substrate is cleaned, is dried, afterwards by the glass base before and after grinding The weight difference of plate calculates grinding rate.In addition, being scraped to glass baseplate surface two sides using the surface examining device of laser instrument formula The quantity of trace and pit is calculated, and A will be evaluated as less than the situation of 20/one side, by 20 less than 100/one side Situation be evaluated as B, situation more than 100/one side is evaluated as into C.If A and B, then can suppress the product of the damage of glass It is raw.Grinding rate is represented so that sample 4 to be set to 100% relative value.As a result it is shown in table 1.

In table 1, mix ratio represents the mix ratio (matter of this 3 kinds of compositions of raw material abrasive particle, binding agent, binding agent aggregation inhibitor Amount part).

[table 1]

As shown in table 1, it is known that：The grinding abrasive particle of the sample 1,2 regenerated with regard to being not added with binding agent, below 800 DEG C Although at a temperature of the sample 1 fired do not produce the damage of glass substrate, comprcssive strength is little, and grinding rate is low. In addition we know, although the comprcssive strength of sample 2 fired at a temperature of more than 800 DEG C is big, grinding rate is high, produce The damage of many glass substrates.

On the other hand, the grinding abrasive particle of the sample 3～5 for regenerating with regard to adding binding agent, it is known that：Comprcssive strength is In the range of 0.1MPa～20MPa, grinding rate is high, it is suppressed that the generation of the damage of glass substrate.Particularly, with regard to the addition of The grinding abrasive particle of the sample 4,5 of binding agent aggregation inhibitor, it is known that：Although comprcssive strength is same degree with sample 3, grind Speed is sufficiently high, does not produce the damage of glass substrate.

It should be noted that using microscope to the addition of the raw material abrasive particle of the sample 4 and 5 of binding agent aggregation inhibitor Aggregation is observed, and results verification is to the substantially equal size of the size of the binding agent aggregation inhibitor for existing and being added Hole.In addition, the surface of the grinding abrasive particle for the sample 3～5 that with the addition of binding agent, has carried out the element point based on EDX Butut, results verification is to being configured with binding agent.

(firing temperature dependence)

In addition, the impact in order to investigate firing temperature, by firing temperature 800 DEG C, 1000 DEG C are changed to, in addition with Used slurry is regenerated into (sample 6,7) under the conditions of the identical of sample 3.As a result, with regard to sample 6, comprcssive strength it is average It is worth for 14MPa, the relative value of grinding rate is 112, it is B grades to damage the degree for producing.On the other hand, the pressure resistance of sample 7 The meansigma methodss of degree are 53MPa, and the relative value of grinding rate is 112, and it is B grades to damage the degree for producing.Wherein, compare in detail The degree for producing is damaged, results sample 3 is 31/face, on the other hand, sample 7 is 87/face.I.e., it is known that：According to firing The difference of temperature, also generates difference in B grades.

(continuously grinding detection)

In addition, using the regeneration slurry of sample 1,3～5, being carried out continuously 5 batches (substrate processing piece number is 500) Above-mentioned 1st milled processed, have rated damage the degree for producing afterwards.As a result, sample 1 is C grades, but other samples are respectively With the grade identical grade shown in table 1.Speculate this is because, due to the comprcssive strength of the regeneration slurry of sample 1 it is low, thus quilt Milled processed is destroyed, and little particle increases.

(2) with regard to the embodiment of the 2nd embodiment

In order to confirm the effect of second embodiment of the present invention, following experiments have been carried out.Specifically, for as raw material The used ground slurry of abrasive particle, as shown in table 2 and table 3, makes condition different and is regenerated, for regeneration after grind Mill abrasive particle (sample 11～13,12A, 13A), the broken required time of determination sample 11,12A, 13A, in addition, for Sample 11～13 determines comprcssive strength, and then determines grinding rate when having carried out milled processed.In addition, with regard to sample 11～ 13, have rated the generation degree of the damage produced in glass substrate.

