CN101134301A - Polishing pad, method of manufacturing the polishing pad, and cushion layer for polishing pad - Google Patents

Abstract

A polishing pad capable of stably performing, with a high polishing speed, the flattening processing of the materials requiring a high degree of surface flatness such as silicon wafers for semiconductor devices, magnetic disks, and optical lenses, comprising a polishing layer formed of a hardening composition hardened by energy ray and having the irregularities formed by the photolithography method provided on the surface thereof and a polishing layer resin formed of distributed abrasive grains having an ionicity radical of 20 to 1500 eq/ton, whereby the productions such as sheeting and surface finishing of grooves can be performed easily, excellent accuracy of thickness and high and uniform polishing speed can be provided, a variation in quality among individuals can be eliminated, a change of processing pattern can be performed easily, micro processing is allowed, burrs are prevented from occurring in forming the irregularities, slurry-less measure is taken, abrasive grains can be mixed at a high density, and the possibility of occurrence of scratch due to coagulation of abrasive grains can be reduced even if the abrasive grains are distributed.

Description

Grinding pad and manufacture method thereof and grinding pad cushion

The application is that application number is 200510054379.5, the applying date is that November 28 calendar year 2001, denomination of invention are grinding pad and manufacture method thereof and grinding pad with please in the division of the application for a patent for invention of cushion.

Technical field

The present invention relates to a kind of grinding pad, its can carry out the grinding pad of fine Surface Machining easily and utilize as it is characterized by industrial, and can be used as with stable and high grinding rate and the material of the requirement height surface of the optical material of silicon wafer, memory disc, disk, optical lens or the speculum etc. used as semiconductor device, glass plate, metal etc. is carried out the grinding pad that planarization process handles and use.Grinding pad of the present invention, be particularly suitable for silicon wafer and on be formed with the equipment (multilager base plate) of oxide skin(coating), metal level etc., before stacked these layers of formation, carry out using in the operation of planarization.

The invention still further relates to the manufacture method of above-mentioned grinding pad and the cushion of grinding pad.

Background technology

Typical example as the material that requires the height surface can exemplify the disk of making semiconductor integrated circuit monocrystalline silicon (IC, LSI), that be called silicon wafer.Silicon wafer for the reliable semiconductor of the various films that are formed for circuit production engages, requires in each film production process surface processing flatly accurately in the manufacturing process of IC, LSI etc.

Usually, grinding pad is fixed on and is called on the rotatable support disk of pressing nog plate (platen), and semiconductor wafer is fixed on and can carries out on the disk that is known as grinding head of revolution motion.By rotatablely moving of both sides, between pressure nog plate and grinding head, produce relative velocity, the solution (slip) that is dispersed with the grinding-material of the subparticle (abrasive particle) of suspended silica system or ceria system etc. in alkaline solution or acid solution is flowed, Yi Bian grind, planarization process between the gap of grinding pad and wafer.At this moment, when grinding pad moves in wafer surface, on wafer surface, push abrasive particle at contact point.Therefore,, carry out the grinding of machined surface, reduce by the jump of grinding-material or surface roughness by the slip dynamic friction effect between wafer surface and the abrasive particle.The so-called CMP processing of such attrition process.

＜(I) grinding pad 〉

As the mirror ultrafinish liner of the semiconductor wafer that is used for above-mentioned grinding step, be well known that the grinding pad of polyurethane foam build, be the grinding pad of the abrasive cloth type of dipping polyurethane resin in the nonwoven, the cascade type grinding pad that these 2 kinds of liners are fit together at polyester.

As the grinding pad of described polyurethane foam build, using the cavitation rate usually is about 30～35% polyurethane foaming body thin plate.And it also is known disperseing the technology of the grinding pad of hollow molecule or water soluble polymer powder etc. in the matrix resin at polyurethane etc. that the spy shows to be put down in writing in the flat 8-500622 communique.

In addition, in these grinding pads, flow, keep slip as purpose with what improve slip, it also is known forming concavo-convex grinding pads such as bar ditch or through hole on the grinding layer surface.Form concavo-convex known technology as grinding layer, open the spy that flat 11-48129 communique, spy are opened flat 11-58219 communique or the special flat 11-70462 communique etc. opened discloses the technology that the operator uses utensils such as cutter, graver, diamond capstan to carry out at grinding pad.

Above-mentioned known cavitation rate is about 30～35% polyurethane foaming body thin plate, the planarization capability excellence that it is local, but compression ratio is about 0.5～1.0%, less, therefore, because the resiliency deficiency, so be difficult to apply uniform pressure to the entire wafer face.Therefore, establish soft cushion usually in addition at the back side of polyurethane foaming body thin plate, carry out attrition process.

The grinding pad of polyurethane foam build or show the grinding pad put down in writing in the 8-500622 communique the spy all constitutes grinding layer, if the abradant surface abrasion, the face that then becomes new surface constitutes grinding layer.Promptly because whole grinding pad has uniform elastic characteristic, so have problems in the uniformity or the jump characteristic of grinding rate or grinding charge.Promptly when the raw material that constitute the grinding charge surface have nonhomogeneous hardness, exist a soft side to be pruned more, can not obtain the problem of flatness from microcosmic.In addition, when grinding, needing overleaf promptly also must have the operation of applying cushion, so be difficult to the requirement that correspondence reduces cost pressing the nog plate installation side to be arranged on the cushion of dipping polyurethane resin in the nonwoven of polyester system except grinding pad manufacturing process.

These grinding pads, in process of lapping, in the hole on grinding layer surface, accumulate abrasive particle in the slip, swarf etc., grinding rate is reduced, so in grinding the way, need regularly use the head of evaporation diamond abrasive grain, lapped face is created the finishing process on brand-new surface, owing to the hole in the grinding pad does not have inconsistent etc. the reason of evenly dispersion, the size in hole, form, even carry out finishing process, upgrading the surface can not become same surface yet, thereby has the different problem of abrasive characteristic.And become and revise in the operation and can not grind, the reason that production efficiency is descended.Exist in addition when revising operation and cut mat, except grinding grinding charge, the problem that liner is consumed.

In addition, employed slip flows when grinding in order to make, and it is kept, so carry out the concavo-convex processing in groove or concentric circles or hole etc. at abradant surface.As this processing method, adopted by the cutting of graver or cutting machines etc., the method for pressurization etc. by the specified metal mould, preceding two methods exist, and are difficult to prevent the deviation of the quality that the individual difference according to the operator causes; Be difficult to change processing graphic pattern; Microfabrication has limitation; Produce burr during cutting; Produce the problem of scar etc. on by the abradant surface of grinding-material, exist the cost of making metal pattern to rise in one method of back; By pressure, the problem that the rerum natura of processing periphery changes etc.

As the method that solves above-mentioned back problem, proposed in WO9830356 to be put down in writing, use photosensitive composite, remove with ultraviolet ray, laser curing irradiation portion not exposure portion, on supporter the aqueous photoresist of coating, utilize photolithographic abradant surface processing.

When stating aqueous photoresist in the use and being coated with, if make the to a certain degree liner of thickness,, launch after crossing certain hour, going wrong aspect the precision of thickness because of the cause of aqueous resin.As in order to improve this problem, produce and import pad etc., will cause the decline of efficient.In addition, because be aqueous before the exposure, so the management of product (temperature treatment etc.) difficulty till before the exposure solidification, depositing of goods is also difficult, becomes the main cause that reduces operating efficiency.In addition, can not solve the problem of in process of lapping, regularly introducing finishing process.

Summary of the invention

The object of the present invention is to provide the Surface Machining etc. of a kind of thin plateization, groove etc. to produce easily, thickness and precision excellence, grinding rate height, can obtain the grinding pad of uniform grinding rate.

In addition, in the cascade type grinding pad of stacked cushion, for make and grinding layer between elastic characteristic variant, and raising abrasive characteristic, open flat 11-48131 communique as the spy and put down in writing, the section of carrying out is cut apart the processing of intermediate layer portion, and at this moment also exists and above-mentioned same problem.Like this, in grinding mat,, carry out various concavo-convex processing at grinding layer or the layer beyond it, but all do not eliminate above-mentioned problem points in order to improve abrasive characteristic.

Another object of the present invention is to, solve the above-mentioned problem points of putting down in writing, a kind of heterogeneity that does not have by the quality of individual difference is provided, and can change processing graphic pattern easily, can carry out microfabrication, can be corresponding various by grinding-material, and form can deckle-edged grinding pad and manufacture method thereof when concavo-convex.

Another purpose of the present invention is to provide that a kind of grinding rate is fast, the uniformity or the jump excellent of grinding charge, and there is no need pressing the nog plate installed surface that the grinding pad of cushion is set.

The grinding pad of above-mentioned foaming build, because be low, the soft mat of spring rate, as shown in Figure 6, the state deflection that grinding layer 31 itself will become with the circuit Figure 32 in the semiconductor wafer in the process of lapping, dielectric film 34 between the pattern 33 is exceedingly ground, from microcosmic, ground the planarization characteristics existing problems of object.In addition, the grinding pad of foaming build, the spring rate that improves its grinding layer has limitation, and the raising of planarization characteristics also has limitation.

Up to now, as the rerum natura of grinding layer, the grinding that improves spring rate is lined with following.1. the hydraulic pressure modulus when grinding layer applies the compression stress of 4～20psi is the grinding pad (spy opens flat 6-21028 communique) of 250psi for the compression stress of lpsi.2. use the grinding pad (spy opens the 2000-202763 communique) of tensile elasticity rate as the grinding layer below the above 500Mpa of 1Mpa.3. crooked elastic rate is 3500～4000kg/cm ²Grinding pad (spy opens the 2001-105300 communique).But, being documented in above-mentioned grinding pad in these, though planarization characteristics obtains raising to a certain degree, can't say to obtain sufficient planarization characteristics.

Another object of the present invention is to provide the grinding pad of the planarization characteristics excellence of being ground object.

Use polyurethane thin plate in the past, the grinding pad that is provided with cushion have following problem.

(1), uses dipping to have the nonwoven of the resin in continuous hole widely, but have the problems such as variation of the compression property that the immersion by the disperse of nonwoven, slip liquid causes as cushion.

(2) though bring into use foaming polyurethane plastic foams, there is the stabilisation difficulty of foamed state in making, and owing to has hole, the problem big the residual deformation of repeated load with independent hole.

A further object of the present invention is to provide the disperse of compression property few, and the variation of the compression property that is caused by the immersion of slip is little, and can reduce the cushion to the residual deformation influence of repeated load of grinding layer.

＜(II) grinding pad of no slip 〉

As the grinding pad that uses at CMP, also known following technology.

1. at the elastic polyurethane layer, (U.S.'s special permission 3,504,457) of stacked synthetic leather layer as grinding layer.

2. the nonwoven at foamed polyurethane layer applying dipping polyurethane constitutes (spy opens flat 6-21028 communique)

3. it is characterized in that, be provided with lapped face, be provided with the rigid element of selected thickness and rigidity by described lapped face, and in order to give identical in fact power to described rigid element, and elastomeric element is set by described rigid element, described rigid element and described elastomeric element are given elastic bending power to described lapped face, bringing out bending, and should bending be fit to all shapes on described machining object surface and keep the rigidity of being controlled (spy opens flat 06-077185 communique) for the local shape on described machining object surface in the control of described lapped face.

4. it is characterized in that having big top layer A of vertical coefficient of elasticity EA and the little B of lower floor of vertical coefficient of elasticity EB, and the abrasive cloth (spy opens flat 11-156724 communique) of bigger than the vertical coefficient of elasticity of described B floor at least intermediate layer M is set between two-layer A and B.

5. constitute by grinding layer, intermediate layer and the soft bottom higher than grinding layer elasticity, and the divided liner in intermediate layer (spy opens flat 11-48131 communique).

Problem points below the above-mentioned various grinding pads of being put down in writing in 1.～5. exist.

1. in this mode, about comprehensive uniformity, elastic polyurethane layer performance homogenising is applied to the effect of the load on the wafer, because use soft synthetic leather on the grinding layer of top layer, though do not have the problem of cut etc., exist in the bad problem of small field planarization characteristics.

2. in the lamination of polyurethane and nonwoven, nonwoven is brought into play and the above-mentioned identical effect of elastic polyurethane layer 1., and obtains uniformity.In addition, because grinding layer also has the foamed polyurethane layer of hard, so than synthetic leather planarization characteristics excellence, but do not reach in recent years, to the raising of small field planarization characteristics requirement level or the level that in the grinding of metal film, requires.In addition, the method for attempting the hardness by further raising hard polyaminoester layer can improve planarization characteristics, but at this moment causes a large amount of cuts occurring, and is impracticable.

3. grinding layer, rigid layer, elastic layer structure are, the planarization characteristics that the grinding layer on the top layer has suitable hardness variation not cause cut, hardness not to have to improve improves at the 2nd layer rigid layer.This will solve the problem points of above-mentioned 2. mode, but at this moment the thickness of grinding layer is designated as below 0.003 inch, and when using in this thickness reality, grinding layer is reamed, and have the short shortcoming of life of product.

4. the basic thought of this mode is identical with above-mentioned 3. mode, limits the spring rate scope of each layer, so that obtain more scope of efficient, but in this mode, the method for few of in fact realization is difficult to make grinding pad.

5. the basic thought of this mode is also identical with above-mentioned 3. mode, in order further to improve the uniformity in the wafer face, middle rigid layer is divided into the size of regulation.But,, can not supply with cheap grinding pad at this operation of cutting apart cost cost.

In addition, these need make the high slip of price flow in process of lapping 1. to 5. grinding pad, thereby relate to the rising of manufacturing cost.Therefore, just developing a kind of so-called bonded-abrasive formula grinding pad that contains abrasive particle at grinding layer.Such bonded-abrasive formula grinding pad need not make the slip of high price flow in grinding step as free abrasive formula grinding pad.

As bonded-abrasive formula grinding pad, a kind of 6. grinding pad of this spline structure of mixed oxidization cerium particulate (spy opens the 2000-354950 communique, the spy opens the 2000-354950 communique) in foaming polyurethane resin is for example disclosed.But there is the excessive concentration of the abrasive particle in the grinding layer in this grinding pad, and desire will improve grinding rate, then has to and with the problem of slip.

In addition, disclose and a kind ofly 7. disperseed abrasive particle, be coated on the grinding pad (spy opens the 2000-190235 communique) of this spline structure on the film then at the binder solution in being dissolved in solvent.But this grinding pad just mixes resin and abrasive particle in solvent, so there is the cohesion that causes particulate, is easy to generate the problem of cut.

In addition, disclose a kind of 8. on base material, with the fixing granulation particulate that 2 cohesions of 1 abrasive particle below the 0.5 μ m is made its 1～30 μ m that does not contain adhesive resin as grinding agent of adhesive resin, the polishing pad of this spline structure (spy opens the 2000-237962 communique).But this grinding pad is though owing to effectively abrasive particle is joined in the resin, so condense abrasive particle energetically, exist this agglomerate easily to produce the problem of cut.

In addition, 9. disclose a kind of is resin material below the average grain diameter 50 μ m of solid at normal temperatures and maximum particle diameter that the abrasive particle of 2 μ m mixes, and then it is filled into the grinding pad (spy opens the 2000-190232 communique) that pressurized, heated is shaped in the metal pattern.But this grinding pad exists in the initial stage and is difficult to mix equably fat coccoid and abrasive particle coccoid, and as improving the wear particle concentration in the grinding pad, then the resin as bonding agent reduces the problem that is shaped.

As above-mentioned explanation, present situation does not have and can meet the demands with bonded-abrasive formula liner.

Another object of the present invention is to, forming fine pattern on the semiconductor wafer as being used for, in the grinding pad that polishing semiconductor wafer in the operation of the small concavo-convex planarization of this pattern is waited with pad and use, provide a kind of that adapt to no slip and abrasive characteristic well, the few grinding pad of generation of cut.

Another object of the present invention is to; on being used in semiconductor wafer, form fine pattern and in the grinding pad in the operation of the small concavo-convex planarization of this pattern; provide a kind of adaptation not have slip; can be mixed into extremely high concentration to abrasive particle, although and the cut that disperses abrasive particle to cause with high concentration ground by the abrasive particle cohesion produce few polishing semiconductor wafer liner.

＜(I) grinding pad 〉

The present invention is the grinding pad with grinding layer, it is characterized in that, described grinding layer is to use the solidification compound by energy line curing to form, and described grinding layer have from the teeth outwards by photoetching process form concavo-convex.

Described grinding pad, the production of Surface Machining such as its thin plateization, groove etc. is easy, the thickness and precision excellence, the grinding rate height can obtain uniform grinding rate.

Described grinding layer, it is desirable at load is below 1.49 for the confficient of static friction between the glass of 4400gf, the coefficient of kinetic friction is below 1.27.

In the described grinding pad, it is desirable to described solidification compound and contain the solid macromolecule compound.

In described grinding pad, can be directly grinding layer as grinding pad, also overleaf (reverse side of abradant surface) stacked cushion as grinding pad.

Has in the grinding pad of grinding layer, it is desirable to described grinding layer and do not have the hole, and dynamic elastic modulus ratio is more than the 200Mpa that the dynamic elastic modulus ratio of described cushion is lower than the dynamic elastic modulus ratio of described grinding layer.

In the past, the spring rate of grinding layer was same as described above, was the spring rate that hydraulic pressure modulus, tensile elasticity rate, crooked elastic rate etc. are all measured under static conditions arbitrarily.But, during actual the grinding, rotating with grinding pad as the semiconductor wafer that grinds object etc., grinding pad is subjected to being subjected to periodically pressurization, release repeatedly.Therefore among the present invention, the difference of the grinding layer areal deformation amount of grinding pad is conceived to think that the dynamic elastic modulus ratio corresponding to the spring rate under the dynamic condition inquires into.Its result, find by using the ratio high material of grinding layer dynamic elastic modulus ratio in the past, be that dynamic elastic modulus ratio is the material of the above high dynamic elastic modulus ratio of 200Mpa, can solve by problem that take place, that relate to the planarization characteristics of grinding object in the grinding layer grinding pad of in the past low dynamic elastic modulus ratio.

Dynamic elastic modulus ratio of the present invention is the value that is equivalent to the elasticity item of dynamic viscoelastic, the rigidity of the material when expression applies dynamic vibration or distortion.The pad that this class dynamic elastic modulus ratio is high, as shown in Figure 5, for periodic distortion, the deflection of grinding pad 31 is few, and the flatness of the dielectric film 34 between the pattern 33 of the circuit Figure 32 in the semiconductor wafer is good.

The dynamic elastic modulus ratio of described grinding layer is to be desirable more than the 2000Mpa, the upper limit of the dynamic elastic modulus ratio of grinding layer has no particular limits, if but dynamic elastic modulus ratio is too high, on semiconductor wafer, produce scar (cut) easily, so dynamic elastic modulus ratio it is desirable to below the 2Gpa, better is below the 1.5Gpa, it is desirable to below the 1Gpa especially.It is desirable to dynamic elastic modulus ratio especially and be 200Mpa～2Gpa, better be 200Mpa～1Gpa.In addition, it is desirable to grinding layer is the layer that does not have the hole.For the dynamic elastic modulus ratio that makes grinding layer is more than the 200Mpa, the layer that it is desirable to not contain with foaming body etc. the hole forms grinding layer.

It is desirable to,, also have the dynamic elastic modulus ratio cushion lower than the dynamic elastic modulus ratio of grinding layer except the dynamic elastic modulus ratio with grinding layer is a described grinding layer more than the 200Mpa.When grinding layer has high dynamic elastic modulus ratio, though being ground all bending, the warpages of object uprises, but by cushion is set, the grinding layer of high rigidity and the tracing ability that is ground between the object become good, are eliminated by cushion and are ground all fluctuating bendings of object etc.Therefore, even use the high grinding layer of dynamic elastic modulus ratio, can not damage yet ground object by the uniformity in the abradant surface (planarization characteristics).As long as the dynamic elastic modulus ratio of cushion lower than the dynamic elastic modulus ratio of grinding layer, just has no particular limits, and it is desirable to about 0.1～100Mpa, and that better is 0.1～50Mpa, planarization characteristics is good when it is desirable to 0.1～30Mpa especially.

In grinding pad of the present invention, it is desirable to described grinding layer is to be made of grind table surface layer and back layer, described back layer is to use the solidification compound by energy line curing to form, and described back layer have from the teeth outwards by photoetching process form concavo-convex.

Grinding pad with said structure has following effect: promptly, the irregular of quality that is not caused by individual difference differs, and easily changes processing graphic pattern, but microfabrication can be adapted to variously by grinding-material, and forms and does not produce burr when concavo-convex.

In above-mentioned grinding pad, better is, above-mentioned back layer is to use the solidification compound by energy line curing to form, and above-mentioned back layer have by photoetching process form concavo-convex.

Stacked cushion also can relax at the suffered pressure of abradant surface in addition, has the effect that improves abrasive characteristic.In addition, because of not needing the operation that cushion is stacked, so cost is low, and have with grinding layer bonding consumingly, and the grinding pad of incorporate cushion.

In the grinding pad of the present invention, grinding layer is made up of grind table surface layer and back layer, and the hardness of described grind table surface layer is higher than the hardness of described back layer, and its difference of hardness is more than 3 with Shore D hardness.

By such formation, it is fast to access grinding rate, the uniformity of grinding charge or jump excellent, there is no need the grinding pad at the cushion of pressing the nog plate installed surface to fit to form with different materials.Promptly, form the low back layer of hardness, needn't and press the grinding pad of establishing cushion between the nog plate in addition at grinding pad and become from the grinding layer surface to being installed in the installed surface direction side of pressing nog plate by at grinding pad itself.Difference of hardness became the grinding pad that must stackedly use the cushion that forms with identical in the past another kind of material less than 3 o'clock.

Back layer, can form hardness reduces to pressure nog plate installed surface side continuously from grinding layer, also can be the high sandwich construction of hardness ratio pars intermedia that becomes the back layer surface element of pressing nog plate installed surface side, also can be in addition the hardness of back layer surface element and pars intermedia identical be 2 layers of structure that back layer forms homogeneous hardness.Difference of hardness is the difference between the lowest hardness part of back layer.Under the situation of sandwich construction, the hardness of the abradant surface of grinding pad and back layer surface element can be similar to identical, at this moment can distinguish the surface and the back side of grinding pad, and with them as abradant surface.In addition, superficial layer and the back of the body and the hardness approximately equal of layer, and the hardness ratio in intermediate layer they when low, difference of hardness is the difference of hardness between superficial layer or back layer and the intermediate layer.

Above-mentioned grinding pad, described grinding layer and back layer, thereby be by load energy line on the thin plate that forms by solidification compound, pine for at least aly form described difference of hardness, because of can form easily have decide the grinding pad of difference of hardness, so desirable.

Load is meant heating or irradiation energy line, make unreacted solidification compound thin plate according to each one form fixed difference of hardness and solidifying.The formation of difference of hardness is to be undertaken by control load.To the control of load, when heating, be to be undertaken by control temperature, time etc.; And the occasion of energy line is by to the control of illuminate conditions such as the intensity of energy line, irradiation time or by adjustment of components selection such as the permeability of solidification compound, light trigger or addition etc. is carried out.

Grinding pad of the present invention it is desirable to described grinding layer and uses identical solidification compound integrally formed continuously with described back layer.

Can make the incorporate grinding pad of grinding layer and cushion more easily thereby become.

The compression ratio of the grinding layer of grinding pad if consider resiliency, it is desirable to more than 0.5%.Better is more than 1.5%.The compressive recovery rate of the grinding layer after the processing if consider the resiliency of grinding layer, is desirable more than 50%.

In order to improve the spring rate of grinding layer, can pass through mechanical foaming or chemical blowing, foam.

What it is desirable to form on the surface of grinding layer is concavo-convex, is the groove that the slip that uses when grinding flows.

What it is desirable to form on the surface of grinding layer is concavo-convex, is the groove that the slip that uses when grinding accumulates.

Grinding pad of the present invention is that semiconductor wafer or precision machinery glass substrate are desirable to grind object.

The present invention is the manufacture method with grinding pad of grinding layer, it is characterized in that making described grinding layer by following photoetching process.

(1) by containing initator and energy line reactive compounds at least, and by the be shaped thin plate chemical industry preface of lamellar formed body of the solidification compound of energy line curing;

(2) induce modification to described lamellar formed body irradiation energy line, change the deliquescent exposure process of described lamellar formed body solvent;

(3) the described lamellar formed body behind the irradiation energy line utilizes solvent to remove the described solidification compound of part, thereby forms the developing procedure of the pattern of jog at least on one side.

Described manufacture method is a photoetching process, can produce by this photoetching process, but the quality that does not cause by individual difference irregular differ, easily change the processing graphic pattern microfabrication, can be adapted to various by grinding-material and form the grinding pad that does not produce burr when concavo-convex.

Described grinding layer and described back layer are to use by the hardening resin composition of energy line curing integrally formedly continuously, it is characterized in that having: with the thin plate chemical industry preface of the lamellar thin plateization of described hardening resin composition; Exposure process across mask material irradiation energy line; And the uncured solidification compound of dissolving removal, form concavo-convex developing procedure.

By having the method for described formation, can enough operations make the concavo-convex of grinding layer surface and have the back layer of buffer part, thereby obtain grinding pad cheaply.

The exposure process of grinding layer and the exposure process of back layer can carry out separately respectively, also can carry out from the two sides simultaneously.

Possess integrally formed grinding layer and back layer continuously at described grinding pad, the hardness height of the described back layer of hardness ratio of described grinding layer, this difference of hardness is in the manufacturing of the grinding pad more than 3 with Shore hardness, it is desirable to by load energy line on the lamellar formed body of described solidification compound, pine at least a, and form described difference of hardness.

Grinding pad of the present invention can not have cushion to use individually, in addition, can stackedly have with film, the nonwoven of the different compression properties of grinding layer, weave cotton cloth etc.

In addition, the present invention is the grinding pad that contains grinding layer and cushion at least, it is characterized in that it is more than the 200Mpa that grinding layer does not have hole and dynamic elastic modulus ratio, and the dynamic elastic modulus ratio of cushion is lower than the dynamic elastic modulus ratio of grinding layer.

In the described grinding pad, being formed with the mobile groove of slip that uses when grinding on the surface of grinding layer is its desirable form.In addition, in the described grinding pad, the groove that is formed with the slip that uses when storage grinds on the surface of grinding layer is its desirable form.Quilt as described grinding pad grinds object, and desirable can exemplify semiconductor wafer or precision machinery glass substrate.

Another invention of the application is the grinding pad that possesses grinding layer and back layer, it is characterized in that the described back side of the hardness ratio floor height of described grinding layer, and its difference of hardness is counted more than 3 with Shore D hardness.

In described grinding pad, it is desirable to be formed with the mobile groove of slip of use when making grinding on the surface of grinding layer.

In described grinding pad, it is desirable to be formed with the groove of the slip that uses when storage grinds on the surface that makes grinding layer.

In described grinding pad, it is desirable to be ground object is semiconductor wafer or precision machinery glass substrate.

＜(I) grinding pad cushion 〉

Grinding pad cushion of the present invention is the grinding pad cushion that is made of grinding layer and cushion, it is characterized in that compressive recovery rate is more than 90%.

Described cushion, compression property discrete few, the compression property that is caused by the immersion of slip liquid changes little, can reduce by the influence to the residual deformation of the repeated loading of grinding layer.

Described grinding pad is ideal with cushion to contain the compound with caoutchouc elasticity.

In addition, it is desirable grinding pad being carried out concavo-convex processing with the surface (pressing nog plate bonding plane side) of cushion.

By pressing the bonding side of nog plate to implement the concavo-convex processing of groove or shape for lugs etc., reduce its area.Thus, increased by the stress of load, and make compress variation big, thereby can make compression ratio big.

This is concavo-convex, is ideal with groove structure, network structure.

The pad the abradant surface side occur sometimes, if Shore hardness less than 50, then hardness is low excessively, and if compression ratio be more than 2.0%, the problem of then planarization precise decreasing.Compressive recovery rate also caused compressing sometimes less than 50% o'clock, and is undesirable.

In addition, by improving the rigidity of abradant surface side, described planarization precision is improved, but the uniformity in the face reduces.Therefore, require to be provided with cushion, to improve all compression ratio, the compressive recovery rates of liner.

Grinding pad of the present invention is to be ideal more than 90% with cushion with compressive recovery rate.

＜(II) grinding pad of no slip 〉

The grinding pad of no slip of the present invention is following pad.

Have in the grinding pad of the grinding layer that is dispersed with abrasive particle in the resin, it is characterized in that, described resin is the resin that contains the ion radical of 20～1500eq/ton scope.Form the resin of the grinding layer of the grinding pad that constitutes the invention described above, the ion base unit weight is 20～1500eq/ton, can contain abrasive particle with stable dispersity and carry out compoundization, contain to high concentration and also can reduce the cut that the cohesion by abrasive particle causes under the situation of abrasive particle.In addition, the ion radical of this resin has water dissolvable or water dispersible, the water by supplying with in the grinding step, and the raising of the compatibility between the grinding charge, and grinding rate is improved, show the abrasive characteristic of flatness, excellent in uniformity.From described point, the ion radical that described resin had it is desirable to more than the 20eq/ton, and even more ideal is more than the 100eq/ton, it is desirable to more than the 200eq/ton especially.In addition, if ion radical is too much, then because water dissolvable or water dispersible became strong, so the ion radical that described resin had it is desirable to below the 1500eq/ton, even more ideal is below the 1200eq/ton, it is desirable to below the 1100eq/ton especially.

Described grinding pad, the resin that forms grinding layer is that mylar is desirable, and in the total carboxylic acid composition who constitutes mylar, it is desirable more than the % that the ratio of aromatic dicarboxylic acid is 40 moles.

Form the resin of grinding layer, be not particularly limited and can use various resins, but, it is desirable to mylar from importing the point of ionic group easily.In addition, consider the abrasiveness on grinding layer surface, form the glass transition temperature of the resin of grinding layer, it is desirable to more than 10 ℃, even more ideal is 20～90 ℃.Be 40 moles more than the % for example, can make glass transition temperature within above-mentioned scope by the ratio that makes the aromatic dicarboxylic acid among the total carboxylic acid composition who constitutes mylar.Even more ideal is, and to make the described moisture content of aromatic dicarboxylic acid be 60 moles more than the %.

In addition, grinding pad of the present invention, be to have the grinding pad that abrasive particle is dispersed in the grinding layer that forms in the resin, it is characterized in that, the main chain of described resin is, the polyester that in total carboxylic acid's composition, contains 60 moles of aromatic dicarboxylic acids more than the %, and the side chain of described resin is the polymer that contains hydrophilic functional group's free radical polymerization monomer.

In addition, grinding pad of the present invention, be to have the grinding pad that abrasive particle is dispersed in the grinding layer that forms in the resin, it is characterized in that, the main chain of described resin is the polyester-polyurethane of the polyester that contains 60 moles of aromatic dicarboxylic acids more than the % in total carboxylic acid's composition as main composition component, and the side chain of described resin is the polymer that contains hydrophilic functional group's free radical polymerization monomer.

In the described grinding pad, the proportion that it is desirable to form the resin of grinding layer is 1.05～1.35 scope, and glass transition temperature is more than 10 ℃.

Form the proportion of the resin of grinding layer, it is desirable to 1.05～1.35 scope,, when making grinding layer, produce viscosity, grind well, so desirable at lapped face when glass transition temperature is more than 10 ℃ the time.

In described grinding pad, the resin that it is desirable to form grinding layer is to be that resin and the mixed with resin below 30 ℃ more than 60 ℃ forms with glass transition temperature.

As resin used in this invention, that disperse abrasive particle, it is desirable to glass transition temperature is the structure that resin more than 60 ℃ and the resin below 30 ℃ mix more than 2 kinds.If just glass transition temperature is the resin more than 60 ℃, then is coated with, produces the contraction of filming sometimes when dry, and film and not anti-ly produce wrinkle from the teeth outwards in its stress.In addition, if be that resin below 30 ℃ is coated with glass transition temperature only, though then film coated surface is good, become the surface of bonding, the frictional resistance when grinding rises significantly, and can't carry out stable grinding.Therefore, need the different resin more than 2 kinds of hybrid glass transition temperature, seek its balance.

The glass transition temperature of this resin is being desirable more than 50 ℃, and another glass transition temperature is being desirable below 20 ℃.If be that resin more than 50 ℃ forms grinding layer only with glass transition temperature, crack at coated surfaces when dry, can't obtain good filming.

In described grinding pad, the average grain diameter that it is desirable to abrasive particle is 5～1000nm.

Abrasive particle is that the slight grain abrasive particle of 5～1000nm is an ideal with average grain diameter.If the average grain diameter of abrasive particle diminishes, to the dispersed variation of resin, it is mixed become difficulty with described ion radical, be more than the 5nm so it is desirable to the average grain diameter of abrasive particle, better is more than the 10nm, it is desirable to more than the 20nm especially.In addition, when grinding,, be below the 1000nm so it is desirable to the average grain diameter of abrasive particle because may bring very major injury to grinding charge with the grinding layer that contains the big abrasive particle of average grain diameter, even more ideal is below the 500nm, it is desirable to below the 100nm especially.

In described grinding pad, it is desirable to abrasive particle is at least a a kind of being selected from silica, cerium oxide, aluminium oxide, zirconia, ferrous oxide, chromium oxide and the diamond.

In described grinding pad, the content that it is desirable to the abrasive particle in the grinding layer is 20～95 weight %.

Because if the content of the abrasive particle that contains in the grinding layer tails off, then can not obtain sufficient grinding rate, so in order to improve grinding rate, the content that it is desirable to abrasive particle is more than 20 weight %, better is more than the 40 weight %, it is desirable to especially more than the 60 weight %.In addition, if abrasive particle to contain quantitative change many because damage the formability of grinding layer sometimes, be below the 95 weight % so it is desirable to the content of abrasive particle, even more ideal is below the 90 weight %, it is desirable to especially below the 85 weight %.

In described grinding pad, it is desirable at grinding layer bubble being arranged.In addition, the average grain diameter of bubble is that 10～100 μ m are desirable.

The grinding pad that has bubble in grinding layer can access more stable high grinding rate.Bubble diameter (average diameter) has no particular limits, but in order to obtain stable grinding rate, it is desirable to bubble diameter is more than the 10 μ m, and even more ideal is more than the 20 μ m.In addition, big if bubble diameter becomes, then make easily with the contacted real area of polished object to descend, in order to obtain high grinding rate, it is desirable to bubble diameter is below the 100 μ m, even more ideal is below the 50 μ m.The ratio of the bubble in the grinding layer can be made suitable decision according to grinding charge etc., normally, the grinding layer volume about 5～40%, it is desirable to 10～30%.

Grinding pad of the present invention it is desirable to described grinding layer and forms on polymeric substrate.

As described polymeric substrate, it is desirable to polyester thin plate, acrylic sheet, ABS resin substrate, Merlon thin plate or vinyl chloride resin thin plate.It is desirable to especially, described polymeric substrate is the polyester thin plate.

In described grinding pad, can use grinding layer to be formed on the polymeric substrate.As described polymeric substrate, have no particular limits, described illustrative be desirable, but, it is desirable to the polyester thin plate especially from aspects such as cementability, intensity, environmental loads.

In described grinding pad, the thickness that it is desirable to grinding layer is 10～500 μ m.

In addition, grinding pad of the present invention is characterized in that, has in the structure that is formed with stacked cushion than grinding layer flexible material on the polymeric substrate of grinding layer.

In described grinding pad, A Si card C (Asker C) hardness that it is desirable to described cushion is below 60.

In described grinding pad, it is desirable to, stacked cushion be by the nonwoven of polyester fiber, in this nonwoven the dipping polyurethane resin, polyurethane resin foaming body or polyethylene resin foaming body.

In the present invention, be dispersed with the polymeric substrate and the more soft cushion of Bi Qi of the resin bed (grinding layer) of abrasive particle by stacked support, improve the uniformity of the grinding rate on whole of the silicon wafer after the grinding.Employed in the present invention this cushion, in order to ensure the uniformity of wafer, A Si card C hardness is to be desirable below 60.And cushion of the present invention, in order to realize A Si card C hardness below 60, it is desirable to use by the nonwoven of polyester fiber, in this nonwoven the dipping polyurethane resin.It is desirable to use polyurethane resin foaming body or polyethylene resin foaming body especially.The thickness of this cushion in order not influence the uniformity of grinding in grinding, it is desirable to the scope of 0.5mm～2mm.

In described grinding pad, the thickness of grinding layer is that 250 μ m～2mm are desirable.

Described grinding pad, the bonding strength of grinding layer and polymeric substrate when carrying out the crosscut test, extant number is to be desirable more than 90.

Described grinding pad it is desirable to bonding agent or two sides adhesive tape polymeric substrate and buffering laminating be lumped together.

Described grinding layer it is desirable to the adhesive strength of polymeric substrate and cushion, has the intensity more than the 600g/cm in 180 degree disbonded tests.

Grinding pad of the present invention it is desirable to be formed with groove at grinding layer.

It is desirable to described groove is clathrate.In addition, the separation of groove is desirable below 10mm.In addition, groove is that concentric circles is desirable.In addition, the degree of depth of groove is to be desirable more than the 300 μ m.

Can implement groove processing at the grinding layer of grinding pad of the present invention.When not having groove on the grinding layer, when grinding wafers, wafer is attached to grinding layer and produces great frictional force, to such an extent as to can not keep wafer sometimes, can not grind.The machining shape of groove of the present invention can be a shape arbitrarily, if for example, can exemplify perforation shape, radial slot shape, clathrate, concentric circles, helical form, circular-arc etc., it is desirable to clathrate or concentric circles.The degree of depth of groove of the present invention, the viewpoint from drainage, grinding slag discharge property etc. it is desirable to the above degree of depth of 300 μ m.In addition, form in the present invention under the situation of clathrate groove, the spacing of groove is desirable at least below 10mm.If separation is greater than 10mm, the attaching of above-mentioned wafer takes place in the formation deleterious of groove.The preparation method of groove of the present invention has no particular limits, and the example as wherein can exemplify: by the grinding of using grinding tool, form the method for groove; By the cutting of metal cutting cutter, form the method for groove; By the laser of carbon dioxide gas volumetric laser etc., form the method for groove; Before having the resin bed of abrasive particle, coating, dry mixed, form the method for groove to the mould extruding; Be completed into the coating layer groove of squeezing groove shape afterwards, form the method for groove etc.

Description of drawings

Fig. 1 is the sectional view of the structure of expression grinding pad.

Fig. 2 is illustrated in to place mask material on the lamellar formed body of solidification compound and expose, and has the figure of situation of the grinding layer of the recess that connects at thickness direction with formation.

Fig. 3 is illustrated in to place mask material on the lamellar formed body of solidification compound and expose, and has the figure of the state of concavo-convex grinding layer with formation.

Fig. 4 be illustrated in form on the two sides of lamellar formed body of hardening resin composition of single layer structure concavo-convex, as the figure of the operation of grinding pad.

Fig. 5 is the concept map of the grinding of the expression grinding object that uses grinding pad of the present invention.

Fig. 6 is the concept map of the grinding of the expression grinding object that uses grinding pad in the past.

The specific embodiment

＜(I) grinding pad 〉

The structure of in Fig. 1, having represented grinding pad.

Fig. 1 (a) is the figure of the grinding pad 41 of the common structure that is made of grinding layer 42 and cushion 45 of expression.Fig. 1 (b) is the lamellar formed body that the solidification compound that solidifies by the irradiation energy line is used in expression, form the figure of the grinding layer 42 of grind table surface layer 43 and back layer 44, when back layer 44 has as the characteristic of cushion, can directly use as grinding pad.Fig. 1 (c) is the example at the grinding pad of the also stacked cushion 45 of back layer 44 sides of the grinding layer 42 shown in Fig. 1 (b).

In the present invention, when using the energy line reactive composition to form grinding layer or grinding pad, the energy line reactive composition comprises initator and energy line reactive compounds.As the energy line reactive compounds, it can be the energy line reactive polymer compound of solid, it also can be the energy line reactive polymer compound of liquid, but under the situation of the energy line reactive polymer compound of liquid, it is desirable to also contain solid macromolecule compound (macromolecule resin).In addition, become by energy line and to be insoluble under the situation of solvent, it is desirable to use the energy line reactive polymer compound of solid and the energy line reactive polymer compound of liquid to be used as the energy line reactive compounds, carry out (following sometimes the energy line reactive compounds is called photocurable compound) fast so that make by the reaction of energy line.

Solid among the present invention is meant at 25 ℃ do not have mobile material, and flowability is meant when placing its material on smooth face, can see the material of sprawling after a period of time.Rubber or viscoelastic material are sprawled because of not seeing through the time, so be included into solid scope of the present invention.

Solid energy ray-curable composition of the present invention is meant by energy line, take place chemical reaction particularly polymerisation, do not have a mobile composition indoor.Here said energy line is meant luminous ray, ultraviolet ray, electronics line, ArF laser, KrF laser etc.

As energy ray-curable compound, particularly photocurable compound, so long as carry out the compound of polymerization, cross-linking reaction, all can use with regard to unrestricted by light, can use monomer, oligomer, polymer or their mixture.As relevant compound, (methyl) acrylate that can exemplify multivalence alcohol (has (methyl) acrylate of phenyl ring, (methyl) acrylate of polyoxyalkylene polyol in acrylate and/or methacrylate, epoxy (methyl) acrylate, the molecule, these can use separately, also can make up more than 2 kinds and use.As each (methyl) esters of acrylic acid, specifically can exemplify following compound.

Acrylate or methacrylate as polyalcohol, can exemplify the diethylene glycol dimethylacrylate, tetraethylene glycol diacrylate, six propylene glycol diacrylates, the trihydroxymethyl propane triacrylate, pentaerythritol triacrylate, 1,6-hexanediyl ester, 1,9-nonanediol diacrylate, dipentaerythritol five acrylate, the trihydroxymethyl propane trimethyl acrylic ester, low butadiene glycol diacrylate, the lauryl methyl acrylate, polyethyleneglycol diacrylate, N, N-dimethylamine propyl Methacrylamide, the trihydroxymethyl propane triacrylate, trihydroxymethyl propane trimethyl acrylic ester etc.

As epoxy acrylate, can exemplify 2,2-two (4-methacryloxy phenyl) propane, 2,2-two (4-acryloxy phenyl) propane, trihydroxymethyl propane one glycidol ether or diglycidyl ether acrylate or methacrylate, the hydroxyl of the epoxy resin (bisphenol-type epoxy resin) of bisphenol-A/chloropropylene oxide system with the derivative of acrylic or methacrylic acid estersization etc.

In addition, as (methyl) acrylate that has phenyl ring in the molecule, can exemplify low molecule unsaturated polyester (UP) of phthalic anhydride-season pentanediol-acrylic acid condensation product etc. etc.

As (methyl) acrylate of polyoxyalkylene polyol, can exemplify methoxy poly (ethylene glycol) acrylate, phenoxy group polypropylene glycol acrylate, methoxyl group polypropylene glycol methacrylate, phenoxy group polyethylene glycol acrylate, phenoxy group polypropylene glycol methacrylate, phenoxy group polypropylene glycol acrylate, methoxyl group polypropylene glycol methacrylate, Nonylphenoxy polyethylene glycol acrylate, Nonylphenoxy polyethylene glycol methacrylate-styrene polymer, Nonylphenoxy polypropylene glycol acrylate, Nonylphenoxy polypropylene glycol methacrylate etc.

Substitute above-mentioned (methyl) acrylate, or together to use carbamate system to solidify the property compound, especially use carbamate system (methyl) acrylate compounds with (methyl) acrylate also be desirable form.Solidify the property compound as carbamate system, obtain by the vinyl polymerization compound that reacts multifunctional active dydrogen compounds and polyisocyanate compounds and have a reactive hydrogen base.

Polyisocyanate compounds as constituting carbamate system curing property compound can use without restriction at the known compound of polyurethane field.Can exemplify particularly 2,4-toluene di-isocyanate(TDI) (TDI), 4,4 '-aromatic diisocyanate of methyl diphenylene diisocyanate (MDI) etc.; Aliphatic such as HDI, IPDI or alicyclic diisocyanate class; Xyxylene vulcabond etc.

Vinyl polymerization compound as having the reactive hydrogen base that constitutes carbamate system curing property compound specifically can exemplify the compound that 2-hydroxy ethyl methacrylate or 2-hydroxypropyl acrylate etc. have hydroxyl and ethene unsaturated group.

Solidify the multifunctional active dydrogen compounds of property compound as constituting carbamate system, can exemplify low molecular weight polyols such as making ethylene glycol or propane diols, molecular weight and be the PPG of cyclic ether open loop of the oxirane, expoxy propane, oxolane etc. of 400～8000 polyoxypropylene polyol, polyethylene glycol, polyoxygenated tetramethylene polyalcohol etc.; The PEPA that constitutes by the dicarboxylic acids and the ethylene glycol of adipic acid, azelaic acid, phthalic acid etc.; Or as the PEPA of the ring-opening polymerization polymer of the lactone of ε-caprolactone etc.; Polycarbonate polyol etc.In these polyol compounds, use the polyalcohol of polyethers system to be ideal, because improve the effective of compression property like this.These carbamate system curing property compounds can use separately, also can mix more than 2 kinds and use.

Carbamate system curing property compound for example can be according to following method manufacturing.