Process 1：Foreign body removal is processed

Process 2：Solid-liquid separation process

Process 3：Break process

Concentration according to solid constituent is the mode of 10 weight %～30 weight %, to the 2nd solid-liquid point by process 2 Add water in resulting solid constituent, ultrasonic irradiation is carried out with frequency 20kHz using homogenizer, so as to carry out solid Composition it is broken.It should be noted that the time of break process is not fixed, carry out to by fully crushing.

Process 4：Granulating and drying process

Concentration according to solid constituent is the mode of 10 weight %～30 weight %, is added in the solid constituent to after crushing Water, makes raw material slurry, and according to table 2 and table 3 pore creating material and binding agent are with the addition of.The addition of binding agent is included by addition and used The used ground slurry of the colloidal silica (mean diameter under used state be 3nm～20nm) crossed is entering OK.Pore creating material has used corn starch, wheat flour.

Process 5：Firing is processed

The block of raw material abrasive particle is put into into crucible, is fired 2 hours with 600 degree in muffle furnace, make the set of raw material abrasive particle Body.

Process 6：Break process

For the aggregation of raw material abrasive particle, ultrasonic irradiation is carried out with frequency 20kHz using homogenizer, so as to carry out solid Crushing for composition, produces grinding abrasive particle.

Process 7：Big particle removal is processed

(measure of comprcssive strength)

According to JIS R1639-5, the comprcssive strength of the grinding abrasive particle by processing 7 each sample for obtaining is surveyed It is fixed.As a result it is shown in table 3.In table 3, with the scope and meansigma methodss of measured value illustrate from each sample it is random extract out n (n=20 with On) comprcssive strength of individual sample.

(evaluation of the degree that grinding rate, damage are produced)

Grinding wear particle concentration：10 weight %

Milling time：60 minutes

After the 1st milled processed has been carried out, glass substrate is cleaned, is dried, afterwards by the glass base before and after grinding The weight difference of plate calculates grinding rate.In addition, being scraped to glass baseplate surface two sides using the surface examining device of laser instrument formula The quantity of trace and pit is calculated, and A will be evaluated as less than the situation of 20/one side, by 20 less than 100/one side Situation be evaluated as B, situation more than 100/one side is evaluated as into C.If A and B, then can suppress the product of the damage of glass It is raw.Grinding rate is represented so that sample 12 to be set to 100% relative value.As a result it is shown in table 3.

In table 2 and table 3, mix ratio represents the mix ratio (mass parts) of this 3 kinds of compositions of raw material abrasive particle, pore creating material, binding agent.

[table 2]

The sample 11 regenerated with regard to being not added with pore creating material, it is known that：60 are needed till fully crushing in above-mentioned process 6 Minute.So, it is impossible to fully crushed with the relatively shorter time, it is impossible to obtain being suitable for the grinding mill of the size of milled processed Grain.

(firing temperature dependence)

In addition, the impact in order to investigate firing temperature, by firing temperature 500 DEG C, 800 DEG C are changed to, in addition with Sample 11,12A, 13A is each under the conditions of identical by the regeneration of used slurry, have rated as described above it is broken required for Time, it is as a result identical.

[table 3]

The sample 12,13 regenerated with regard to adding pore creating material, as shown in table 3, it is known that：Comprcssive strength be 0.1MPa～ In the range of 20MPa, grinding rate is high.In addition we know, although sample 12,13 is the material for adding binding agent and regenerating, The damage of glass substrate is not almost produced.

It should be noted that the aggregation of the raw material abrasive particle of sample 12,13 is observed using microscope, as a result really Recognize the hole of the size for having substantially equal with the size of the pore creating material for being added.In addition, for the sample that with the addition of binding agent The surface of the grinding abrasive particle of product 12,13, has been carried out based on the distribution diagram of element of EDX, and results verification is to being configured with binding agent.

More than, the system of manufacture method, grinding abrasive particle, ground slurry and glass substrate to the ground slurry of the present invention The method of making has been described in detail, but the present invention is not limited to above-mentioned embodiment, it is of course possible to without departing from the present invention's Various improvement and change are carried out in the range of purport.