(1) as the ethylene glycol and the diisocyanate cpd of multi-functional active dydrogen compounds, equivalent proportion (NCO/OH) with NCO and reactive hydrogen base is 2, react terminal prepolymer as NCO, make compound and the terminal prepolymer of NCO then, react with NCO/OH=1 with hydroxyl and ethene unsaturated group.

(2) compound and diisocyanate cpd with hydroxyl and ethene unsaturated group are reacted as the compound with NCO base and ethene unsaturated group with NCO/OH=2, this compound and polyol compound are reacted with NCO/OH=1.

As carbamate system curing property compound, as the commercial goods UA-306H, UA-306T, UA-101H, Actilane167, Actilane270, Actilane200 (AKCROSCItEMIALS society) etc. are arranged, can suitably use.

As aqueous photoreactive compound, so long as the material that carries out chemical reaction by light just can use without restriction, but in order to improve sensitivity, the sensitization basic weight amount concentration that it is desirable in the applying unit molecule is high.Sensitization basic weight amount concentration is the ideal that is more than the 30 weight %.Specifically can exemplify the following alkyl diol dimethylacrylate of C7, trihydroxymethyl propane trimethyl acrylic ester, dipentaerythritol acrylate etc., but be not limited to these.These aqueous photoreactive compounds can it is desirable to the photoreactivity macromolecular compound of solid with the macromolecular compound of solid and with two macromolecular compounds as solid.

The photoreactivity macromolecular compound of the solid that uses as the constituent material of solidification compound is so long as the material that carries out chemical reaction by light just makes volume without restriction, particularly

1. import the compound that contains active ethylene group or aromatic series polycyclic compound at high molecular main chain or side chain:

With polyvinyl cinnamate, to the unsaturated polyester (UP) of phenylene diacrylate and ethylene glycol polycondensation; Material at polyvinyl alcohol esterification cinnamylidene acetate: import cinnamoyl, mute cinnamyl, styryl phenyl residue, isocoumarin residue, 2,5-dimethoxy stilbene residue, stibazole at high molecular main chain or side chain

Residue, thymine residue, the α-phenyl maleic anhydride sensitization bases such as imines, anthracene residue, 2-counmalin that contract;

2. on high molecular main chain or side chain, import diazo or nitrogen base repeatedly;

To the paraformaldehyde condensation product of the salt addition product of the paraformaldehyde condensation product of the paraformaldehyde condensation product of diazonium diphenylamine, benzene diazo-4-(anilino-)-phosphate, methoxybenzene diazo-4-(anilino-), polyethylene-to nitrogen benzal resin repeatedly, nitrogen acrylate etc. repeatedly.

9. on main chain or side chain, import the macromolecule of phenol ester;

Import the macromolecule, unsaturated polyester (UP), unsaturated polyurethanes, unsaturated polyester acid amides of the two keys of unsaturated carbon-carbon of (methyl) acryloyl group etc., on side chain, import the polyacrylic acid, epoxy acrylate, novolaks acrylate etc. of the two keys of unsaturated carbon-carbon with ester bond.

In addition, can be used in combination various photosensitive polyimides, photonasty polyamic acid, photonasty polyamide-imide etc. and phenolic resin and the nitrilo compound that changes.In addition, polyamide and the light cationic polymerization initiators that imports epoxy resin or chemical crosslinking type position can be used in combination.Also can be used in combination natural rubber, synthetic rubber, thermoprene and two repeatedly nitrilo compound.

When using solidification compound to make grinding pad of the present invention, in solidification compound, add desirable form of light trigger foot.As initator, so long as produce cracking etc. by the irradiation absorption energy-amount of energy line, and produce the polymerization activity kind, the known compound of initiated polymerization etc. can be used without restriction.For example can exemplify the material that causes photo-crosslinking, cause photopolymerisable material (radical polymerization, cationic polymerization, anionic polymerisation), by light, change material that structure changes dissolution characteristics, produce the material of acid etc. etc. by light.

As the optical free radical polymerization initiator, when for example near the ultraviolet ray the i line (365nm) being used as light source. can exemplify aromatic series ketone, benzoin class, benzyl derivative, imidazoles, bifurcation piperidine derivatives, N-phenyl amino acid, two repeatedly nitrilo compounds etc.Specifically can exemplify following compound.

Aromatic series ketone: benzophenone, 4,4 ＇-two (dimethylamino) benzophenone, 4,4 ＇-two (diethylin) benzophenone, 4-methoxyl group-4 ＇-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4 one morpholino phenyl)-butane-l-ketone, 2-ethyl are feared quinone, phenanthrenequione etc.

Benzoin class: methylbenzene accidental cause, ethylo benzene accidental cause etc.

Benzyl derivative: benzyldimethylketal etc.

Imidazoles: 2-(o-chlorphenyl)-4,5-diphenyl-imidazole dimer: 2-(o-chlorphenyl)-4,5-two (m-methoxyphenyl) imidazoles dimer; 2-(o-fluorophenyl)-4,5-phenyl is narrowed the azoles dimer; 2-(o-methoxyphenyl)-4,5-diphenyl is narrowed the azoles dimer; 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer: 2-(2,4-Dimethoxyphenyl)-4,5-diphenyl is narrowed azoles dimer etc.

Bifurcation piperidine derivatives: 9-phenyl bifurcation pyridine, 1,7-two (9,9 ＇-bifurcation pyridine base) heptane etc.

Described light trigger can use more than 2 kinds alone or in combination.The addition of these light triggers with respect to solidification compound, it is desirable to about 0.001～20 weight %.

As the light cationic polymerization initiators, can exemplify by the acidic material of light.Particularly, aryl diazonium is arranged

Salt, diaryl iodine Salt, triarylsulfonium salt, triaryl strontium salt, dialkyl group benzoyl methyl sulfonium salt, dialkyl group-4-hydroxyphenyl sulfonium salt, sulphonic acid ester, iron-aromatic compound, silanol-aluminium complex etc.

Among the present invention as the solid macromolecule that constitutes solidification compound, for mechanical property such as the spring rate (Young rate) that improves grinding pad, volume hardness, compression ratio, compressive recovery rate or for reduce before the light reaction grinding pad in time thickness change and can add.Can exemplify the polyolefin of poly-(methyl) acrylate, polyvinyl alcohol, polyester, polyamide, polyurethane, polyimides, polyamide-imide, Merlon, polyethylene or polypropylene etc. or their compound, mixture etc., so long as the solid macromolecule that can achieve the above object is unqualified.

Solidification compound can use commercially availablely, and as photoelectric sheet, can use the solidification compound that makes lamellar sale.

Energy ray-curable composition of the present invention is used in explanation with reference to the accompanying drawings, has the method for concavo-convex grinding layer from the teeth outwards by the photoetching process manufacturing.

The grinding layer that Fig. 2 is illustrated in the grinding pad forms concavo-convex situation.Use the lamellar formed body 1 of solidification compound to be formed between base film 5 and the diaphragm 3.Be sidelong grinding-material M to diaphragm 3, irradiation quantitative light L.On mask MS of coverage portion and transmittance section MP be configured to form decide the concavo-convex of pattern, by the irradiation of light, form the exposure 1S of portion and unexposed 1H.If solidification compound is a minus, when removing unexposed 1H (developing procedure), forms by lamellar formed body and to be formed with the concavo-convex grinding layer 1 of wishing pattern with solvent etc.

Grinding pad of the present invention is during for no foaming body, wafer or glass plate etc. by grinding-material between adsorption phenomena takes place, for example sometimes in the process of lapping of wafer, the generation wafer breaks away from the situation of its fixed station.If grinding pad is a foaming body, this grinding pad and be difficult to become big problem then by the adsorption phenomena between the grinding-material.Think this be because, when grinding pad is foaming body, on the surface of grinding layer, have a lot of micropores, see it is the state of fluffing from microcosmic, so and reduced by the friction between the grinding-material, make absorption not become big problem.

According to above-mentioned phenomenon, discussion is in the result of the coefficient of friction of certain load lower-glass and grinding pad, set the pattern of lapped face, making confficient of static friction is below 1.49, the coefficient of kinetic friction is 1.27 o'clock, even grinding pad under the situation of no foaming body, also can prevent wafer or glass plate etc. by the adsorption phenomena between the grinding-material.

The concave-convex effect of described lapped face also is applicable to the occasion of removing finishing process in the grinding step.Finishing process is meant, because accumulate abrasive particle in the slip, lapping rejects etc. in the hole of lapped face in process of lapping, grinding rate descended, so at set intervals, use the head of evaporation diamond abrasive grain, finishing lapped face, and the operation of the abradant surface that breaks.Cancel described finishing process,, when using grinding pad of the present invention, also can keep the effect of above-mentioned coefficient of friction as the grinding pad that does not have finishing.

But above-mentioned finishing process do not comprise in order to improve the flatness of grinding pad, and the finishing of repairing when beginning to grind.

By in this grinding layer 1 stacked back layer, can obtain grinding pad as cushion.

In example shown in Figure 2, concavo-convex recess is to connect grinding layer, for example is suitable for hole processing.Fig. 3 is the concavo-convex formation method that illustration also is suitable for groove processing.Lamellar formed body 11 is identical with Fig. 2, is formed between base film 13 and the diaphragm 17, be sidelong mask material M in concavo-convex formation, and base film face 13 sides does not have mask material, exposes.Base film face 13 sides form the cured layer 15 that all is exposed, and form unexposed 11H, the 11S of exposure portion in diaphragm 17 sides, by developing procedure, become the grinding layer 11 with recess 11S and protuberance 11H.Adjust the light of irradiation base film face 13 sides, the cured layer 15 of thickness that feasible formation is decided.

The thickness of concavo-convex recess can suitably be set according to purposes, material etc., is not limited, and adjusts concave depth, and being 2/3 of the above and liner thickness of 100 μ m (0.1mm) be ideal with in.Concave depth also can be adjusted by developing.

The example of making grinding layer has been described in above-mentioned example, also can have similarly formed concavo-convex as the back layer of cushion.

In the manufacture method of Fig. 2, use known filler material if substitute base film 5, then become the grinding pad that possesses cushion.In addition, substitute base film 5, use known grinding pad, and, use to be fit to the material that cushion forms, also can form grinding pad as solidification compound.

Grinding layer 1 and back layer can form respectively across the intermediate layer.The intermediate layer can be solidified the solidification compound that uses among the present invention and used, and also can use other material.Also can make grinding layer with the method shown in Fig. 3, peel off after the base film, the base film with in its alternate figures 2 forms lamellar formed body, and utilizes method shown in Figure 2 to form back layer.

In Fig. 4, illustration the example formed by grind table surface layer and back layer of grinding layer.In this example illustration manufacturing, form at surface and the back side concavo-convex, the example of the continuous integrally formed grinding pad of grind table surface layer and back layer.As the lamellar formed body 25 of grinding pad is by constituting protected film 26,28 linings in the two sides of lamellar formed body as the layer of grind table surface layer 21 with as the layer of back layer 23.Form the diaphragm 26 of face and the diaphragm 28 that back layer 23 forms face at grind table surface layer 21; put the mask material M1 of the relief pattern that is fit to abradant surface and the mask material M2 that suitable back layer 23 forms the relief pattern of face respectively; by this mask material M1, M2; carry out exposure process with light L, then carry out developing procedure and make grinding pad.

Among the present invention,, be dissolved in then and make concaveconvex shape in the solvent to the lamellar formed body irradiation energy of solid line.

Following method is arranged during the irradiation energy line, promptly directly according to desired concaveconvex shape, the method of the energy line of irradiating laser or throttling or at the stacked portion that sees through and the non-film that sees through portion of one side, from the method for this pellicular front irradiation energy line with corresponding concaveconvex shape.In addition, at this moment, can under vacuum, shine for improving the degree of adhesion of film and lamellar constituting body.

In addition, in the irradiation of energy line, also can solidify, till the thickness that does not influence depth of pattern, carry out from face that constitutes pattern and the face irradiation energy linear light of opposing side.

In addition, by regulating from the exposure intensity at the back side, from the exposure intensity on surface, the thickness direction that can produce at pad has hardness distribution, the grinding pad with best thickness direction balance.

Among the present invention,, the permeation parts of energy line and non-permeation parts be there are differences to the dissolubility of solvent, optionally remove with appropriate solvent by chemical reaction by energy line.As solvent, there is no particular limitation, can suitably select according to employed raw material.Difference is according to circumstances removed efficient in order to improve, and uses to certain temperature removing solvent heating sometimes.

Pattern as the pad surface, can exemplify cylindric, coniform, straight-line groove, orthogonal slot, pyramid type, hole or their complex etc., there is no particular limitation but for concaveconvex shape, width, spacing, the degree of depth etc., according to by abrasive particle size or the shape or the hardness of the slip of the hardness of grinding-material or elastic characteristic, use, when stacked, according to the hardness of the layer beyond the grinding layer, elastic characteristic etc., select the concaveconvex shape of suitable each condition.

In addition, grinding pad of the present invention is under the situation of no foaming body, and being adsorbed between the abrasive body of wafer or glass plate etc., sometimes the problem of the fixed station of generation wafer disengaging wafer in process of lapping.Under the situation for foaming body, on the surface of grinding layer, have a lot of micropores, be the state of fluffing on the microcosmic, and reduced, and the absorption between the wafer is difficult to become big problem by the friction between the abrasive body.Therefore, in the present invention, the result who inquires into as the basis with the coefficient of friction of glass under the certain load and grinding pad, when use makes the coefficient of kinetic friction is below 1.27, when confficient of static friction is a picture on surface below 1.49, remove the problems referred to above, be ideal.

In addition, The above results also is suitable for cancelling the situation of the finishing process in the grinding step.Finishing process is meant, the occasion of foaming body is because accumulate abrasive particle in the slip, lapping rejects etc. in the hole of lapped face in process of lapping, grinding rate is descended, so at set intervals, use the head of evaporation diamond abrasive grain, finishing lapped face, and the operation of the abradant surface that breaks.Cancel described finishing process, and as the grinding pad do not repaired, when using grinding pad of the present invention, above-mentioned coefficient of friction is also effective.

But above-mentioned finishing process do not comprise in order to improve the flatness of grinding pad, and the finishing of carrying out when beginning to grind.

In addition, in process of lapping, also can not cut pad surfaces and by with brush washing, reduce obstruction in concavo-convex with water under high pressure washing etc.

Grinding pad of the present invention, under the wavelength of the energy line that uses, transmitance is to be desirable more than 1%.If less than 1%, the irradiation of light can be not enough, can not react effectively.

In the grinding pad of the present invention, in the method as the grinding layer that is manufactured on the grinding pad that has difference of hardness on the surface element that constitutes grinding layer and back layer or the pars intermedia or grinding pad, can be solidification compound, for example the composition of energy content line solidification compound or heat-curable composition makes lamellar formed body, carries out at least a of this formed body load energy line, heat then.Particularly, be used to induce the energy line or the heat of the reaction and the curing of these solidification compounds, make grinding pad of the present invention by control.

Use contains the energy ray-curable compound compositions, make the method for difference of hardness in grinding layer and back layer, at least a method of the transmitance of illuminate conditions such as the intensity of energy line that for example can be by control irradiates light etc., irradiation time, control solidification compound etc. is implemented.Method according to the control permeability, the irradiation energy line is absorbed in layer bit by bit, reduce along arriving lamellar formed body internal direction exposure intensity from energy line irradiation portion, in the difference that cross-linking reaction takes place, form the difference of mechanical properties such as hardness thus between near grinding layer of energy line source and back layer.

In addition, the interpolation by controlling above-mentioned additive or the refractive index of each composition of composition can be controlled the transmitance of solidification compound, and by luminous energy is changed in layer, cause the difference of layer interior cross-linking reaction, and make mechanical properties such as hardness in the grinding layer, compression property variant.Therefore, the grinding pad that can form grinding layer and cushion on 1 layer thin plate simultaneously has necessary case hardness and resiliency simultaneously, can improve the flatness and the uniformity of grinding charge.

Lamellar formed body when making above-mentioned grinding pad or constituting the grinding layer of grinding pad can be made lamellar formed body with sheet moulding method in the past by composition is mixed, and uses ultraviolet homenergic line source photocuring then and gets.In addition, can utilize also that the method for coating composition obtains on base material.

Solvent during, mix the back decompression and remove down to desolvate and form lamellar formed body as 1 composition of solidification compound.Perhaps also can form after the lamellar formed body dry, the removal in before the curing or curing back.

The thickness of grinding pad is set according to use is suitable, and there is no particular limitation, for example uses in the scope of 0.1～10mm.The thickness of grinding pad, that better is 0.2～5mm, it is desirable to 0.3～5mm especially.During in addition stacked back layer, the thickness of grinding layer is that 0.1～5mm is desirable, and that better is 0.2～3mm, it is desirable to 0.3～2mm especially.

Grinding layer is made into the lamellar formed body that makes solidification compound foaming by mechanical foaming or chemical blowing, and to make the layer of foaming body also be desirable form by carrying out exposure process, developing procedure then.

In diaphragm or supporter, use not overslaugh exposure and energy line is had the film of the material of permeability.Diaphragm and base film can be same also can be different.As supporter, can be thin objects such as base film, also can be the object of plastic plate uniform thickness.As this film or supporter, can use known resin film, for example PET film, polyamide film, Kapton, aromatic polyamide resin film, polypropylene film etc., carry out the demoulding as required and handle.Lamellar formed body can cover the two sides with film.

Lamellar formed body does not have adhesiveness, and directly puts under the situation of problems such as bonding or pollution that there is not mask material in mask material yet, can not have diaphragm or base film.

As diaphragm, if use static when preventing to peel off etc. be coated with the diaphragm of antistatic agent, then dust etc. is difficult to enter, so ideal.Unqualified for concavo-convex shape, width, spacing, the degree of depth etc., according to by abrasive particle size or the shape or the hardness of the slip of the hardness of grinding-material or elastic characteristic, use, have under the stacked occasion, according to the hardness of the layer beyond the grinding layer, elastic characteristic etc., select the concaveconvex shape of suitable each condition.

Concavo-convex by on the grinding layer surface, making, the effect of the retentivity of the mobile or raising slip of the slip that can be improved or the elastic characteristic on raising grinding layer surface.When layer formation is concavo-convex overleaf, can give the resiliency that is fit to back layer.

Grinding layer in the grinding pad of the present invention can use the solidification compound that contains the Thermocurable compound that reacts, solidifies by heat to form.As the method for using described heat-curable composition to make difference of hardness at the surface element or the pars intermedia of grinding layer and back layer, for example can implement by the heat that composition is given in control, by heat manufacturing variation in load, and promptly be subjected to produce between the part of a large amount of heats and the low-temp. portion difference of cross-linking reaction in high-temperature portion, thus, on the mechanical properties of hardness etc., form difference.

As heat-curing resin,, just use without restriction so long as be cured the compound of reaction by heat.Bisphenol A type epoxy resin particularly; Bisphenol f type epoxy resin; The bis-phenol phenolic resin varnish type epoxy resin; The cresols phenolic resin varnish type epoxy resin; The ester based epoxy resin; Ethers epoxy resin; Urethane-modified epoxy resin; Alicyclic type epoxy resin with skeleton of cyclohexane or bicyclopentadiene, fluorenes etc.; Hindered phenolic epoxy resin; The epoxy resin of amino based epoxy resin etc.; The maleic anhydride imide resin that contracts; The compound that contains NCO; Melmac; Phenolic resin, acrylic resin etc.These can use more than 2 kinds alone or in combination.In addition, these heat-curing resins adding curing agent being made the solidification compound use also is desirable form.

As curing agent, can exemplify two (4-aminophenyl) sulfones, two (4-phenalgin ketone) methane, 1,5-diamines naphthalene, p-phenylenediamine (PPD), m-phenylene diamine (MPD), o-phenylenediamine, 2,6-dichloro-1,4-phenylenediamine, 1, aromatic amine compounds such as 3-two (to aminophenyl) propane, MXDP; Ethylene diamin(e), diethylentriamine, tetren, diethyl amino propylamine, 1,6-hexamethylene diamine, the Meng aliphatic amine compounds such as alkene diamines, IPD, two (4-amino-3-methyl bicyclic hexyl) methane, polymethylene diamines, polyether diamine; The aliphatic anhydride of polyamine amides compound, lauryl succinyl oxide, poly-adipic anhydride, poly-azelaic acid acid anhydride etc.; The alicyclic acid anhydrides of hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride etc.; The aromatic anhydride of phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerine three trimellitates etc.; The phenolic resin class; The amino resins class; The Lauxite class; The melmac class; Dicyan diamides and two hydrazine compound classes; The imidazolium compounds class; Lewis acid and Brensted acids, poly-thiol compound class; Isocyanates and END CAPPED GROUP isocyanate compound class etc., but be not limited to these.These curing agent and its use level are suitably selected to use according to the heat-curing resin that uses.

In addition, in the present invention, in the solidification compound by heat or energy line curing,, can add as required and grind abrasive particle or other various additives for improving abrasiveness, mechanical property, processability etc.For example can exemplify antioxidant, ultra-violet absorber, antistatic agent, pigment, filler, the macromolecule resin that does not have photo-curable or Thermocurable, tackifier, thermal polymerization inhibitor etc.As grinding abrasive particle, difference has no particular limits according to grinding object, can exemplify the silica (silica) that is made of several microns or particulate below it, aluminium oxide (aluminium oxide), cerium oxide (ceria) etc.

In addition, when grinding layer does not have the hole to be ideal, join the preferably middle solid bubble of bubble in the grinding layer.

In above-mentioned the present invention, lamellar formed body is to utilize common coating process or sheet moulding method to make.As common coating process, can adopt the heating or be dissolved in the solvent, carry out the coating process of scraper or spin coating etc.As the sheet moulding method, can adopt heating back working pressure machine, pressure roller etc., perhaps from the extrusion molding method of mould, roll known sheet moulding methods such as processing method.

Among the present invention, lamellar formed body can various forms use.For example sheet is justified shape, band shape, roller shape, band shape etc.Preferably, select according to the mode of grinding.

The solidification compound that use is particularly solidified by light by energy line, coating, when being shaped lamellar formed body, according to device, the mechanical condition used, also can comprise light trigger or photoreactive compound etc. is dissolved in the solvent mixing, then before being shaped or after being shaped except that the operation of desolvating.

In addition, grinding pad of the present invention can carry out stacked with other laminal object.As other stacked object, object, the spring rate ratio that can exemplify the compression ratio resiliency bigger than grinding pad grind bed hedgehopping and give the object of grinding pad with rigidity etc.

As the compression ratio resiliency object bigger, can exemplify foamed resins such as polyurathamc, polyethylene foamed, bipeltate than grinding pad; The not foaming macromolecular material of rubber, gelling material etc.; Nonwoven; The nonwoven of impregnating resin, the cloth of fluffing, etc.During the object of stacked these resiliencies, improve the uniformity of grinding rate that see on the microcosmic, part.

Spring rate is higher than the spring rate of grinding pad and gives the object of rigidity to grinding pad, can exemplify resin film or plate into PETG, nylon, Merlon, polypropylene, polyvinyl chloride, Vingon, polyacrylate etc.; The metal forming of aluminium, copper, stainless steel etc.; Deng.By stacked these rigidity materials, grind the object periphery excessively prune or the occasion of the grinding object that a plurality of raw material expose under the grinding flatness be improved.

In order to improve flatness, to guarantee the uniformity of grinding rate, it is desirable at the object of resiliency and the stacked layer that gives rigidity in centre of grinding pad of the present invention.

In addition, as laminating method, can adopt bonding agent or any means such as two sides adhesive tape, heat fusing.

The grinding layer of grinding pad of the present invention needs only its dynamic elastic modulus ratio more than 200Mpa, and there is no particular limitation to form material for it.For example can exemplify the admixture of mylar, polyurethane resin, polyether resin, acrylic resin, ABS resin, polycarbonate resin or these resins or photoresist etc.Wherein it is desirable to mylar, polyurethane resin or photoresist.

(mylar)

Mylar, by one or more, be selected from the polyvalent carboxylic acid that contains dicarboxylic acids and their ester formation property derivative and-kind or two or more, be selected from the polyalcohol that contains ethylene glycol and constitute; Or constitute by ester formation property derivative of hydroxycarboxylic acid and they; Or constitute by cyclic ester; Mylar is that their polycondensations are got.

As dicarboxylic acids, can exemplify with oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-pentamethylene dicarboxylic acids, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,5-norbornane dicarboxylic acids, dimeric dibasic acid etc. are saturated aliphatic dicarboxylic acids or their ester formation property derivative of example; With fumaric acid, maleic acid, itaconic acid etc. is unsaturated aliphatic dicarboxylic acids or their ester formation property derivative of example; With inclined to one side phthalic acid, M-phthalic acid, terephthalic acid (TPA), 5-(alkali metal) sulfo-M-phthalic acid, the peaceful acid of biphenyl, 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-biphenyl sulfo group dicarboxylic acids, 4,4 '-biphenyl ether dicarboxylic acids, 1,2-two (phenoxy group) ethane-p, p '-dicarboxylic acids, pamoic acid, anthracene dicarboxylic acids etc. are aromatic dicarboxylic acid or their ester formation property derivative of example.In these dicarboxylic acids, it is desirable to terephthalic acid (TPA) and naphthalene dicarboxylic acids, it is desirable to 2,6-naphthalene dicarboxylic acids especially.

As the polyvalent carboxylic acid beyond these dicarboxylic acids, can exemplify ethane tricarboxylic acids, tricarballylic acid, BTCA, Pyromellitic Acid, trimellitic acid, trimesic acid, 3,4,3 ', 4 '-biphenyltetracarboxyacid acid and their ester form property derivative etc.

As glycol, can exemplify with ethylene glycol, 1,2-propane diols, 1,3-propane diols, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-hexamethylene diethanol, 1,10-decanediol, 1,12-dodecanediol, polyethylene glycol, poly-trimethylene glycol, poly-tetramethylene glycol is the aliphatic alcohol of example; Hydroquinones, 4,4 ' one dihydroxy bis-phenols, 1,4-two (β-hydroxy ethoxy) benzene, 1,4-two (β-hydroxyl ethoxyphenyl) sulfones, two (p-hydroxybenzene) ether, two (to hydroxyphenyl) sulfone, two (p-hydroxybenzene) methane, 1,2-two (p-hydroxybenzene) ethane, bisphenol-A, bisphenol-c, 2,5-naphthalene glycol, be the aromatic alcohols of example at the alcohol of these pure addition of ethylene oxide.In these alcohol, it is desirable to ethylene glycol and 1,4-butanediol.

Polyalcohol as beyond these alcohol can exemplify Pehanorm, trimethylolethane, trimethylolpropane, pentaerythrite, glycerine, hexanetriol etc.

As hydroxycarboxylic acid, can exemplify lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, P-hydroxybenzoic acid, (2-hydroxyl-oxethyl) benzoic acid, 4-hydroxyl cyclohexane-carboxylic acid or their ester are formed property derivative etc.

As cyclic ester, can exemplify ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide etc.

(polyurethane resin)

Polyurethane resin is that PIC and polyalcohol also have chain extender together to react as required and get.These polyurethane resins can react described composition is blanket, also can prepare isocyanates terminal amino group Ethyl formate prepolymer from PIC and polyalcohol, again reaction chain growing agent and obtaining.As polyurethane resin, it is desirable to isocyanates terminal amino group Ethyl formate prepolymer and chain extender the reaction and.

As PIC, the one example is 2,4-and/or 2,6-vulcabond toluene, 2,2 '-, 2,4 ' one and/or 4,4 '-isocyanic diphenyl methane, 1,5-naphthalene diisocyanate, to with the metaphenylene vulcabond, dimellyl diisocyanate, the xyxylene vulcabond, diphenyl-4,4 ' one vulcabond, 1,3-and 1,4-tetramethyl xylylene diisocyanate, the tetramethylene vulcabond, 1,6-HDI, 12 methylene vulcabond, cyclohexane-1,3-and 1,4-vulcabond, 1-isocyanato--3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane vulcabond (=different that Buddhist ketone vulcabond), two-(4-NCO cyclohexyl) methane (=hydrogenation MDI), 2-and 4-NCO cyclohexyl-2 ' NCO cyclohexyl-methane, 1,3-and 1,4-two-(isocyanates ylmethyl)-cyclohexane, two (4-NCO-3-methylcyclohexyl) methane etc.PIC, suitably select the storage period of needs during according to injection moulding, simultaneously because need make isocyanates terminal amino group Ethyl formate prepolymer become low melting viscosity, so use separately or with the form of the mixture more than 2 kinds.

As polyalcohol, can exemplify the pure and mild low molecular polylol of macromolecular multi-component.As polyalcohol, use macromolecule polyol usually.As macromolecule polyol, can exemplify polyester, polyethers, Merlon, polyestercarbonate, polyether carbonate, polyesteramide of C-terminal for example etc.

As the polyester of C-terminal, can exemplify the reaction product of dihydroxylic alcohols and two alkaline carboxylic acids, but in order to improve hydrolytic resistance, the distance between ester bond it is desirable to be the combination of long-chain composition for well.As dihydroxylic alcohols, there is no particular limitation, for example ethylene glycol, 1,3-and 1,2-propane diols, 1,4-and 1,3-and 2,3-butanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, hot pentanediol, cyclohexanedimethanol, 1,4-two (methylol) cyclohexane, 2-methyl-1,3-propane diols, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, diethylene glycol, DPG, triethylene glycol, tripropylene glycol, dibutylene glycol etc.

As two alkaline carboxylic acids, aliphatic, alicyclic, aromatic series and/or hetero ring type are arranged, for making isocyanates terminal amino group formic acid esters prepolymer become aqueous or low melting viscosity, aliphatic or alicyclic two alkaline carboxylic acids are desirable, when using fragrant family, with aliphatic or alicyclic and with being desirable.As these carboxylic acids, unqualified, for example can exemplify dimer (fatty acid) yls such as butanedioic acid, adipic acid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), naphthalene dicarboxylic acids, cyclohexane dicarboxylic acid (neighbour,, to), oleic acid etc.

As the polyester of C-terminal, can have the part of carboxyl terminal.For example can use the polyester of hydroxycarboxylic acids such as lactones such as ε-caprolactone or ε-hydroxycaproic acid.

As the polyethers of C-terminal, can exemplify the starting compound with hydrogen atoms and the reaction product of alkylidene oxide such as for example oxirane, expoxy propane, epoxy butane, styrene oxide, oxolane, epoxychloropropane or these alkylidene oxide mixtures.As starting compound, can exemplify water, bisphenol-A or be used to make the above-mentioned dihydroxylic alcohols of the polyester of C-terminal with hydrogen atoms.

Merlon as C-terminal, can exemplify 1,3-propane diols, 1, the reaction product of glycol photoreactive gas (phosgene), diaryl carbonate (for example diphenyl carbonate) or ring type carbonic esters (propene carbonate) such as 4-butanediol, 1,6-hexylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol and/or polytetramethylene glycol.

As low molecular polylol, the dihydroxylic alcohols that uses in the time of can exemplifying the polyester of making described C-terminal.

Chain extender is to have at least 2 compound bearing active hydrogen endways.As such compound, can exemplify organic diamine compound or above-mentioned illustrative low molecular polylol.Wherein it is desirable to the organic diamine compound.As the organic diamine compound, there is no particular limitation, for example can exemplify 3,3 '-dichloro-4,4 '-diamines diphenyl methane, chloroaniline modification dichloro diamines diphenyl-methane, 1,2-two (2-aminophenyl sulphur) ethane, 1,3-propane diols-two-p-aminobenzoic acid ester, 3,5-two (methyl mercapto)-2,6-toluenediamines etc.

Grinding pad of the present invention also has cushion except grinding layer.Cushion is layered in the opposition side of the abradant surface of grinding layer.This cushion is lower than the dynamic elastic modulus ratio of grinding layer.As long as cushion has the dynamic elastic modulus ratio lower than grinding layer, just there is no particular limitation.The macromolecule foamed resins such as nonwoven, polyurethane foam, polyethylene foam of the impregnating resins such as polyester non-woven fabric of nonwoven or dipping polyurethane for example; Rubbery such as butadiene rubber, isoprene rubber resin; Photoresist etc.Cushion, according to the kind or the grinding condition that are ground object, suitable selection performance cushion characteristic.

The formation of grinding layer, cushion is not particularly limited, and can make in all sorts of ways.For example on substrate, be coated with and respectively form after the material dry formation.As substrate, there is no particular limitation, can exemplify raw-material polymeric substrates such as polyester system, polyamide-based, polyimides system, polyamide-imide system, acrylic acid series, cellulose-based, polyethylene-based, polypropylene-based, polyolefin, polyvinyl chloride, polycarbonate-based, phenol system, polyurethane series resin.Wherein, from viewpoints such as cementability, intensity, carrying capacities of environment, it is desirable to especially with polyester based resin as raw-material polyester film.The thickness of substrate is generally about 50～250 μ m.As coating process, have no particular limits, dipping be can be suitable for and method, spread coating, rolling method, spray-on process, other various print processes are coated with.In addition, can by to the metal pattern that carries out of fixed cast such as metal pattern be shaped or use the thin plateization of calender, extruder, forcing press to form each layer.

The thickness of grinding layer, cushion under the above-mentioned situation is with to the difference of the rigidity of grinding pad requirement, use and difference is not limited, and grinding layer is about 0.5～2mm usually, and cushion is about 0.5～2mm.

Grinding layer and cushion normally fit together with the two sides adhesive tape.When applying grinding layer and cushion, can remove the substrate that forms each layer, also can directly use.In addition, when applying grinding layer and cushion, other layer such as all right stacked intermediate layer.Can fit at cushion and be used to be attached to the splicing tape of pressing on the nog plate.

In addition, the grinding layer of grinding pad of the present invention it is desirable to not have the hole, so compare with the grinding pad of the grinding layer with foaming system, seems and the more important thing is and grind when being ground object, at grinding layer with ground between the object and keep slip.For at grinding layer with ground between the object and keep slip, and in order to get rid of effectively and to accumulate the bits that produced when grinding, it is desirable on the abradant surface of grinding layer, to make groove that slip flows or the part that is used to be detained slip.They combinations can be made.For example grid groove, perforation, concentric circles groove, cylindric, coniform, straight-line groove, orthogonal slot, pyramid type, their complex etc.Unqualified for concaveconvex shape, width, spacing, the degree of depth etc., according to size or shape or hardness, the grinding condition etc. of the slip abrasive particle of the hardness of being ground the object material or elastic characteristic, use, select the concaveconvex shape of suitable each condition.Processing to surface configuration, use at grinding layer under the situation of grinding pad of photoresist and can use photoetching process to carry out, method that can be by using machine cut or laser when using the material beyond the photoresist, use the method etc. that have groove, have a metal pattern of concaveconvex shape to carry out.

In addition, the compression ratio of the grinding layer of grinding pad of the present invention is an ideal with 0.5～10%.When compression ratio is lower than 0.5%, be difficult to reduce the uniformity in the face easily along with the bending of grinding object etc.On the other hand, if compression ratio greater than 10%, then for the wafer that has pattern etc., occurs in the phenomenon that local jump flatness reduces sometimes.

Among the present invention, grinding layer, cushion etc. compression ratio and compressive recovery rate be, the grinding layer after the processing is utilized the cylindric pressure head of diameter for 5mm, with the system TMA of mark Sainz society, measure T1, T2 at 25 ℃, try to achieve according to following formula.

Compression ratio (%)=100 (T1-T2)/T1

Compressive recovery rate (%)=100 (T3-T2)/T1

T1; From 60 seconds load 30Kpa (300g/cm of no load condition experience ²) stress the time lamella thickness

T2: the lamella thickness during from 60 seconds load 180Kpa stress of T1 state experience

T3: placed 60 seconds at no-load condition from the T2 state, then the lamella thickness of stress in the time of 30 seconds of load 30Kpa.

＜(I) grinding pad cushion 〉

Grinding pad cushion of the present invention can be in energy ray-curable resin, heat-curing resin, the hot plasticity resin any one, but considers the processing of groove etc., it is desirable to the energy ray-curable resin, it is desirable to light-cured resin especially.As the energy ray-curable resin, can use and grinding layer constituent material identical materials.

In addition, as constituting grinding pad of the present invention with the composition of cushion, compound with caoutchouc elasticity, so long as hysteresis is little, it is just passable that rubber like has the resin of high compression rate, for example butadiene polymer, isoprene copolymer, styrene-butadiene polymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrenic block polymers, styrene-ethene-butadiene-styrene block copolymer, acrylonitrile-butadiene copolymer, polyurethane rubber, ECD, haloflex, silicon rubber, polyester based thermoplastic elastomer, polyamide-based thermoplastic elastomer (TPE), the polyurethane series thermoplastic elastomer (TPE), fluorine based thermoplastic elastomer etc.

In above-mentioned cushion constituent material, during mixed plasticizer, can further improve compression ratio.The plasticizer that uses has no particular limits, for example repefral, diethyl phthalate, dibutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, phthalic acid two-phthalic acid ester of 2-Octyl Nitrite, diisononyl phthalate, diisooctyl phthalate, phthalic acid tricosane ester, butyl benzyl phthalate, dicyclohexyl phthalate, tetrahydrophthalic acid ester etc.; Adipic acid two-2-Octyl Nitrite, dioctyl adipate, diisononyl adipate, diisodecyl adipate (DIDA), adipic acid two (fourth diethylene glycol (DEG)), adipic acid-di-n Arrcostabs, azelaic acid two-2-Octyl Nitrite, dibutyl sebacate, di-n-octyl sebacate, decanedioic acid two-2-Octyl Nitrite, dibutyl maleate, maleic acid be two-fatty group dibasic acids such as 2-Octyl Nitrite, dibutyl fumarate; Triethyl phosphate, tributyl phosphate, tricresyl phosphate-2-Octyl Nitrite, triphenyl phosphate, phosphoric acid trimethylbenzene phenolic ester, etc. phosphate; Chloroalkane hydrocarbon, citroflex A-4, epoxy plasticiser, polyester are plasticizer etc.

Below, to use the situation of light-cured resin to describe in the manufacture method of grinding pad of the present invention with cushion as example.Under the situation of using other resin, also can utilize according to the method for this method and make cushion.

Among the present invention, at first make after the mixture of polymer that melting mixing adds additive such as above-mentioned light trigger, monomer, plasticizer, being shaped, it is lamellar to be processed as.As the melting mixing method, there is no particular limitation, can adopt the above temperature of Tg (glass transition temperature) that is warming up to polymer in biaxial extruder to carry out the method for melting mixing.In addition, the processing method as thin plate there is no need to limit applicable known method so far.Methods such as for example roller coat applies, cutter coating, scraper coating, scraper plate coating, gravure coating, metal mold coating, reversing coating, spin coated, curtain coating, spraying and applying.In addition, also can carry out being shaped to the metal pattern of cast such as the metal pattern of appointment.

When needing further to improve the compression ratio of the thin plate of making by said method, use known up to now photoetching method,, form pattern, photocuring desirable shape part on thin plate with the optical wavelength that is suitable for composition.Uncured part is used the solvent flush away, forms concaveconvex shape thus.

If apply load to the cushion that obtains like this, stress concentrates on the protuberance base of the jog that forms when forming pattern.Evenly disperse if this protuberance forms in the liner face, then protuberance similarly is absorbed in, the performance buffering effect.

Embodiment

Below, according to embodiment, the present invention is described in further detail, but the present invention is not limited to the following examples.

＜evaluation method 〉

(mobile evaluation)

With the sample of institute's sizing, shape, thickness (radius 5cm, thickness are the circle of 2mm), be placed on horizontal stand above, under the environment of 20 ℃ of temperature, humidity 65%, place.Measure diameter of a circle at regular intervals, with the amount of movement of assess sample.

(mensuration of confficient of static friction, the coefficient of kinetic friction)

Measure according to ASTM-D-1894.Particularly, use the sample of 50mm * 80mm,, under the condition of load 4.4kgf, draw speed 20cm/min, measure as being used the soda-lime glass of selling on the market (transparent panel glass) by the object material.

(hardness)

(a) grinding layer is the situation of individual layer

Measure Shore D hardness according to JIS K6253.

(b) grinding layer situation about constituting by grind table surface layer and back layer

With the grinding layer of slicer after thickness direction is divided processing equally, truncation surface and the face of opposing side as measuring the surface, are measured the Shore hardness of grinding layer (surface) and installed surface (back side) respectively according to JIS K6253.The hardness on surface and the hardness approximately equal at the back side are measured the hardness in intermediate layer (hardness of cut-out portion be lower than measure cut-out portion this moment), and obtain and superficial layer between difference of hardness.

When measuring difference of hardness, changing locates obtains the hardness of 5 points, draws the mean value of these hardness.The same a plurality of objects of replication confirm whether measured value is accurate then.If this measured value is wrong, measure same object more repeatedly, until there not being nonhomogeneous hardness.

(dynamic elastic modulus ratio)

(thickness: arbitrarily) part that cuts out is as the Measurement of Dynamic Viscoelasticity sample with the little bulk of 3mm * 40mm.The correct width and the thickness of each thin plate after cutting out with the micrometer measurement.Use dynamic viscoelastic spectrometer (made, the existing aieis skill of this making of rock is ground) in the mensuration, measure dynamic elastic modulus ratio E.Express condition determination at this moment below.Condition determination is to measure temperature: 40 ℃, add strain: initial stage load: 20g, frequency: 1HZ 0.03%.Express dynamic elastic modulus ratio in the table 1.(compression ratio, compressive recovery rate)

Utilize the cylindric pressure head of diameter, measure the T1～T3 that process the back grinding layer with the system TMA of maxsayieis society at 25 ℃, and try to achieve according to following formula for 5mm.

Compression ratio (%)=100 (T1-T2)/T1

Compressive recovery rate (%)=100 (T3-T2)/(T1-T2)

T1: keep 60 seconds 30Kpa (300g/cm from no load condition ²) lamella thickness during the stress load

T2: the lamella thickness during from T1 state maintenance 180Kpa stress load in 60 seconds

T3: placed 60 seconds the lamella thickness when keeping 30Kpa stress load in 60 seconds then from the T2 state at no-load condition.

(grind and estimate A)

(grinding rate)

The SiO that on monocrystalline silicon surface, forms 500nm (5000 dust) ₂The wafer of film is used to judge as rapidoprint, grinds evaluation under the following conditions.

As lapping device, used common as test lapping device lapmaster/LM15 (4 inches of corresponding Ф).As mill base slurry, use ceria (CeO ₂) colloidal sol (producing chemical society system daily).On grinding head, under adsorbed water/standard pad (backing) material (NF200), keep wafer as machined material, the grinding pad sample is posted in presses nog plate (grinding pad supporter) to fix, at grinding pressure 20kPa (200g/cm ²), the relative velocity between grinding head and the pressure nog plate is 30m/min, mill base slurry feed speed 110cm ³Carry out 2 minutes grinding operations under the condition of/min, measure grinding rate.

Estimate when concerning between milling time and the grinding rate, be not inserted through the finishing process that the sander of evaporation diamond abrasive grain carries out in the process of lapping, residue in the material on the concave-convex surface of grinding layer, utilize brush to carry out on the spot (insitu) washing, carry out the grinding of being fixed time simultaneously, measure grinding rate.

(Evaluation for Uniformity)

To the diameter after grinding is 25 place's abradant surfaces of the wafer of 101.6mm (4 inches of Ф), decides Rmax, Rmin with the contact pilotage instrumentation.Use the numerical value (%) that calculates by formula 100 * (Rmax-Rmin)/(Rmax+Rmin) as estimating all inhomogeneity indexs of wafer.

(repeatability evaluation)

With the drafting department after the observation by light microscope processing.

(grind and estimate B)

As lapping device, use SPP600S (this work mechanism of ridge society system), estimate following abrasive characteristic.As grinding condition, in process of lapping, add silica slurry (SS12, Kai Baote society system) with the flow of 150ml/min as slip.Grind load and be 350g/cm ², grind base plate rotating speed 35rpm, wafer rotation 30rpm.

(grinding rate)

Grind the object that 1 μ m heat oxide film is arranged under these conditions on 8 inches silicon wafer, grind, calculate the grinding rate (dust/minute) of silicon thermal oxidation film by milling time into about 0.5 μ m.The determining film thickness of oxide-film uses interfere type determining film thickness device (chiseling electronics society system greatly).

(planarization characteristics)

On 8 inches silicon wafer, deposit after the heat oxide film of 0.5 μ m, the pattern of stipulating forms, and then deposit the oxide-film of 1 μ m with p-TEOS, the patterned wafer of making initial stage jump 0.5 μ m, this wafer is ground in above-mentioned condition, grind the back and measure each jump, estimate planarization characteristics.Measure 2 jumps as planarization characteristics.One of them is local jump, and this is that width is the jump in the pattern arranged with the spacing of 30 μ m of the line of 270 μ m, measures the jump after 1 minute.Another is a cutting output, at width is in the pattern arranged with the spacing of 270 μ m of line that the pattern arranged with the spacing of 30 μ m of the line of 270 μ m and width are 30 μ m, measures the cutting output of the 270 μ m distances of jump when 2000 dusts are following on top of the line of above-mentioned 2 kinds of patterns.The numerical value of local jump is low, the oxide-film that expression produces for relying on the pattern on the wafer concavo-convex, and it is fast to reach smooth speed within a certain period of time.In addition, if the cutting output in space is few, expression does not wish that the cutting output of the part of pruning is few, the flatness height.