Symbol description

1 grinding abrasive particle

3 raw material abrasive particles (abrasive particle)

5 binding agents

7 binding agent aggregation inhibitors (pore creating material)

9 holes

The block of 10 raw material abrasive particles

The aggregation of 20 raw material abrasive particles

Claims

1. a kind of manufacture method of ground slurry, it is the slurry of the grinding abrasive particle comprising the milled processed for glass substrate The manufacture method of material, it is characterised in that the manufacture method possesses：

The addition for adding binding agent in the raw material slurry of the raw material abrasive particle comprising the raw material as the grinding abrasive particle is processed；

Make comprising the binding agent raw material slurry be dried and make containing the binding agent raw material abrasive particle block be dried at Reason；With

At the firing of the aggregation for being fired and making the raw material abrasive particle containing the binding agent to the block of the raw material abrasive particle Reason.

2. the manufacture method of ground slurry as claimed in claim 1, wherein, the binding agent includes silica dioxide granule.

3. the manufacture method of ground slurry as claimed in claim 1 or 2, wherein, the mean diameter of the binding agent be 3nm～ 20nm。

4. the manufacture method of the ground slurry as any one of claims 1 to 3, wherein, the manufacture method further has It is standby to crush the aggregation of the raw material abrasive particle and the break process of the making grinding abrasive particle,

The mean diameter of the grinding abrasive particle made by the break process is 0.5 μm～10 μm.

5. the manufacture method of the ground slurry as any one of Claims 1 to 4, wherein, in the addition is processed, enter One step adds the binding agent aggregation inhibitor for suppressing the mutual coagulation of the binding agent,

In the dried, the binding agent is distributed in the raw material by the binding agent aggregation inhibitor In the block of abrasive particle.

6. the manufacture method of ground slurry as claimed in claim 5, wherein, in the firing is processed, by the original The block of material abrasive particle is fired and makes at least a portion of the binding agent aggregation inhibitor disappear.

7. the manufacture method of the ground slurry as described in claim 5 or 6, wherein, the binding agent aggregation inhibitor is polysaccharide Class.

8. the manufacture method of the ground slurry as any one of claim 1～7, wherein, the temperature below 800 DEG C is entered The row firing.

9. the manufacture method of the ground slurry as any one of claim 1～8, wherein, in the dried, lead to Crossing to be spray-dried is dried the raw material slurry comprising the binding agent.

10. the manufacture method of the ground slurry as any one of claim 1～9, wherein, the raw material slurry is included in Cerium oxide particles used in the milled processed of glass substrate.

A kind of 11. grinding abrasive particles, it is the grinding abrasive particle used in the milled processed of glass substrate, it is characterised in that at this In grinding abrasive particle, silica dioxide granule is present between ceria or zirconic granule as binding agent.

12. a kind of ground slurries, it is characterised in that it includes the grinding abrasive particle described in claim 11.

13. a kind of manufacture methods of glass substrate, it is characterised in that using by any one of claim 1～10 Described in grinding abrasive particle or claim 12 described in ground slurry that the manufacture method of ground slurry makes, claim 11 Ground slurry and the surface of glass substrate is ground.

A kind of 14. manufacture methods of ground slurry, it is the grinding of the grinding abrasive particle comprising the milled processed for glass substrate The manufacture method of slurry, it is characterised in that the manufacture method possesses：

The addition for adding pore creating material in the raw material slurry of the raw material abrasive particle comprising the raw material as the grinding abrasive particle is processed；

Make comprising the pore creating material raw material slurry be dried and make containing the pore creating material raw material abrasive particle block be dried at Reason；With

The block of the raw material abrasive particle is fired and makes at least a portion of the pore creating material disappear, so as in the pore creating material The interstitial firing in part of the block of the raw material abrasive particle being located at is processed.

The manufacture method of 15. ground slurries as claimed in claim 14, wherein, it is described to make in the block of the raw material abrasive particle The mean diameter of hole agent is 3 μm～20 μm.

The manufacture method of 16. ground slurries as described in claims 14 or 15, wherein, in the addition is processed, further Addition is configured at the binding agent on the surface of the raw material abrasive particle,

In the dried, the binding agent is distributed in the block of the raw material abrasive particle by the pore creating material In.

17. a kind of manufacture methods of glass substrate, it is characterised in that using by any one of claim 14～16 Ground slurry that the manufacture method of ground slurry makes and the surface of glass substrate is ground.