(grind and estimate C)

On monocrystalline silicon surface, form the SiO of 5000 dusts ₂The wafer of film is used to judge as rapidoprint, grinds evaluation under the following conditions.

As lapping device, used common as test lapping device nanofactor/NF-300 (3 inches of corresponding Ф).As mill base slurry, use silica (SiO ₂) slip (fujimi society system).On grinding head, under adsorbed water/standard pad (backing) material (S=R301) condition, keep wafer as machined material, the grinding pad sample is posted in presses nog plate (grinding pad supporter) to fix, at grinding pressure 20kPa (200g/cm ²), the relative velocity between grinding head and the pressure nog plate is 50m/min, carries out 2 minutes grinding operations under the condition of mill base slurry feed speed 25cc/min, measures grinding rate.

(Evaluation for Uniformity)

To the diameter after grinding is 14 place's abradant surfaces of the wafer of 7.62cm (3 inches of Ф), decides Rmax, Rmin with the contact pilotage instrumentation.Use the numerical value (%) that calculates by formula 100 * (Rmax-Rmin)/(Rmax+Rmin) as estimating all inhomogeneity indexs of wafer.

(embodiment 1)

(embodiment 1-1)

Utilize kneading machine to mix epoxy acrylate (EX5000 Kyoeisha Chemical Co., Ltd. system, butanone solvent, solid content composition 80%) 125g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, decompression removes down and desolvates, and obtains the Photocurable composition of solid.Clamp said composition with film, push under 100 ℃, 10 atmospheric pressure with forcing press, obtaining thickness is the lamellar formed body of 2mm.To this lamellar formed body irradiation ultraviolet radiation, be decorated with the film of desired pattern then in the face of opposition mounting, irradiation ultraviolet radiation, stripping film is rubbed with the hands with brush in toluene solvant, develops.In 30 fens kinds of 60 ℃ of dryings, obtain grinding pad.

For this grinding pad, carried out grinding evaluation according to grinding evaluation A method.

(embodiment 1-2)

Utilize kneading machine to mix polyurethane resin (Co., Ltd.'s system, toluene/butanone (1/1 weight) solvent, solid content composition 30% spin in bylonUR-1400 Japan) 200g, trimethylol-propane trimethacrylate 40g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, remove and desolvate, obtain the Photocurable composition of solid.Clamp said composition with film, push under 100 ℃, 10 atmospheric pressure with forcing press, obtaining thickness is the lamellar formed body of 2mm.To this lamellar formed body irradiation ultraviolet radiation, oppose that at it face mounting is decorated with the film of desired pattern then, irradiation ultraviolet radiation, stripping film develops.In 30 fens kinds of 60 ℃ of dryings, obtain grinding pad.Following evaluation is carried out similarly to Example 1.

(embodiment 1-3)

Utilize kneading machine to mix urethane acrylate (UF503LN Kyoeisha Chemical Co., Ltd. system, butanone solvent, solid content composition 70%) 145g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, remove and desolvate, obtain the Photocurable composition of solid.Clamp said composition with film, push under 100 ℃, 10 atmospheric pressure with forcing press, obtaining thickness is the lamellar formed body of 2mm.To this lamellar formed body irradiation ultraviolet radiation certain hour, oppose that at it face mounting is decorated with the film of desired pattern then, irradiation ultraviolet radiation, stripping film develops.In 30 fens kinds of 60 ℃ of dryings, obtain grinding pad.Following evaluation is carried out similarly to Example 1.

(embodiment 1-4)

Utilize kneading machine to mix polyurethane resin (Co., Ltd.'s system, toluene/butanone (1/1 weight) solvent, solid content composition 30% spin in bylonUR-8400 Japan) 258g, 1,6-hexanediyl ester 22.5g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, decompression removes down and desolvates, and obtains the Photocurable composition of solid.Clamp said composition with film, push under 100 ℃, 10 atmospheric pressure with forcing press, obtaining thickness is the lamellar formed body of 2mm.To this lamellar formed body irradiation ultraviolet radiation, be decorated with the film of desired pattern then in the face of opposition mounting, irradiation ultraviolet radiation, stripping film develops.In 30 fens kinds of 60 ℃ of dryings, obtain grinding pad.Following evaluation and embodiment 1-1 similarly carry out.

(comparative example 1-1)

Mix aqueous urethane acrylate 100g and benzyldimethylketal 1g, obtain aqueous Photocurable composition.Said composition is poured into obtain in the mould of institute's sizing, shape decide the lamellar formed body of thickness.To this lamellar formed body irradiation ultraviolet radiation, be decorated with the film of desired pattern then in the face of opposition mounting, irradiation ultraviolet radiation, stripping film develops.In 30 fens kinds of 60 ℃ of dryings, obtain grinding pad.

(comparative example 1-2)

As grinding pad, used IC1000 A21 (rodieru society system) as the polyurathamc grinding pad.Under the device identical, grinding condition, estimate grinding rate with embodiment 1-1.And mensuration grinding rate.For the evaluation of milling time and grinding rate, in grinding, add respectively the correction operation that the sander of diamond abrasive grain carries out to be arranged and add under the situation of revising operation and carry out by evaporation, grind institute respectively and fix time, measure grinding rate.

The mobile investigation result of having represented each sample of light pre-irradiation at table 1-1.By the result as can be known solid shape sheet moulding body do not have flowability.The Thickness Variation that hence one can see that in time descends.

Table 1-1

	Place after 1 hour	Place after 3 hours
			Embodiment 1-1	No change	No change
Embodiment 1-2	No change	No change
			Embodiment 1-3	No change	No change
Comparative example 1-1	10.5cm	11.9cm

Expression is according to the various exterior view cases of embodiment 1-1 making and the relation between the coefficient of friction below.

Table 1-2

Picture on surface	Wafer breaks away from	Confficient of static friction	The coefficient of kinetic friction
				There is not pattern	Have	1.49	1.27
Perforation	Do not have	1.37	1.23
				The XY grid	Do not have	1.14	1.01
Concentric circles	Do not have	1.10	0.98
				Cylinder	Do not have	0.88	0.72
Cylinder and perforation compound	Do not have	0.51	0.34

Perforation: the 4/cm of number in aperture 1.6mm, hole ²

XY grid: groove width 2.0mm, groove depth: 0.6mm, separation 15.0mm

Concentric circles: groove width 0.3mm, groove depth: 0.4mm, separation 1.5mm

Cylinder: diameter 0.5mm, height 5mm

Express the result of the grinding rate of each sample below.Measure according to grinding evaluation method A.

Table 1-3

	Grinding rate (dust/minute)
		Embodiment 1-1	1160
Embodiment 1-2	1210
		Embodiment 1-3	1290
Comparative example 1-1	1000

The picture on surface of embodiment 1-1～1-3 uses cylinder and concentrically ringed compound.

Represented for embodiment 1-1 (picture on surface is a cylinder and concentrically ringed compound) relation when not adding finishing process during grinding between grinding rate and the milling time among the table 1-4.

Table 1-4

	Grinding rate (dust/minute)
				Embodiment 1-1	Comparative example 1-2 does not have finishing process	Comparative example 1-2 has finishing process
	Grind after 2 minutes	1160	1000				1000
Grind after 20 minutes				1180	800	1120
	Grind after 40 minutes	1150	420				1180

By above result as can be known, grinding rate of the present invention is not having under the finishing process state stablely, and the situation that adds finishing process at comparative example 1-2 is compared, and keeps stable grinding rate.

(embodiment 1-4)

Using with thickness on the non-male and fomale(M﹠F) of the grinding pad that uses in embodiment 1-1 (picture on surface is a concentric circles) is the nonwoven (rodeirnita Co., Ltd. system SUBA400) of the PETG of 50 μ m as the stacked dipping urethanes of two-sided tape of core use.The interference light on perusal surface, the result compares with embodiment 1-1, and the part of wafer is ground inequality and is further improved, and does not almost observe the inequality of grinding.And with the result of contact pin type surface roughness measurement device mensuration concave-convex surface, flatness also is further improved than embodiment 1-1.

(embodiment 2)

(making of grinding pad sample 2-1)

Utilize homogenizer to stir 1,9-nonanediol dimethylacrylate (common prosperity society chemistry (strain) system 1,9-NDH) mixture of 30 weight portions, pentaerythritol triacrylate HDI urethane prepolymer (common prosperity society chemistry (strain) system UA-306H) 70 weight portions and benzyldimethylketal (tsibagayigi (strain) makes irugakyua651) 1 weight portion is 10 minutes, utilize coating machine to be coated with and make in its PET film that is clipped in the coating releasing agent, and make laminal formed body.To the irradiation of the opposition face of abradant surface quantitative ultraviolet, this thin plate, with above-mentioned opposite face on mounting have the mask material of the cancellate pattern of groove width 2mm, spacing width 1.5cm, the irradiation ultraviolet radiation photocuring, peel off the PET film after the curing and remove the developing procedure of unexposed portion with developer solution, drying obtains grinding pad sample 1-1.On the grinding pad, verily reproduced jog at pattern, operability also shortens greatly.

(making of grinding pad sample 2-2～2-1)

2-1 makes grinding pad 2-2～2-12 in the same manner with the grinding pad sample.The solidification compound and the relief pattern that use in table 2-1, have been represented.Proportioning is represented with weight ratio.The raw material that uses is as follows.

1,6-hexanediyl ester: 1,6-HX (holding society's chemistry altogether)

Glycerine dimethylacrylate HDI prepolymer: UA-101H (holding society's chemistry altogether)

Aliphatic urethane acrylate: Actilane 270 (ACROS CHEMICALS society)

Aromatic series urethane acrylate: Actilane 167 (ACROS CHEMICALS society)

Low butadiene acrylate: BAC-45 (Osaka organic chemistry).

(making of grinding pad sample 2-13～2-15)

Utilize kneading machine to mix and stir epoxy acrylate EX5000 (Kyoeisha Chemical Co., Ltd.'s system, butanone solvent, solid content composition 80%) 125g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, decompression removes down and desolvates, and obtains the Photocurable composition of solid.Clamp said composition with film, push under 100 ℃, 10 atmospheric pressure with forcing press, obtaining thickness is the lamellar formed body of 2mm.To this lamellar formed body irradiation ultraviolet radiation, be decorated with the mask film of XY clathrate pattern then in the face of opposition mounting, from the rear side irradiation ultraviolet radiation, stripping film is rubbed with the hands with brush in toluene solvant, develops.In 30 fens kinds of 60 ℃ of dryings, had the concavo-convex grinding pad sample 2-13 of XY clathrate pattern from the teeth outwards.

Change the pattern of mask, obtain grinding pad sample 2-14 (concentric circles), grinding pad sample 2-15 (network-like pattern).Groove width, the spacing of each pattern is wide, diameter, the degree of depth are identical with sample liner 2-1～2-3.

(making of grinding pad sample 2-16～2-18)

Use polyurethane resin bayilonUR-1400 (Co., Ltd.'s system, toluene/butanone (1/1 weight ratio) solution, solid content composition 30% spin in Japan) 200g, trimethylol-propane trimethacrylate 40g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, with grinding pad sample 2-13～2-15 had from the teeth outwards identically XY clathrate pattern concavo-convex grinding pad sample 2-16, have concentric circles concavo-convex grinding pad sample 2-17, have the concavo-convex grinding pad sample 2-18 of network-like pattern.

(making of grinding pad sample 2-19～2-21)

Use polyurethane resin bayilonUR-8400-(Co., Ltd.'s system, toluene/butanone (1/1 weight ratio) solution, solid content composition 30% spin in Japan) 258g, 1,6-hexanediyl ester 22.5g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g are had the concavo-convex grinding pad sample 19 of XY clathrate pattern from the teeth outwards with grinding pad sample 2-13～2-15 identically, are had the concavo-convex grinding pad sample 2-20 of concentric circles, are had the concavo-convex grinding pad sample 2-21 of network-like pattern.

(making of grinding pad sample 2-22)

Use graver, undercut the cancellate pattern of groove width 2mm, spacing width 1.5cm, degree of depth 0.6mm on the foaming polyurethane resin surface, as grinding pad sample 2-22, this will need the very big operating time, and the deviation of grid itself is also very big.

(making of grinding pad sample 2-23)

Use and the identical lamellar formed body of making grinding pad sample 2-13～2-15, do not form relief pattern, make grinding pad sample 2-23.

(evaluation)

According to evaluation method A, 2-1～2-22 grinds evaluation to the grinding pad sample, and has represented its result in table 2-2, table 2-3.At table 2-2, table 2-3, the compression ratio of grinding pad, measurement result and the operation of concavo-convex formation or the repeatability of pattern of compressive recovery rate have together been represented.

The grinding pad of grinding pad sample 2-13～2-15 and the result who the grinding pad sample 2-23 that does not form relief pattern is measured the confficient of static friction and the coefficient of kinetic friction in table 2-4, have been represented.

Table 2-1

The grinding pad sample	The composition of solidification compound	Relief pattern
			1	1 part of 70 parts of benzyldimethylketal of 30 parts of pentaerythritol triacrylate HDIs of 1,9-nonanediol dimethylacrylate urethane prepolymer	The wide 1.5cm degree of depth of groove width 2mm spacing 0.6mm XY clathrate groove
2	The same	The wide 1.5mm degree of depth of groove width 0.3mm spacing 0.4mm concentric circles groove
			3	The same	Diameter: the network-like protuberance of 500 μ m groove widths, 900 μ m degree of depth 0.4mm
	1 part of 70 parts of benzyldimethylketal of 30 parts of aliphatic urethane acrylates of 1,9-nonanediol dimethylacrylate	The wide 1.5cm degree of depth of groove width 2mm spacing 0.4mm XY clathrate groove
				The same	The wide 1.5mm degree of depth of groove width 0.3mm spacing 0.4mm concentric circles groove
6	The same	The network-like protuberance of the wide 900 μ m degree of depth 0.4mm of groove width 500 μ m spacings
				1 part of 60 parts of benzyldimethylketal of 40 parts of aromatic series urethane acrylates of 1,9-nonanediol dimethylacrylate	The wide 1.5cm degree of depth of groove width 2mm spacing 0.4mm XY clathrate groove
8	The same	The wide 1.5mm degree of depth of groove width 0.3mm spacing 0.4mm concentric circles groove
			9	The same	The network-like protuberance of the wide 900 μ m degree of depth 0.4mm of groove width 500 μ m spacings
10	80 parts of benzyldimethylketals of olefin(e) acid ester 10 parts of aromatic series urethane acrylates of 10 parts low butadiene diacrylates are 1 part in 1,9-nonanediol dimethyl	The wide 1.5cm degree of depth of groove width 2mm spacing 0.4mm XY clathrate groove
			11	The same	The wide 1.5mm degree of depth of groove width 0.3mm spacing 0.4mm concentric circles groove
12	The same	The network-like protuberance of the wide 900 μ m degree of depth 0.4mm of groove width 500 μ m spacings

Table 2-2

	Grinding pad sample No.	The hardness Shore D	Compression ratio (%)	Compressive recovery rate (%)	Grinding rate (nm/ branch)	Uniformity (%)	Repeatability	Operability	The disengaging of wafer
										Embodiment 2-1	2-1	71	2.1	90.0	102	12	Well	○	Do not have
Embodiment 2-2	2-2		2.8	91.0	110	8	Well	○	Do not have
										Embodiment 2-3	2-3		3.2	90.8	100	7	Well	○	Do not have
Embodiment 2-4	2-4	78	1.9	89.0	128	4	Well	○	Do not have
										Embodiment 2-5	2-5		2.2	90.5	141	3	Well	○	Do not have
Embodiment 2-6	2-6		2.4	91. 0	115	3	Well	○	Do not have
										Embodiment 2-7	2-7	68	3.1	79.3	113	8	Well	○	Do not have
Embodiment 2-8	2-8		3.9	80.0	118	6	Well	○	Do not have
										Embodiment 2-9	2-9		4.5	81.3	111	6	Well	○	Do not have
Embodiment 2-10	2-10	59	4.7	75.1	136	10	Well	○	Do not have
										Embodiment 2-11	2-11		5.3	76.2	142	9	Well	○	Do not have
Embodiment 2-12	2-12		5.9	76.4	132	7	Well	○	Do not have

Table 2-3

	Grinding pad sample No.	The hardness Shore D	Compression ratio (%)	Compressive recovery rate (%)	Grinding rate (nm/ branch)	Uniformity (%)	Repeatability	Operability	The disengaging of wafer
										Embodiment 2-13	2-13	80	0.8	91.9	103	15	Well	○	Do not have
Embodiment 2-14	2-14		0.7	93.6	108	12	Well	○	Do not have
										Embodiment 2-15	2-15		0.8	95.1	114	10	Well	○	Do not have
Embodiment 2-16	2-16	80	0.9	91.6	102	15	Well	○	Do not have
										Embodiment 2-17	2-17		0.7	92.4	104	11	Well	○	Do not have
Embodiment 2-18	2-18		0.8	92.8	110	9	Well	○	Do not have
										Embodiment 2-19	2-19	72	1.1	82.9	113	11	Well	○	Do not have
Embodiment 2-20	2-20		1.3	83.3	120	8	Well	○	Do not have
										Embodiment 2-21	2-21		1.4	85.0	130	6	Well	○	Do not have
Comparative example 2-1	2-22	52	1.2	76.5	100	30	Bad	×	Take place

The result of table 2-2, table 2-3 represents grinding pad of the present invention, and it is few that the quality that repeatability is good, therefore caused by individuality in the concavo-convex processing irregular differs, and changes pattern easily, operability excellence, and the excellent in uniformity in grinding.And can not produce the problem of disengaging in the process of lapping.

Table 2-4

The grinding pad sample	Pattern	Confficient of static friction	The coefficient of kinetic friction	Wafer breaks away from
					2-13	XY	1.14	1.01	Do not have
2-14	Concentric circles	1.10	0.98	Do not have
					2-15	Network	0.88	0.72	Do not have
2-23	Do not have	1.49	1.27	Have

[embodiment 3]

[making of grinding pad]

(grinding pad sample 3-1)

Utilize homogenizer to stir low butadiene glycol diacrylate (Osaka organic chemistry (strain) system BAC-45) 60 weight and 1,9-nonanediol dimethylacrylate (common prosperity society chemistry (strain) system 1,9-NDH) mixture of 40 weight portions and benzyldimethylketal (tsibagayigi (strain) makes irugakyua651) 1 weight portion is 10 minutes, utilizes coating machine coating to make it to be clipped in the PET film of coating releasing agent and makes the uncrosslinked thin plate of thickness for 2mm.Utilize conventional method for this sample, be cured from the opposition face irradiation ultraviolet radiation light of abradant surface.Peel off the PET film after the curing and obtain grinding pad sample 3-1.

(grinding pad sample 3-2)

Utilize homogenizer to stir 1,9-nonanediol dimethylacrylate (common prosperity society chemistry (strain) system 1,9-NDH) mixture of 40 weight portions, aliphatic urethane acrylate (the system Actilane270 of ACROS CHEMICALS society) 60 weight portions and benzyldimethylketal (tsibagayigi (strain) makes irugakyua651) 1 weight portion is 10 minutes, utilize coating machine coating, make it to be clipped in the PET film of coating releasing agent and make the uncrosslinked thin plate that thickness is 2mm.For this sample, with grinding pad 3-1 similarly irradiation ultraviolet radiation light be cured.Peel off the PET film after the curing, obtain grinding pad sample 3-2.

(grinding pad sample 3-3)

Utilize homogenizer to stir bisphenol A type epoxy resin (oiling siel epoxy resin (strain) system cipicoto 154) 50 weight portions and bisphenol A type epoxy resin (oiling siel epoxy resin (strain) system eipicoto871) 60 weight portions and 2-methylimidazole, 1 weight portion and got mixture 10 minutes, utilize the coating machine coating to make it to be clipped in the PET film of coating releasing agent and make the uncrosslinked thin plate of thickness for 2mm.Apply 150 ℃, apply 90 ℃ heat to the top of this sample, be cured to the bottom.Peel off the PET film after the curing, obtained grinding pad sample 3-3.

(grinding pad sample 3-4)

Utilize homogenizer to stir low butadiene glycol diacrylate (Osaka organic chemistry (strain) system BAC-45) 60 weight portions and 1,9-nonanediol dimethylacrylate (common prosperity society chemistry (strain) system 1,9-NDH) mixture of 40 weight portions and benzyldimethylketal (tsibagayigi (strain) makes irugakyua651) 1 weight portion is 10 minutes, use the coating machine coating then, make it to be clipped in the PET film of coating releasing agent.Shine institute's ultraviolet from the opposition of this sample abradant surface towards plane of exposure, then be arranged with the minus film that diameter is the circle of 50 μ m in abradant surface side mounting, the irradiation ultraviolet radiation photocuring, peeling off the PET film after the curing develops with toluene, drying obtains being arranged with on the abradant surface grinding pad sample 3-4 that diameter is the cylinder of 50 μ m.

(grinding pad sample 3-5)

Utilize homogenizer to stir low butadiene glycol diacrylate (Osaka organic chemistry (strain) system BAC-45) 60 weight portions and 1,9-nonanediol dimethylacrylate (common prosperity society chemistry (strain) system 1,9-NDH) mixture of 40 weight portions and benzyldimethylketal (tsibagayigi (strain) makes irugakyua651) 1 weight portion is 10 minutes, utilize the coating machine coating, make it to be clipped in the PET film of coating releasing agent.Shine institute's ultraviolet from the opposition of this sample abradant surface towards plane of exposure, then represent the minus film of XY groove in abradant surface side mounting, the irradiation ultraviolet radiation photocuring is peeled off the PET film after the curing, and with toluene develop, drying, obtain having on the abradant surface grinding pad sample 3-5 of XY groove.

(grinding pad sample 3-6,7)

Utilize homogenizer stir Actilane200 (AKROS CHEMICALS society system) 100 weight portions and and the mixture of benzyldimethylketal (tsibagayigi (strain) makes irugakyua651) 1 weight portion 10 minutes, utilize coating machine coating, making it to be clipped in the PET film of coating releasing agent and making thickness is the uncrosslinked thin plate of 2mm.

To this uncrosslinked thin plate sample, utilize conventional method to be cured from face side irradiation ultraviolet radiation light as grinding layer.After the curing, peel off the PET film, obtain grinding pad sample 3-6.

And from the face of the abradant surface opposition side of this uncrosslinked thin plate sample, to plane of exposure irradiation ultraviolet radiation light, be arranged with the minus film that diameter is the circle of 50 μ m in abradant surface side mounting then, the irradiation ultraviolet radiation photocuring, peel off the PET film after the curing, develop with toluene, drying obtains being arranged with on the abradant surface grinding pad sample 3-7 that diameter is the cylinder of 50 μ m.

(grinding pad sample 3-8)

Utilize kneading machine to mix polyurethane resin bylonUR-8400 (Co., Ltd.'s system, toluene/butanone (1/1 weight ratio) solution, solid content composition 30% spin in Japan) 200g, trimethylol-propane trimethacrylate 40g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, remove and desolvate, obtain the Photocurable composition of solid.Clamp said composition with film, the working pressure machine pushes under 100 ℃, 10 atmospheric pressure, and obtaining thickness is the lamellar formed body of 2mm.From this lamellar sample, opposite with abradant surface towards plane of exposure irradiation ultraviolet radiation light, then be arranged with the minus film that diameter is the circle of 50 μ m in abradant surface side mounting, the irradiation ultraviolet radiation photocuring, peel off the PET film after the curing, with toluene develop, drying, obtain being arranged with on the abradant surface grinding pad sample 3-8 that diameter is the cylinder of 50 μ m.

(grinding pad sample 3-9)

Utilize kneading machine, mix polyurethane resin bylonUR-8400 (Co., Ltd.'s system, toluene/butanone (1/1 weight ratio) solution, solid content composition 30% spin in Japan) 258g, 1,6-hexanediol dimethacrylate 22.5g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, remove and desolvate, obtain the Photocurable composition of solid.Clamp said composition with film, the working pressure machine pushes under 100 ℃, 10 atmospheric pressure, and obtaining thickness is the lamellar formed body of 2mm.Towards plane of exposure irradiation ultraviolet radiation light, then represent the minus film of XY groove, the irradiation ultraviolet radiation photocuring from this lamellar sample, opposite in abradant surface side mounting with abradant surface.Peel off the PET film after the curing, develop with toluene, drying obtains having on the abradant surface grinding pad sample 3-9 of XY groove.

(grinding pad sample 3-10)

Will be as the IC-1000A21 of commercially available polyurethane system grinding pad as grinding pad sample 3-10.

The evaluation result of in table 3, having represented these liners.The evaluation of abrasive characteristic is to carry out according to grinding evaluation method A.

Table 3

	Use the grinding pad sample	Hardness (Shore D)		Compression ratio (%)	Compressive recovery rate (%)	Grinding rate (nm/ branch)	Uniformity (%)
								Surface (plane of exposure)	The back side
		Embodiment 3-1	3-1							61	52	1.5	90.0	130	8
Embodiment 3-2	3-2			64	55	4.6	89.0	128	4
		Embodiment 3-3	3-3							66	58	1.9	79.6	110	7
Embodiment 3-4	3-4			60	52	1.8	92.3	113	8
		Embodiment 3-5	3-5							58	51	2.0	89.4	140	5
Embodiment 3-6	3-6			65	61	3.7	81.4	21	11
		Embodiment 3-7	3-7							64	60	3.9	84.9	123	8
Embodiment 3-8	3-8			80	75	0.5	91. 6	111	9
		Embodiment 3-9	3-9							72	68	1.4	85.0	139	7
Comparative example 3-1	3-10			52	52	1.2	76.5	100	30

[embodiment 4]

(embodiment 4-1)

(grinding layer)

Form material as grinding layer, used photoresist according to following manufacturing.Utilize kneading machine to mix polyurethane resin (Co., Ltd.'s system, toluene/butanone (1/1 weight ratio), solid content composition 30 weight % spin in bylonUR-8400 Japan) 258g, 1,6-hexanediol dimethacrylate 22.5g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, remove and desolvate, obtain the Photocurable composition of solid.Said composition is clipped in the film, and the working pressure machine pushes under 100 ℃, 10 atmospheric pressure, and obtaining thickness is the lamellar formed body of 1.27mm.To this lamellar formed body irradiation ultraviolet radiation certain hour, place the film that is decorated with desired pattern at the face of opposing side then, irradiation ultraviolet radiation, stripping film develops.Carry out 30 fens kinds of drying at 60 ℃, made grinding layer (non-cavitated).Used surface configuration, become XY grid groove (groove width: 2.0mm, groove depth: 0.6mm, separation: patterned films 15.0mm) as the abradant surface of grinding layer.Cut out diameter 60cm circle from it and be used for grinding layer.The dynamic elastic modulus ratio of the grinding layer that obtains is 350Mpa, and tensile elasticity rate is 860Mpa.

(cushion)

Used and carried out surface finish, the polyethylene of sided corona treatment (DongreiShe makes doreibiefu) (thickness 1.27mm, dynamic elastic modulus ratio 7.9Mpa).

(grinding pad)

Applying two sides adhesive tape on grinding layer, opposite face (ponding chemical industry society system, double tack tape) with abradant surface, and then be stained with cushion.And applying two sides adhesive tape on cushion, opposite face and make grinding pad with grinding layer.

(embodiment 4-2)

In (grinding layer) of embodiment 4-1, except forming material as grinding layer, use utilizes kneading machine to mix polyurethane resin (Co., Ltd.'s system, solvent spin in bylonUR-8300 Japan: toluene/butanone (1/1 weight ratio) solution, solid content composition 30%) 258g, trimethylol-propane trimethacrylate 22.5g, benzyldimethylketal 1g and quinhydrones methyl ether 0.1g, except that the Photocurable composition of the solid that desolvates, similarly make grinding pad then with embodiment 4-1.The dynamic elastic modulus ratio of the grinding layer that obtains is 200Mpa, and tensile elasticity rate is 690Mpa.

(embodiment 4-3)

In (grinding layer) of embodiment 4-1, except forming material as grinding layer, (polyethers is a urethane prepolymer (uniloyiyaru society system to the poly-urethane thin plate of use sheet moulding, ajipuranL-325) and curing agent (4,4 '-methylene-two [2-chloroanilines]) polymer) make grinding layer (non-cavitated) (grinding layer thickness 1.27mm), and use external tool to make the surface configuration of the abradant surface side of grinding layer become XY grid groove (groove width: 2.0mm, groove depth: 0.6mm, separation: process 15.0mm), be cut into beyond the circle that diameter is 60cm, similarly make grinding pad with embodiment 4-1.The dynamic elastic modulus ratio of the grinding layer that obtains is 700Mpa, and tensile elasticity rate is 1050Mpa.

(embodiment 4-4)

In (grinding layer) of embodiment 4-1, except forming material as grinding layer, use the polyester thin plate (PETG) of sheet moulding to make grinding layer (non-cavitated) (grinding layer thickness 1.27mm), and use external tool to make the surface configuration of the abradant surface side of grinding layer become XY grid groove (groove width: 2.0mm, groove depth: 0.6mm, separation: process 15.0mm), be cut into beyond the circle that diameter is 60cm, similarly make grinding pad with embodiment 4-1.The dynamic elastic modulus ratio of the grinding layer that obtains is 795Mpa, and tensile elasticity rate is 1200Mpa.

(comparative example 4-1)

In (grinding layer) of embodiment 4-1, except forming material as grinding layer, used polyurathamc (IC1000, rodriru society system) makes grinding layer (non-cavitated) (grinding layer thickness 1.27mm), use external tool processing to make the surface configuration of abradant surface side of grinding layer become XY grid groove (groove width: 2.0mm, groove depth: 0.6mm, separation: 15.0mm), and be cut into beyond the circle that diameter is 60cm, similarly make grinding pad with embodiment 4-1.The dynamic elastic modulus ratio of the grinding layer that obtains is 190Mpa, and tensile elasticity rate is 200Mpa.

For the grinding pad that in embodiment and comparative example, obtains, estimate grinding rate and planarization characteristics according to grinding evaluation method (B).In table 4, express its result.

Table 4

	The dynamic elastic modulus ratio of grinding layer (Mpa)	Grinding rate (dust/minute)	Local jump (dust)	270 μ m spacing cutting outputs (dust)
					Embodiment 4-1	350	1580	1100	500
Embodiment 4-2	200	2190	400	1500
					Embodiment 4-3	700	1800	800	1400
Embodiment 4-4	795	1350	1100	1300
					Comparative example 4-1	190	2200	1300	4600

By the result shown in the table 4-i as can be known, have in the grinding pad of grinding layer and cushion, the dynamic elastic modulus ratio of grinding layer is 200Mpa, and the dynamic elastic modulus ratio of use cushion is lower than the grinding pad of grinding layer, can improve its planarization characteristics.

(sample 6-1)

Mixing is as styrene-butadiene copolymer (JSR system, SBR1507) 84 weight portions of polymer, as dodecyl methyl acrylate 10 weight portions of monomer, as benzyldimethylketal 1 weight portion of light trigger, as aqueous isoprene 5 weight portions of plasticizer, after the double screw extruder melting mixing, utilize the T mould to extrude.Thin plate is clipped in the PET film that thickness is 100 μ m, and becoming gross thickness with the roller extruding is 2mm, is shaped to uncured buffering thin plate.

To the two sides irradiation ultraviolet radiation of this uncured buffering thin plate, after solidifying, peel off the PET film, as sample 6-1 comprehensively.

(sample 6-2)

An irradiation ultraviolet radiation of the uncured buffering thin plate that from manufacturing process, obtains by sample 6-1, peel off the PET of another side then, on mounting screening negative film (negative) (light transmission part diameter 0.6mm, site center distance 1.2mm), from negative film face irradiation ultraviolet radiation.Postradiation buffering thin plate is immersed in the mixed solvent of toluene/butanone (1/1 weight), rubs the flush away uncured portion simultaneously with nylon bruss with the hands.Obtain to have a concavo-convex buffering thin plate dry in 60 ℃ baking oven, solidify to the male and fomale(M﹠F) irradiation ultraviolet radiation.

Peel off the PET thin plate at the back side, as sample 6-2.The concave depth of sample 6-2 is 0.6mm.

(sample 6-3)

Will be as the cushion of commercially available nonwoven type, SUBA400 (rodieru society system) as sample 6-3.

The characteristic value of below having represented sample.

Table 6-1

	Shore A	Compression ratio (%)	Compressive recovery rate (%)
				Sample 6-1	17	20.4	92.9
Sample 6-2	18	26.8	90.2
				Sample 6-3	52	8.0	88.0

The folded IC-1000 (rodieru society system) as commercially available polyurethane system grinding pad on each sample upper strata estimates abrasive characteristic according to grinding evaluation method C.Following table illustrates the result.

Table 6-2

	Cushion	Grinding rate (dust/minute)	Inner evenness
				Sample 6-1	Sample	192	2.2
Sample 6-2	Sample	188	2.0
				Sample 6-3	Sample	100	3.5

＜(II) no slip grinding pad 〉

The following describes the embodiment of no slip grinding pad of the present invention.

As the resin that forms grinding layer of the present invention, for example can use the ion base unit weight is 20～1500eq/ton scope with being not particularly limited.This resin can be straight chain shape or chain any one, and also can be material in the structure of the additional side chain of main chain.Ion radical, as long as be contained in the resin, then may reside in main chain or the side chain arbitrarily in.

As the ion radical that resin had, can exemplify the anion base of base etc. of carboxyl, sulfonic group, sulfate group, phosphate or their salt (hydrogen salt, slaine, ammonium salt) and/or the cation radical of primary amine or tertiary amine groups etc.In these ion radicals, it is desirable to use carboxyl, carboxylic acid ammonium's alkali, sulfonic group, sulfonic acid alkali metal salts base etc.

As above-mentioned resin, desirable for example polyester based resin, polyurethane series resin, acrylic resin, polyester polyurethane resin etc.Wherein it is desirable to polyester based resin especially.This polyester based resin can carry out modification with urethane, acrylic acid etc.

Below, the typical example as the resin of the ion radical with above-mentioned scope illustrates polyester based resin.

(mylar)

Mylar is polycondensation polyacid and polyalcohol and obtain on substantially.

Polybasic carboxylic acid mainly is to be made of omega-dicarboxylic acids and its acid anhydrides etc.As dicarboxylic acids, for example can exemplify aromatic dicarboxylic acids such as terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, two phenyl dicarboxylic acids.The use amount of aromatic dicarboxylic acid is that 40 moles of polybasic carboxylic acid composition are desirable more than the %, better is 60 moles more than the %.In the described aromatic dicarboxylic acid, it is desirable to terephthalic acid (TPA), phthalic acid, these content in aromatic dicarboxylic acid are desirable more than the % at 50 moles.

Dicarboxylic acids as beyond the aromatic dicarboxylic acid can exemplify aliphatic dicarboxylic acids such as butanedioic acid, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid; The alicyclic dicarboxylic acid of 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, dimeric dibasic acid, trimer acid, tetrameric acid etc. etc.

In addition, as omega-dicarboxylic acids, fumaric acid, maleic acid, itaconic acid, citraconic acid, hexahydro-phthalic acid, tetrahydrophthalic acid, 2,5-norbornane dicarboxylic acids or their acid anhydrides etc. be can also exemplify and the aliphatic of unsaturated double-bond or alicyclic dicarboxylic acid etc. contained.

As the polybasic carboxylic acid composition, can use tricarboxylic acids such as trimellitic acid, trimesic acid, Pyromellitic Acid and tetrabasic carboxylic acid etc. as required.

As the polyol component among the present invention, can exemplify ethylene glycol, propane diols, 1,3-propane diols, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, DPG, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, the spiroglycol, 1,4-phenylene glycol, the ethylene oxide adduct of 1,4-phenylene glycol, polyethylene glycol, polypropylene glycol, poly-tetramethylene glycol, the tristane dimethanol, dimer diol, the glycol of hydrogenation dimer diol etc., the ethylene oxide adduct of bisphenol-A and propylene oxide adduct etc., the glycols of the ethylene oxide adduct of hydrogenated bisphenol A and propylene oxide adduct etc.

In addition, as required,, can exemplify trihydroxylic alcohols such as trimethylolethane, trimethylolpropane, glycerine, tetrahydroxylic alcohols such as pentaerythrite as polyalcohol.

As polyalcohol, can use glycerin monoallyl ether, trimethylolpropane-propylene ether, pentaerythrite-allyl ether etc. to contain the polyol component of unsaturated double-bond.

Except above-mentioned polybasic carboxylic acid and polyalcohol, can use P-hydroxybenzoic acid, in the mylar to the aromatic hydroxyl dicarboxylic acids of (hydroxy ethoxy) benzoic acid etc.

The number-average molecular weight of mylar, 3000～100000, better is 4000～30000.(importing of ion radical)

There is no particular limitation for the method for importing ion radical in the resin.Import the method for ion radical in the mylar, in the time of can exemplifying the polycondensation polyester, use to have and the polybasic carboxylic acid of carboxyl and the nonreactive ion radical of hydroxyl and/or the method for polyalcohol.As described composition, for example can exemplify sulfo group terephthalic acid (TPA), 5-sulfoisophthalic acid, 4-sulfosalicylic phthalate, 4-sulfo group naphthalene-2,7-dicarboxylic acids, 5[4-sulfophenoxy] M-phthalic acid etc. contain sulfonic polybasic carboxylic acid compound, also have their slaine etc.In addition, can use sulfosalicylic acid etc. to contain sulfonic monocarboxylic acid compound and their slaine, thus, can be at the terminal ion radical that imports of macromolecule.

When importing ion radical in mylar, also the described polyester that can obtain the condensation of polybasic carboxylic acid and polyalcohol is as main skeleton, and importing has the side chain of ion radical on this skeleton.Introduction method with side chain of ion radical can exemplify, use contain the polymerism unsaturated double-bond as polybasic carboxylic acid and/or polyalcohol, in polyester, import two keys, on glycerol polymerization have the method for the free radical polymerization monomer of ion radical.As free radical polymerization monomer, can use material with illustrated ion radical with being not particularly limited.Free radical polymerization monomer is not limited to have the material of described ion radical, can with have ionic material and use.In addition, the main chain of described mylar and the ratio of side chain are not particularly limited, and it is desirable to main chain/side chain and count 40/60～95/5 scope with weight ratio.

Except said method,, can modulate the mylar of the ion base unit weight of above-mentioned scope by remaining carboxyl on the end of adjusting mylar.For example in the polymerization latter stage of mylar, polybasic acid anhydride more than 3 yuan such as adding trimellitic anhydride, pyromellitic acid dianhydride, phthalic anhydride with to a lot of carboxyls of the terminal importing of resin, can be made the polyester based resin of above-mentioned ion base unit weight.

Import to the anion base of carboxyl in the mylar, sulfonic group etc., can be beforehand with salify, also can be by post processing, after neutralizing with ammonia, alkali metal, amine etc., effectively utilize as ion radical.Can exemplify salt such as Li, Na, K, Mg, Ca, Cu, Fe as slaine, it is desirable to K salt especially.

Resin with described ion radical of the present invention can use separately, perhaps as required also with more than 2 kinds.In addition, described resin of the present invention can also be used with the resin that becomes curing agent under molten condition or solution state.For example,, it can be mixed with polyimide resin, epoxy resin, isocyanate compound etc., and then also can a part react with these for polyester based resin.

(method for making of aqueous dispersion)

Resin with ion radical of the present invention, therefore the ion radical with 20～1000eq/ton scope has the aqueous dispersion ability, by self-emulsification, can make it become the aqueous dispersion of microcosmic.Described ion radical is being necessary aspect the solubility of bringing into play resin, the water dispersible.The particle diameter of a described differential prose style free from parallelism is that 0.0l～1 μ m is desirable.

Concrete grammar as self-emulsification, under the occasion of the resin (polyester based resin) that has carboxyl, sulfonic group, sulfate group, phosphate as ion radical, can adopt (1) with resin dissolves in water-soluble organic compounds, (2) add the cation that neutralizes, (3) add entry, (4) utilize azeotropic, dialysis etc. to remove the order of water-soluble organic compounds.

Have as ion radical carboxyl, sulfonic group, sulfate group, phosphate salt (slaine, ammonium salt) base etc. anion base or have primary amine groups or the occasion of the resin (polyester based resin) of the cation radical of tertiary amine groups etc., can adopt (1) with resin dissolves in water-soluble organic compounds, (2) add water, (3) utilize azeotropic, dialysis etc. to remove the order of water-soluble organic compounds.These can together add emulsifying agent, surfactant etc. when carrying out self-emulsification.

As described water-soluble organic compounds, can use methyl alcohol, ethanol, propyl alcohol, acetone, butanone, oxolane, two ideally The lower water-soluble natural pond agent of boiling point such as alkane, butyl cellosolve, ethyl cellosolve.

As the cation supply source that is used to neutralize, can use amines such as alkali-metal hydroxide, alkali-metal carbonate, alkali-metal bicarbonate, ammonia, triethylamine, MEA, diethanol amine, triethanolamine, dimethylethanolamine, diethyl ethylene diamine, monomethyl diethanol amine, monomethyl-ethanolamine, isophorone, amine alcohols, cyclic amine etc.

As the resin that forms grinding layer of the present invention, the main chain that for example can use resin for the content of the aromatic dicarboxylic acid in total carboxylic acid composition be 60 moles more than the % polyester or with the polyester-polyurethane of this polyester composition as the main composition composition; And side chain is the polymer that contains hydrophily functional group's free radical polymerization monomer.

As the condition of above-mentioned side chain, it is desirable to the radical polymerization mould assembly polymer of monomers that side chain satisfies following (1)～(2) essential condition.Be that side chain is.

(1) in constituting the radical polymerization mould assembly polymer of monomers of side chain, the e value of Q-e value is that be subjected to electronics monomer and the e value more than 0.9 is-weight of the sub-property of power supply monomer below O.6 and account for 50 weight % of total free radical polymerization monomer at least.

(2) in the polymer of the free radical polymerization monomer of formation side chain, the aromatic series free radical polymerization monomer accounts for 10 weight % of total free radical polymerization monomer at least.

The composition that is used for the free radical polymerization monomer of above-mentioned side chain, mainly be by combination with following monomer, constitute as necessary free radical polymerization monomer, promptly the e value of the Q-e value that proposes of Alfrey-Price be more than 0.9, it is desirable to more than 1.0, better be free radical polymerization monomer more than 1.5 and e value be below-0.6, it is desirable to below-0.7, even more ideal be monomer below-0.8.

When the e value was very big negative value, expression had the substituting group of strong power supply, because excessively exist and the irrelevant electronics of key that exists in the unsaturated bond part, so two keys of expression and be partial to bear by the electric charge of the free radical of its generation.On the contrary, the e value be very big on the occasion of the time, expression has the electrical substituting group of strong suction, because the electron deficiency of nonintervention key, so two keys of expression and just be partial to by the electric charge of the free radical of its generation.During the copolymerization free radical polymerization monomer, if combination has the free radical polymerization monomer of the sub-substituent of power supply be e value for the monomer of very big negative value and free radical polymerization monomer with electron-attracting substituent be the e value be very big on the occasion of the opposite monomer of electronic states such as monomer, the any free radical that then generates in polymerization process is the monomer of easy addition all, all are the positive and negative opposite monomers of e value, and this tendency become remarkable under the very big situation of the difference of e value.As mentioned above, the phenomenon that copolymerization takes place between the monomer of a great difference is in fact easily arranged, block copolymerization does not take place, and copolymerization at random more successfully takes place easily, can make the composition of the actual side chain that obtains more approach the composition that adds by utilizing the e value.

In addition, unsaturated bond in the resin that is modified, it is the allyl compound that comes from unsaturated dicarboxylics such as maleic acid, itaconic acid or glycerin monoallyl ether etc. with hydroxyl or carboxyl, the e value of these compounds, because maleic acid, itaconic acid etc. have carboxyl as substituent electrophilic in unsaturated bond portion, so its e value is 1.0～3.0 (under the situation of diester 1.0～2.0), be greatly on the occasion of, electric charge just is partial in the unsaturated bond; And under the situation of allyl compound, since allylic resonance, the great negative value for-1.0～2.0, and unsaturated bond is partial to bear.When carrying out grafting, by using for the unsaturated bond in the resin that is modified, the copolymerization height (promptly in e value positive and negative on the contrary and its e value difference big) free radical polymerization monomer, can suppress not take place fully the phenomenon of homopolymerization with the resin reaction that should be modified.The e value that is copolymerization for very big on the occasion of the resin that is modified of maleic acid, be that the very big monomer of monomer and negative value in the combination of monomers below-0.6 more than 0.9 carries out copolymerization easily with the necessary e value of the present invention, thereby grafting efficiency improves, and the allylic resin that is modified with very big negative e value, easily with very big on the occasion of monomer carry out copolymerization, so at this moment grafting efficiency also improves, the amount of the homopolymers of the free radical polymerization monomer that the resin that can both reduce does not in any case have and be modified reacts.In addition, the invention is characterized in, is the monomer more than 0.9 and the combination ratio of-0.6 following monomer by the e value, suppresses gelation.In the past, in the modification of being undertaken by free radical polymerization monomer that contains the unsaturated bond resin, unsaturated bond amount in the resin that is modified after a little while, can not carry out grafting fully, and the homopolymers of generation free radical polymerization monomer, in addition, unsaturated bond amount in the resin that is modified for a long time, because the combination between the graft side chain, produce gelation, make the scope of the actual unsaturated bond that can utilize in the resin that is modified extremely narrow, but in the present invention, by the e value is the monomer more than 0.9 and the combination ratio of-0.6 following monomer, also can suppress gelation under the very many situations of the amount of unsaturated bond.Under the situation of the monomer of the e of above-mentioned scope value, above-mentioned effect is not low in combination.

In addition, side chain used herein, as above-mentioned, its side chain composition is that the e value by Q-e value that will be in radical polymerization is free yl polymerizating monomer more than 0.9 and e value for the combination of the monomer below-0.6 constitutes as essential mixture, and comprises fragrant family free radical polymerization monomer in this composition.Present inventors etc. are to because modification, various rerum naturas are the reason of declines such as mechanics rerum natura, resistance to water found that of discussion of carrying out repetition particularly, when modified resin is the polyester of fragrant family and polyester polyurethane resin (hereinafter to be referred as base resin), its mechanical property of composition according to side chain changes, particularly fragrant family free radical polymerization monomer is utilized as a composition of side chain, under the situation with the intermiscibility that improves main chain and side chain, suppress the decline of mechanical property significantly.As side chain, when not using fragrant family free radical polymerization monomer fully, the intermiscibility of observing main chain and side chain is low, and the degree of stretching of particularly filming in the various rerum naturas descends significantly.

(mylar)

Described mylar is meant that the aromatic dicarboxylic acid composition accounts for the above polyester of 60 moles of % of total acid composition, what it was desirable consists of: the dicarboxylic acids with polymerism unsaturated double-bond is or/and ethylene glycol, with respect to total dicarboxylic acids composition or total glycol component, the polyester of 0.5～20 mole of % of combined polymerization.Aliphatic and/or alicyclic dicarboxylic acid are 0～40 mole of %.As aromatic dicarboxylic acid, can exemplify terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, two phenyl dicarboxylic acids etc.

As aliphatic dicarboxylic acid, can exemplify butanedioic acid, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid, dimeric dibasic acid etc.; As the alicyclic dicarboxylic acid, can exemplify 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid and its acid anhydrides etc.

As dicarboxylic acids with polymerism unsaturated double-bond, can exemplify as α, β-unsaturated dicarboxylic, fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, as alicyclic dicarboxylic acid with unsaturated double-bond, can exemplify 2,5-norbornane dicarboxylic anhydride, tetrahydrophthalic anhydride.Wherein it would be desirable fumaric acid, maleic acid, itaconic acid, 2,5-norbornane dicarboxylic anhydride.

In addition, as required, can use P-hydroxybenzoic acid, to hydroxycarboxylic acids such as (2-hydroxyl-oxethyl) benzoic acid or hydroxyl trimethylace tonitric, γ-butyrolactone, ε-caprolactones.

In addition, glycol component is to be that 2～10 aliphatic ethylene glycol and/or carbon number are that 6～12 the alicyclic ethylene glycol and/or the ethylene glycol of ether-containing key constitute by carbon number, as carbon number 2～10 aliphatic ethylene glycol, can exemplify ethylene glycol, 1,2-propane diols, 1,3-propane diols, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl propane diol, hydroxyl trimethylace tonitric season pentadiol ester, dihydroxymethyl heptane etc.As carbon number is 6～12 alicyclic ethylene glycol, can exemplify 1,4-cyclohexanedimethanol, three ring trihydroxy methyls in the last of the ten Heavenly stems etc.

Ethylene glycol as ether-containing key, can exemplify on 2 each phenol hydroxyl of diethylene glycol, triethylene glycol, DPG, bisphenols respectively addition of ethylene oxide or expoxy propane 1～several moles glycols that obtains, 2,2-two (4-hydroxyl ethoxyphenyl) propane etc. for example.As required, also can use polyethylene glycol, polypropylene glycol, polytetramethylene ethylene glycol.

The mylar that uses among the present invention, as the dicarboxylic acids composition, use with respect to the total acid composition be 0.5～20 mole of % have the dicarboxylic acids of polymerism unsaturated double-bond the time, aromatic dicarboxylic acid is 60～99.5 moles of %, it is desirable to 70～99 moles of %, aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid are 0～40 mole of %, it is desirable to 0～30 mole of %.If aromatic dicarboxylic acid is less than 60 moles of %, the anti-expansion of filming, the decline of anti-bubble (blister) property after processability of then filming and bend pipe distiller (retort) are handled.In addition, if aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid surpass 40 moles of %, then not only hardness, stain resistance, the decline of the distiller of anti-bend pipe property, and because the aliphatic ester bond reduces than aromatic series ester bond hydrolytic resistance, so the problem of the degree of polymerization reduction etc. of polyester appears between storage life sometimes.

Dicarboxylic acids with polymerism unsaturated double-bond is 0.5～20 mole of %, it is desirable to 1～12 mole of %, and that even more ideal is 1～9 mole of %.When the dicarboxylic acids with polymerism unsaturated double-bond during less than 0.5 mole of %, can't carry out effective grafting to the acrylic monomers composition of mylar, and the main homopolymers of only being made up of the free radical polymerization monomer composition that generates can not obtain target modified resin.

When the dicarboxylic acids with polymerism unsaturated double-bond, when surpassing 20 moles of %, the decline of various rerum naturas is big, and in the later stage of graft reaction, excess stickiness rises, and is entangled on the mixer, and evenly the carrying out of overslaugh reaction, so undesirable.

As ethylene glycol, can exemplify glycerin monoallyl ether, trimethyl propane monoallyl ether, pentaerythrite monoallyl ether etc. with polymerism unsaturated double-bond.

When use contained the ethylene glycol of polymerism unsaturated double-bond, with respect to total glycol component, its ratio can be 0.5～20 mole of %, it is desirable to 1～2 mole of %, better be 1～9 mole of %.When the total amount of ethylene glycol with polymerism unsaturated double-bond and dicarboxylic acids during less than 0.5 mole of %, can't carry out effective grafting to the radical polymerization mould assembly monomer composition of mylar, the main homopolymers of only being made up of radical polymerization mould assembly monomer composition that generates can not obtain target modified resin.

When polyester imports the polymerism unsaturated bond, use dicarboxylic acids or/and ethylene glycol, but have the ethylene glycol of polymerism unsaturated double-bond and the total amount maximum of dicarboxylic acids and can reach 20 moles of %, if surpass 20 moles of %, then the decline of various rerum naturas is big, and in later stage of graft reaction, excess stickiness rises, be entangled on the mixer, and evenly the carrying out of overslaugh reaction, so undesirable.

In above-mentioned mylar copolymerization have 0～5 mole of % 3 officials can more than polycarboxylic acids and/or polyalcohol, as the above polycarboxylic acids of 3 officials energy, can use (anhydrous) trimellitic acid, (anhydrous) Pyromellitic Acid, (anhydrous) benzophenone tetrabasic carboxylic acid, trimesic acid, ethylene glycol bis (trimellitate), glycerine three (trimellitate) etc.On the other hand, as the above polyalcohol of 3 officials energy, can use glycerine, trimethylolethane, trimethylolpropane, pentaerythrite etc.Above polyacid and/or the polyalcohol of 3 officials energy, it is desirable to respect to total acid composition or total glycerine composition is 0～5 mole of %, can be in the scope copolymerization of 0.5～3 mole of %, if but above 5 moles of %, can not pay sufficient processability.

The weight average molecular weight of described mylar is in 5000～100000 scope, it is desirable to weight average molecular weight in 7000～70000 scope, 10000～50000 scope that better is.If weight average molecular weight is below 5000, various rerum naturas descend, and if weight average molecular weight more than 100000, carrying out in the process of graft reaction, high viscosityization, evenly the carrying out of overslaugh reaction.

(polyurethane resin)

Polyurethane resin of the present invention is by PEPA (a), organic diisocyanate compound (b) and also is made of the cahin extension agent with reactive hydrogen base (c) as required, weight average molecular weight is 5000～100000, urethane bond content is 500～4000 equivalents/106g, and the polymerism double bond content is average 1.5～30 in every chain.The PEPA that uses among the present invention (a) is to use as dicarboxylic acids composition and glycol component illustrative compound in one of polyester and makes, and it is desirable to two terminal groups is that hydroxyl, weight average molecular weight are 500～10000 PEPA.Identical with the situation of polyester, be used for aromatic dicarboxylic acid composition in the present invention's the PEPA at least at 60 moles more than the %, it is desirable to 70 moles more than the %.

Be widely used for the aliphatic polyester polyols in the polyurethane resin, for example make spent glycol or season pentanediol the water resistance of polyurethane resin of adipate ester extremely low.As an example, soak 20 days reduced viscosity conservation rates afterwards in 70 ℃ of warm water and be 20～30%, lower, with respect to this, with the terephthalate of identical ethylene glycol, the isophthalate resin as PEPA, reduced viscosity conservation rate under the same conditions is 80～90%, and is higher.Therefore, for the enhanced water resistance energy of filming, be necessary to use with the PEPA of aromatic dicarboxylic acid as main body.In addition, PEPA, PCDL, polyolefin polyhydric alcohol etc. also can be shared with these PEPAs required.

As the organic isocyanate compound (b) that uses among the present invention, can exemplify and be HDI, the tetramethylene vulcabond, 3,3 '-dimethoxy-4,4 '-the biphenylene vulcabond, terephthaldehyde's group diisocyanate, between the xyxylene vulcabond, 1,3-vulcabond hexahydrotoluene, 4,4 '-the vulcabond bicyclohexane, 4,4 '-the vulcabond cyclohexyl methane, IPDI, 2,4-toluene support vulcabond, 2,6-toluene support vulcabond, to phenylene diisocyanate, methyl diphenylene diisocyanate, between phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3 '-dimethyl-4,4 ' one biphenylene vulcabond, 4,4 '-the vulcabond diphenyl ether, 1,5-naphthalene diisocyanate etc.

The cahin extension agent with reactive hydrogen base (c) of Shi Yonging as required, for example can exemplify ethylene glycol, propane diols, season pentanediol, 2,2-dimethyl-1, the glycols, 1 of 3-propane diols, diethylene glycol, spiral shell ethylene glycol, polyethylene glycol etc., amines such as 6-hexamethylene diamine, propylene diamine, 1,6-hexamethylene diamine.

Described polyurethane resin, it is a kind of with PEPA (a), organic diisocyanate (b) and the cahin extension agent (c) that will have the reactive hydrogen base as required needing it, the mixed proportion that makes the reactive hydrogen base/NCO of (a)+(c) is 0.4～1.3 (equivalent proportion), reacts the polyurethane resin that obtains.

When the ratio of reactive hydrogen base/NCO (a)+(c) surpassed this scope, polyurethane resin fully macromolecule quantized the rerum natura of filming that can not obtain wishing.The polyurethane resin that uses among the present invention is used known method, in solvent in the presence of the catalyst under 20～150 ℃ the reaction temperature or do not have to make under the condition of catalyst.Solvent as at this moment using can exemplify ketones such as butanone, hexone, cyclohexanone; Aromatic hydrocarbon such as toluene, dimethylbenzene; Ester such as ethyl acetate, butyl acetate class.As being used to promote catalyst for reaction, can use amine, organo-tin compound etc.

The polyurethane resin that uses among the present invention in order to improve the graft reaction efficient of free radical polymerization monomer, on average contains the two keys of 1.5～30 polymerisms in each root urethane chain, it is desirable to contain 2～20, and even more ideal is to contain 3～15.

Importing about the two keys of this polymerism has 3 kinds of following methods.

1) makes unsaturated dicarboxylics such as containing maleic acid, itaconic acid, norbornane dicarboxylic acids in the PEPA.

2) make the ethylene glycol that contains allyl ether in the PEPA.

3), use the ethylene glycol that contains allyl ether as cahin extension agent.

These can get up to use alone or in combination.1) it is to be subjected to electronics by force 0.9 or more that the two keys of the polymerism in the main chain that is imported in have e value, by 2), 3) to have the e value be the sub-property of strong power supply below-0.6 for the polymerism pair keys that import.

That considers to import to two keys of polymerism in the basic resin in this wise is subjected to electronics or the size of the sub-property of powering and amount, and be directed to this, to free radical polymerization monomer also consider to power sub-property and be subjected to combined method, the amount ratio of electronics monomer, and to offer the grafting reaction be main points of the present invention.

The theory in the past that forms for grafting or block polymer is, the two key numbers of polymerism on every main chain are to have 1 in the main chain or on the end.In fact, in the several patents method formerly, in fact the two key numbers of polymerism that import in the main chain are statistical distribution, are the ratio of 0 chain composition so increased on every main chain, and grafting efficiency reduces thus.If but improved two key amounts, would cause gelation and make suitable scope extremely narrow.With respect to this,, has the advantage that satisfies grafting efficiency and avoid the suitable wide ranges of 2 requirements of gelation based on the method for the present invention of replacing property of the reaction principle between free-radical polymerised chemical seed.

(free radical polymerization monomer)

Usually, in free-radical polymerized, the e value of the Q-e value that is proposed by Alfrey-Price is the value that the unsaturated bond electronic state partly of free radical monomer is represented on experience ground, do not have when the Q value under the situation of big-difference very, be of value to the explanation copolyreaction, record these values at Polymer Handbook 3rd ed.John Wiley andSons. etc.

As the e value of the Q-e value that must use among the present invention is free radical polymerization monomer more than 0.9, be the substituent monomer that partly has electrophilic at unsaturated bond, can use fumaric monoalkylester and dimethyl ester, maleic acid and its acid anhydrides such as fumaric acid, fumaric acid one ethyl ester, DEF, dibutyl fumarate; Maleic acid monoesters and maleic acid diesters such as ethyl maleate, diethyl maleate, dibutyl maleate; Itaconic acid, itaconic acid monoesters and itaconic acid diester; At least a above mixture that the maleic anhydride of phenyl maleimide etc. contracts and selects in imines, the acrylonitrile etc. it would be desirable maleic anhydride and ester thereof, fumaric acid and ester class thereof.

As the e value of the Q-e value that must use among the present invention is radical polymerization mould assembly monomer below-0.6, it is the substituent monomer that on unsaturated bond, has the sub-property of powering, perhaps conjugated system monomer, can use ethene such as styrene, α-methyl styrene, t-butyl styrene, N-vinylpyrrolidone is free radical polymerization monomer; Vinyl acetate such as vinyl acetate; Vinyl ethers such as vinyl-n-butyl ether, VINYL ISOBUTYL ETHER; Allyls such as allyl alcohol, glycerin monoallyl ether, pentaerythrite monoallyl ether, trimethylolpropane allyl ether are free radical polymerization monomer; At least a above mixture of selecting in the butadiene etc. it would be desirable that ethene such as styrene is free radical polymerization monomer.

In the present invention, needing the e value is the combination for the radical polymerization mould assembly monomer below-0.6 of radical polymerization mould assembly monomer more than 0.9 and e value, it is combined in total radical polymerization mould assembly monomer, occupies at least more than the 50 weight %, and better is more than the 60 weight %.In addition, for the unsaturated bond that contains in the resin that is modified, in 2 kinds of above-mentioned radical polymerization mould assembly monomers, the high free radical polymerization monomer of copolymerization (promptly with the resin that is modified in the not big monomer of e value difference of unsaturated bond) content in total free radical polymerization monomer is desirable more than 20 weight %, and the content of the low free radical polymerization monomer of copolymerization (with the not little monomer of e value difference of unsaturated bond in the resin that is modified) in total free radical polymerization monomer is desirable more than 20 weight %.When the former during less than 20 weight portions, can not obtain sufficient grafting efficiency for main chain, free radical polymerization monomer generation homopolymerization.If the latter then produces gelation in the process of grafting less than 20 weight %, can't successfully carry out grafting.

In addition, as required can with other free radical polymerization monomer of above-mentioned neccessary composition copolymerization, can use the e value to be-0.6～0.9 free radical polymerization monomer.For example acrylic acid, methacrylic acid and as their ethyl acrylate, EMA etc. of ester class; As the free radical polymerization monomer that contains nitrogen-atoms can acrylamide, methacrylonitrile etc. contains in each molecule of monomer usually in the monomer of a free-radical polymerised pair of key and selects one or more uses.Thus, regulate side chain Tg or and main chain between intermiscibility, and can import functional group arbitrarily.

Aromatic series free radical polymerization monomer as necessary in the side chain composition can exemplify the free radical polymerization monomer with aromatic rings, can pass through styrene derivatives such as styrene, α-methyl styrene, 1-chloro-4-methyl-benzene; The reactant of acrylic acid-2-hydroxyl ethyl esters (HEA) such as phenoxyethyl acrylate, phenoxy group ethyl-methyl acrylate, benzyl acrylate, benzyl methacrylate and methacrylic acid-2-hydroxyl ethyl ester (HEMA) and aromatic compound; The ester of phthalic acid derivatives such as 2-acryloyl ethoxy hydrogen phthalic acid ester and HEA, HEMA; And the reactant of acrylic acid, methacrylic acid and phenyl glycidyl ether etc., promptly by 2-hydroxyl-3-phenoxypropane (methyl) acrylate etc., import aromatic rings at side chain.Among the present invention, the usage ratio of described aromatic series free radical polymerization monomer, total relatively free radical polymerization monomer more than 10 weight portion %, it is desirable to it would be desirable more than the 30 weight % more than the 20 weight portion % at least.

(grafting reaction)

Graft polymers among the present invention is by the polymerism unsaturated double-bond in above-mentioned base resin, graft copolymerization free radical polymerization monomer and getting.Graft polymerization reaction among the present invention is under the state that the base resin that contains the two keys of polymerism is dissolved in the organic solvent, reaction radical initiator and free radical polymerization monomer mixture and carry out.Reaction product after the grafting reaction finishes does not have the monomer-polymer of grafting to form usually except graft polymers by the base resin of not accepting grafting with base resin.Usually, when the ratio of low, non-grafting base resin of the graft polymers ratio in the reaction product and the independent polymer of non-grafting was high, the effect of modification was low, and observed owing to the film baneful influence of albefaction etc. of non-grafting homopolymers.Therefore, it is important selecting graft copolymer to generate the high reaction condition of ratio.

When base resin is carried out the grafting reaction of free radical polymerization monomer, be dissolved in the base resin in the solvent to heating down, can add free radical polymerization monomer mixture and radical initiator simultaneously, after also can splashing into certain hour respectively, the stirring certain hour continues to heat and reacts.In addition, one of desirable example of the present invention is that the e value that adds in advance with the two keys of polymerism of base resin differs little free radical polymerization monomer, add free radical polymerization monomer, the initator that the e value with the two keys of polymerism of base resin differs greatly with certain hour then, under the certain hour stirring, heat then and react.

Before the reaction, add base resin and solvent, stir rising temperature for dissolving resin down to reactor.The weight ratio of base resin and solvent is desirable in 70/30～30/70 scope.At this moment consider the reactivity of base resin and free radical polymerization monomer and the dissolubility of solvent, weight rate is adjusted into the weight rate that can react equably in the polymerization process.The temperature of grafting reaction is desirable at 50～120 ℃.Adapting to the desirable base resin of the object of the invention and the weight ratio of free radical polymerization monomer is in base resin/side chain portion, is 25/75～99/1 scope, it would be desirable 50/50～95/5 scope.If the weight rate of base resin below 25 weight %, the excellent properties that can not bring into play the base resin of above-mentioned explanation fully be high working property, excellent in water resistance, and various base material between stickiness.When the weight rate of base resin when 99 weight % are above, not similar in polyester or the polyester polyurethane resin by the ratio of the base resin of grafting, the effect of modification is low, and is undesirable.

The weight average molecular weight of the grafted chain part among the present invention is 1000～100000.When carrying out glycerol polymerization by graft reaction, make the weight average molecular weight of grafted chain part be controlled at common difficulty below 1000, grafting efficiency descends, and can not pay the functional group to base resin fully, so undesirable.In addition, the weight average molecular weight of grafted chain part is 100000 when above, and the viscosity of polymerisation rises significantly, can not carry out as the polymerisation under the homogeneous system of purpose.Here the control of Shuo Ming molecular weight, be can splash into time, polymerization time, reaction dissolvent by suitably composite initiator amount, monomer, monomer is formed or chain-transferring agent or polymerization inhibitor carry out as required.

(radical initiator)

As the radical polymerization initiator that uses among the present invention, can utilize organic peroxide class or the organic azo-based compound class known.That is,, can exemplify benzoyl peroxide, t-butyl peroxy trimethyl ethyl ester as organic peroxide, as organic azo-compound, can exemplify 2,2 '-azodiisobutyronitrile, 2,2 ' one azo (2,4-methyl pentane nitrile) etc.

When selecting the radical initiator compound, be necessary to consider that the free radical formation speed that its compound carries out under the temperature in reaction is half-life (Half-Life).Usually, selected radical initiator, making the value of the half-life under this temperature is desirable 1 minute to 2 hours scope.Being used to carry out the use amount of free-radical grafting initiator having, is with respect to free radical polymerization monomer, more than 0.2 weight %, it is desirable to more than the 0.5 weight % at least.

In order to regulate the length of grafted chain, use chain-transferring agent as required, for example n-octyl mercaptan, dodecyl mercaptans, mercaptoethanol.At this moment, it is desirable to respect to free radical polymerization monomer, is the scope of 0～20 weight %.

(reaction dissolvent)

As reaction dissolvent, for example can utilize the ketone of butanone, hexone, cyclohexanone etc.: aromatic hydrocarbons such as toluene, dimethylbenzene; Widely used solvents such as ester such as ethyl acetate, butyl acetate class.But the selection of reaction dissolvent that is used for grafting reaction is of crucial importance.The condition that need possess as desirable reaction dissolvent is 1) dissolubility, 2) as the adaptability of radical polymerization bonding solvent, 3) boiling point of solvent, and 4) dissolubility of solvent in water.1) dissolving or dispersion base resin in, it well is important making a chain part of the graft copolymer of being made up of the unsaturated monomer mixture and the dissolving of non-grafting homopolymers simultaneously as far as possible.2) in, importantly solvent self decomposes that radical initiator (bringing out decompositions) or the combination between specific organic peroxide and specific ketones solvent do not cause resembling the explosion risk reported and has suitable little chain transfer constant as the reaction dissolvent of radical polymerization.3) usually because the grafting addition reaction of free radical polymerization monomer is exothermic reaction,, it is desirable under the circulation condition of solvent, carry out in order to keep stationary temperature.4) can not the say so essential necessary condition of graft reaction self indispensability, when in base resin, importing the hydrophilic functional group by modification, when in water, disperseing its modified resin to be purpose, from industrialized viewpoint, it is desirable to 1)～3) necessary condition under the solvent selected can freely be dissolved in organic solvent in the water, the perhaps mutual dissolubility height between water and the organic solvent.When satisfying above-mentioned the 4th necessary condition, the grafting reaction product that following of heated condition contains solvent directly with in the alkali compounds and after add water and form aqueous dispersion.Even more ideal is can freely dissolve or the boiling point of the organic solvent that dissolubility is high mutually is lower than the boiling point of water.At this moment, from aqueous dispersion, outside system, discharge organic solvent by simple distillation according to above-mentioned formation.

In order to implement grafting reaction dissolvent of the present invention, can be that single solvent also can be a mixed solvent.Boiling point is higher than 250 ℃ solvent, and evaporation rate is slow excessively, can not discharge fully by the high-temperature baking of filming.Boiling point is at the solvent below 50 ℃, and when it was carried out the grafting reaction as solvent, cracking was the initator of free radical under the temperature below 50 ℃ because must use, so operational danger increase is undesirable.

When being dispersed in the polyester that generates or polyester polyurethane resin in the water as purpose, can be used in the reaction dissolvent of graft reaction, desirable solvent as dissolving or disperseing base resin and free radical polymerization monomer mixture and its polymer are dissolved preferably can exemplify ketone for example butanone, hexone, cyclohexanone; The ring-type ethers is oxolane, two for example

Alkane: gylcol ether is propylene glycol monomethyl ether, propylene glycol propyl ether, ethylene glycol ethyl ether, butyl glycol ether for example; The carbitol class is methyl carbitol, ethyl carbitol, BC for example; The lower member ester class of glycols or glycol ether is ethylene acetate, ethyl cellosolve acetate for example; Ketols is DAA for example; N-substitutional amine-group is N for example, N-dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone etc.

When in single solvent, carrying out the grafting reaction, can from the organic solvent that dissolves base resin well, select a kind of.In addition, when in mixed solvent, carrying out, perhaps only from above-mentioned organic solvent, select multiple the reaction, perhaps from the organic solvent that dissolves above-mentioned base resin well, select at least a sometimes, add at least a reaction the in the organic solvents such as the lower alcohols dissolve base resin hardly, low-grade carboxylic acid's class, rudimentary amine again, can in any solvent, react.

(method for making of water-dispersion type polyester or polyester polyurethane resin)

The hydrophilic functional group that grafting reaction product of the present invention can import by grafting with neutralization such as alkali compounds, and carry out aqueous dispersionization.The radical polymerization mould assembly monomer that contains the hydrophily functional group in the radical polymerization mould assembly monomer mixture and do not contain the ratio of hydrophily functional group's radical polymerization mould assembly monomer, with the kind of the monomer of selecting, supply with the grafting reaction the weight ratio of base resin/side chain portion relevant, the acid value of grafting body is with 200～4000 equivalents/10 ⁴G is desirable, and even more ideal is 500～4000 equivalents/10 ⁴G.As alkali compounds, it is desirable to film when forming or the compound of mixed curing agent, volatilization when baking is cured, it is desirable to ammonia, organic amine etc.As desirable compound, can exemplify triethylamine, N, N-diethyl ethylene diamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanol amine, isopropylamine, the two propylamine of imino group, ethamine, diethylamine, 3-ethoxy propylamine, 3-diethylamine propylamine, tert-butylamine, propylamine, methylamino propylamine, DIMAPA, the two propylamine of methyl-imino, 3-methoxy propanamine, MEA, diethanol amine, triethanolamine etc.Alkali compounds uses and to be, according to the carboxyl-content that contains in the grafting reaction product, at least by part neutralization or neutralization completely, the pH that makes aqueous dispersion is desirable in 5.0～9.0 scope.

When implementing aqueous dispersion, can become the grafting reaction product that melts shape or solid shape (particle, powder) removing the solvent that contains in the grafting reaction product with decompression extruder down etc. in advance, throw in the water that contains alkali compounds, heating is stirred down and is made aqueous dispersion, but preferably react the moment that finishes at grafting, add alkali compounds and water, continue to add thermal agitation, obtain the method (one pot) of aqueous dispersion at once.Under the latter's the situation, as required, can distill the solvent that can mix or distill and remove part or all by common Buddhist with water with the water that is used for grafting reaction.

As crosslinking agent, can exemplify phenolic resins, polyimide resin, polyfunctional epoxy resin, polyfunctional isocyanate's compound and their various block isocyanate compounds, polyfunctional aziridines compound etc.As phenolic resin, can the exemplified by alkyl groups phenol, the formaldehyde condensation products of cresols class.Alkylation particularly (methyl, ethyl, propyl group, isopropyl, butyl) phenol, Pentaphen, 4,4 '-secondary phenolic group butane, p-t-butyl phenol, neighbour, between or paracresol, to cyclohexylphenol, 4,4 '-isopropylidene phenol, to formaldehyde condensation products such as nonyl phenol, POP, 3-pentadecyl phenol, phenol, phenol-orthoresol, p-phenyl phenol, xylenols.

As polyimide resin, for example can exemplify formaldehyde condensation products such as urea, melamine, benzo guanamine, and their carbon number is the alkylether compounds of 1～6 alcohol.Can exemplify methoxylation hydroxymethyl urea, methoxylation methylol N particularly, N-ethylene-urea, methoxylation methylol dicyano diamides, methoxylation melamine methylol, methoxylation methylol benzo guanamine, butoxy melamine methylol and butoxy methylol benzo guanamine etc.It is desirable to methoxylation melamine methylol, butoxy melamine methylol and methylolation benzo guanamine, can distinguish and use separately or and use.

As epoxide, can exemplify the diglycidyl ether of bisphenol-A and its oligomer, the diglycidyl ether of hydrogenated bisphenol A and its oligomer, the phthalic acid diglycidyl ether, the M-phthalic acid diglycidyl ether, the terephthalic acid (TPA) diglycidyl ether, the P-hydroxybenzoic acid diglycidyl ether, the tetrahydrophthalic acid diglycidyl ether, the hexahydro-phthalic acid diglycidyl ether, the butanedioic acid diglycidyl ether, the adipic acid diglycidyl ether, the decanedioic acid diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and PAG 2-glycidyl ethers, the trimellitic acid three-glycidyl ester, the isocyanic acid three-glycidyl ester, 1,4-2-glycidyl oxygen benzene, 2-glycidyl trimethylene urea, the glycerine triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, the pentaerythrite triglycidyl ether, the triglycidyl ether of glycerine alkylene oxide addition product etc.

As isocyanate compound, aromatic series is arranged; Aliphatic vulcabond; The PIC that 3 valencys are above; Low molecular compound, macromolecular compound can.For example can exemplify the tetramethylene vulcabond; HDI; Toluene di-isocyanate(TDI); Methyl diphenylene diisocyanate; Hydrogenated diphenyl methane diisocyanate; The xyxylene vulcabond; , hydrogenation of benzene dimethyl vulcabond; The tripolymer of different that Buddhist ketone vulcabond or these isocyanate compounds; And the macromolecule active dydrogen compounds of these excessive isocyanate compounds and low molecular activity hydrogen compound such as for example ethylene glycol, propane diols, trimethylolpropane, glycerine, minashi sugar alcohol, ethylene diamin(e), MEA, diethanol amine, triethanolamine etc. or various polyester polyols alcohols, PPG class, polyamine class etc. reacts the compound that obtains, contain NCO on the end.

As isocyanate compound, also can be the block isocyanates.As the agent of isocyanates block, can exemplify phenol such as phenol, thiophenol, methyl thiophenol, cresols, xylenols, resorcinol, nitrophenol, chlorophenol; Oximes such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime; Alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols; The alcohols that chlorethanol, 1,3-dichloro-chlorine such as 2-propyl alcohol replace; 3 grades of alcohols such as the tert-butyl alcohol, tert-pentyl alcohol; Lactone such as ε-caprolactone, δ-valerolactam, γ-butyrolactone, β-propiolactone; Other also has aromatic amine, inferior amide-type, acetylacetone,2,4-pentanedione, ethyl acetoacetate, malonic ester isoreactivity methylene compound; Thio-alcohol, imines class, ureas, biaryl compound class sodium sulfite etc.The block isocyanates is, with known method in the past, and above-mentioned isocyanate compound of addition reaction and the agent of isocyanates block and get.

Can use curing agent or promoter simultaneously in these crosslinking agents.Fitting method as crosslinking agent, can exemplify the method that is blended in the base resin, also have dissolved polyester and polyester polyurethane resin in organic solvent solution in advance, in water, disperse the method for this mixed solution again, can select arbitrarily according to the kind of crosslinking agent.Curing reaction, polyester normally of the present invention relatively and polyester polyurethane resin 100 parts (solid content compositions) are mixing cured with 5～40 parts of resins (solid content composition), according to the kind of curing agent,, heat about 1～60 fen kind and carry out 60～250 ℃ temperature range.In case of necessity can and with catalysts or promoter.

(micronize method for making)

Aqueous dispersion with resin dispersion, polyester or polyester polyurethane resin of above-mentioned ion radical by cohesion lentamente, can be made bigger particle diameter.As realizing the slowly method of cohesion, effectively add the ionic compound of electrolyte etc. at aqueous dispersion, improve the method for intrasystem ionic strength.In addition, can use (1) to cut off the scanning of ion radical (2) by temperature, PH etc. by light decomposition, thermal decomposition or hydrolysis etc., the degree of dissociation (3) of control ion radical is by the method to ion end-blocking ion radical etc.

Among the present invention,, can exemplify the ester compounds that in system, adds the amine alcohol and carboxylic acid, in system, produce amine alcohol and carboxylic acid, improve the method for ionic strength thus by the hydrolysis generation of this ester compounds as the method for slow cohesion.According to this method, it is even can not produce local density unevenness in system, and improves ionic strength, so can access ionic diameter good resin particle uniformly.

(abrasive particle)

As the abrasive particle that is used for the present invention, can not use the grinding abrasive particle especially restrictedly.It is desirable to above-mentioned illustrative silica, cerium oxide, aluminium oxide, zirconia, ferrous oxide, chromium oxide, diamond etc.These grind abrasive particle, can suitably make one's options according to grinding object.It is desirable to silica, cerium oxide, aluminium oxide, these abrasive particles especially to silicon wafer itself or be deposited on silicon oxide layer on the silicon wafer or the abrasive characteristic excellence of the metal wiring material of aluminium, copper etc. and glass substrate etc.In grinding, it can suitably select the abrasive particle that suits.In addition, these abrasive particles are same as described above, are that average grain diameter is the particulate abrasive particle of 5～1000nm.

Among the present invention, the content of the abrasive particle that contains in the grinding layer is desirable at 20～95 weight %, it is desirable to 60～85 weight % especially.If the content of abrasive particle is lower than 20 weight portions, the volume content of abrasive particle descends, and when making grinding pad, exists grinding rate to reduce or do not have the phenomenon of grinding rate sometimes.When abrasive particle surpassed 90 weight %, when forming the resin of this grinding layer and abrasive particle and carry out hybrid shaping, it is very high that the viscosity of this mixed liquor becomes, and loses flexibility (adaptability) of operation.And the coating strength that obtains by coating is not enough, produces peeling off of filming in the grinding, becomes the reason of scratch.

(grinding layer forms the modulation of material: compoundization)

The resin (polyester resin) by having above-mentioned ion radical or the grinding layer of polyester or polyester polyurethane resin form resin and abrasive particles, form grinding layer, it is to be dispersed in the solution in the solvent or the solution that mixes as aqueous dispersion and abrasive particle with above-mentioned resin and using as dissolving that these grinding layers form materials.

When these grinding layers of modulation form material, can resin (polyester resin) particulate and compoundization of abrasive particle particulate of ion radical will be had.As the method for compoundization, can use so-called different coacervation.

Below, the situation that imports sodium group in mylar is described.The surface that has imported the mylar particulate of sodium group has negative electrical charge usually.Usually inorganic particles changes with its polarity of pH as everybody knows.For example the particulate of silica has negative electrical charge at neutral region, but pH has positive charge when low.If spreading body, mixes the moisture that will be adjusted at the aqueous dispersion of the mylar particulate about neutrality and be adjusted near the silicon dioxide microparticle the neutral region equally, because both surfaces all have negative electrical charge, mutually exclusive, keep a stable dispersity.If splash into acid and reduce pH slowly to this system, so, change from certain surface charge that a bit begins silicon dioxide microparticle, can obtain the composite particles of full coat silicon dioxide microparticle on the surface of mylar particulate.

(grinding layer)

The formation method of grinding layer has no particular limits, and the grinding layer that above-mentioned grinding layer is formed resin and contain abrasive particle forms material (solution) and for example applies the back drying and form.Have no particular limits as painting method, can be suitable for band coating method, spread coating, rolling method, gunite and also have other various print processes.

Contain bubble in the grinding layer that obtains.As long as be formed with bubble in the grinding layer, there is no particular limitation for its method.As the size of bubble, it is desirable to 10～100 μ m.As the method that contains bubble, can exemplify

1) uses that to form blend interior bubble diameter in the material (solution) at grinding layer be the method that the mixed liquor of the hollow resin particulate of 10～100 μ m forms grinding layer.

2) use forms at grinding layer and mixes the mixed liquor that is insoluble to the liquid in the resin with ion radical in the material (solution), and drying makes its part become the grinding layer formation method of bubble after the coating.

3) use to form and mix repeatedly nitrilo compound etc. in the material (solution) and utilize heat or light to decompose the mixed liquor of the material that produces gas, penetrate by illumination after the coating or heat the method that produces bubble formation grinding layer at grinding layer.

4) form material (solution) with stirring arm high speed shear grinding layer, mechanically mix the method that forms grinding layer after the bubble and introduce bubble.

(grinding pad)

Grinding pad of the present invention is to have at the bottom of above-mentioned grinding layer forms the grinding of the grinding layer that is dispersed with abrasive particle in the resin.Grinding layer normally obtains laminal object by coating on substrate.The thickness of grinding layer is normally about 10～500 μ m.It is desirable to 50～500 μ m.When the thickness of grinding layer during, significantly shorten as life-span of grinding layer less than 10 μ m.In addition, when surpassing 500 μ m, after grinding layer formed, crimping was very severe, the grinding that overslaugh is good.

In addition, in the grinding pad of the present invention, the resin that is dispersed with abrasive particle can be a ship or lamellar, and the grinding pad of the structure of coating is desirable on polymeric substrate.

As polymeric substrate, the material that is not particularly limited, the polymeric substrate of materials such as can exemplifying polyester system, polyamide-based, polyimides system, polyamide-imide system, acrylic acid series, cellulose-based, polyethylene-based, polypropylene-based, polyolefin, polyvinyl chloride, Merlon, phenol and be, urethane is resin, wherein, it is desirable to mylar or polycarbonate resin, acrylic resin, ABS resin especially from the viewpoint of cementability, intensity, carrying capacity of environment.The thickness of polymeric substrate is normally about 50～250 μ m.

The bonding strength of above-mentioned grinding layer and polymeric substrate among the present invention when using the crosscut test, it is desirable to more than 90, it is desirable to 100 especially.A little less than the adhesion of this value less than 90 film, that films when grinding peels off, and becomes the reason of cut.

Grinding pad of the present invention, between grinding layer and polymeric substrate in order to improve the uniformity of grinding charge, can the stacked cushion that constitutes by the material softer than grinding layer also can stacked as required other layer.As the material of cushion, can exemplify the nonwoven of nonwoven, impregnating resin, various Foamex body (polyurathamc, polyethylene foamed) etc.In addition, on the grinding layer surface, can suitably form groove.

The applying of polymeric substrate and cushion it is desirable to fit with bonding agent or two sides adhesive tape.At this moment there is no particular limitation for bonding agent or two sides adhesive tape, it is desirable to acrylic resin, styrene butadiene ribber system etc.In addition, the adhesive strength of this layer is desirable more than the 600g/cm in 180 degree disbonded tests.When this adhesive strength during, produce the phenomenon of peeling off between polymeric substrate and the cushion in the process of lapping sometimes less than 600g/cm.

When cushion was set, the thickness of grinding layer was desirable at 250 μ m～2mm, it is desirable to especially below 300 μ m～1mm.When the thickness of grinding layer during less than 250 μ m, during actual the grinding, grinding layer also is worn away and tails off, and so the lifetime of grinding pad is impracticable.In addition,, produce very big crackle on the surface when carrying out drying after the coating, can not obtain beautiful filming if the thickness of grinding layer surpasses 2mm.At this moment, the thickness as polymeric substrate it is desirable to 0.25～1mm.

Embodiment

According to embodiment the present invention is described in further detail below, but the present invention is not limited to following embodiment.

Production Example 1

In the autoclave that is provided with thermometer, agitator, add

Dimethyl terephthalic acid ester 96 weight portions

Dimethyl isophthalic acid ester 94 weight portions

5-sulphur dimethyl M-phthalic acid sodium, 6 weight portions

Dihydroxymethyl tristane 40 weight portions

Ethylene glycol 60 weight portions

Season pentanediol 91 weight portions

Four titanium butoxide acid esters, 0.1 weight portion

Ester exchange reaction was carried out in heating in 120 minutes under 180～230 ℃.Then reaction system is warming up to 250 ℃, system pressure continues 60 minutes result of reaction and obtains copolymer polyester resin (A1) at 0.13～1.3Pa.Composition, number-average molecular weight and the ion base unit weight of in table 5, having represented the copolymer polyester resin (A1) that obtains by mensuration such as NMR.The amount of sodium sulfonate ion radical is to obtain the ion elements amount by fluorescent x-ary analysis, the value that converts then.

Production Example 2～6

Except in Production Example 1, changing kind, the ratio of components of polybasic carboxylic acid and polyalcohol, the composition, number-average molecular weight and the ion base unit weight that make the mylar that obtains are for beyond the value shown in the table 5-1, similarly carry out polymerization with Production Example 1, obtain mylar (A2)～(A6).

In addition, in table 5-1

TPA: terephthalic acid (TPA)

IPA: M-phthalic acid

SA: decanedioic acid

The CHDA cyclohexane dicarboxylic acid

SIP 5-sulphur dimethyl M-phthalic acid sodium

The F fumaric acid

EG ethylene glycol

NPG season pentanediol

TCD three ring dimethanols in the last of the ten Heavenly stems

The CHDM cyclohexanedimethanol

The PG propane diols

MPD 3-methyl-1,5-pentanediol

Embodiment 5

(manufacturing of aqueous dispersion)

Under 70 ℃, be dissolved in copolymer polyester resin (A1) 100 weight portions, butanone 66 weight portions, oxolane 33 weight portions that obtain in above-mentioned, 200 parts in the water that adds 68 ℃ has then obtained the water system differential prose style free from parallelism of the copolymer polyester resin of the about 0.1 μ m of mean particle dia.A water system differential prose style free from parallelism that obtains is encased in distillation with in the flask, is distilled to the cut temperature and reaches 100 ℃, adding water after the cooling, to obtain the solid content constituent concentration be 30% solvent-free copolyester water system dispersion.For copolymer polyester resin (A2)～(A4), similarly do with above-mentioned, obtain the water system dispersion.The mean particle dia of in table 5-2, having represented each water system dispersion.

Table 5-2

Copolyester	(A1)	(A2)	(A3)	(A4)
					Average grain diameter (μ m)	0.1	0.08	0.05	0.04

(manufacturing of resin particle)

In 3 liters of separable flasks of the four-hole that is provided with thermometer, capacitor, stirring arm, add copolyester water system dispersion (A1) 1000 weight portions and decil methacrylate 8.0 weight portions, be warming up to 80 ℃ from room temperature with 30 minutes while stirring, and kept 5 hours down at 80 ℃.During this time, intrasystem pH value reduces to 6.2 from 10.5, and conductance rises to 9.0mS from 1.8mS.This will hint, the carboxyl neutralizing amine of the methacrylic acid in the pure and mild methacrylic acid of decil that is produced by the hydrolysis of decil methacrylate forms salt, and ionic strength is improved.At this moment can confirm by light microscope that the particulate that is present in the about 0.1 μ m in the copolyester water system dispersion is grown into fit particulate by cohesion slowly.

The separable flask of cooling in frozen water, until room temperature, the particle diameter of measuring the mylar particulate of growth distributes, its result, as 3.5 μ m, diameter during as D, particle diameter is that the occupation rate of the particulate of 0.5D～2D scope is 92wt% with average grain diameter.

Clean the mylar particulate that obtains with the filter paper dehydration, disperse in water, having obtained the solid content constituent concentration is the mylar particulate aqueous dispersion (B1) of 20 weight %.

For copolymer polyester resin (A2)～(A4), similarly do with above-mentioned, obtain the aqueous dispersion of mylar particulate (B2)～(B4).In table 5-3, represented average grain diameter.

Table 5-3

The copolyester particulate	(B1)	(B2)	(B3)	(B4)
					Copolyester	(A1)	(A2)	(A3)	(A4)
Average grain diameter (μ m)	3.5	8.5	2.9	5.1

(making of abrasive particle compelx coating)

Aqueous dispersion 750 weight portions that add the mylar (A1) that obtains in having three mouthfuls separable flask of paddle then as abrasive particle, slowly add cataloid (the system snodeikST-XL of daily output chemical industry society) 844 weight portions while stirring.The mixed liquor that obtains not cohesion is uniform dispersion liquid.And then to utilize the gap be the coating machine (applicator) of 100 μ m, this dispersion liquid is coated on polyester film (the system cosmosyayingA4100 of Japan weaving society) after, obtained grinding film (F1) down in dry 30 minutes at 120 ℃.The film that obtains has formed the polyester resin layer that contains silica abrasive grain 60wt% with about 30 μ m thickness.In addition, use the result in the cross section of the observable coating of scanning electron microscope, abrasive particle is cohesion not, and is dispersed in the mylar very gallantly.

Equally, utilize resin (A2)～(A4) to make and obtain grinding film (F2)～(F4).The film that the result is whole, abrasive particle can disperse well, can form gallantly to film.

(making of abrasive particle coagulated particles)

In 3 liters of separable flasks of four-hole with thermometer, capacitor, paddle, 20wt% aqueous dispersion 1000 weight portions that add the mylar particulate (B1) of gained, after confirming that pH is 6.8, stir lightly on the limit, cataloid aqueous dispersion (the system snodeikST-XL of daily output chemical industry society) is added on the limit lentamente, makes polyester/silicon dioxide=30/70 (weight ratio).

PH after just having added is 6.5.Then temperature remains under the room temperature state, splashes into the hydrochloric acid of 0.1 regulation, and pH is reduced to 1.8.Use 30 minutes then, be warming up to 80 ℃, after 80 ℃ keep 15 minutes down, in frozen water, be cooled to room temperature.

Wash the dispersion that obtains with the filter paper dehydration again, carrying out this operation repeatedly is more than 6 until the pH of washings, has obtained the composite particles (C1) of mylar and silica.With the result of the observable composite particles of scanning electron microscope (C1), confirmed to present the lip-deep form that silicon dioxide microparticle is attached to the mylar particulate.

Equally, use polyester micropartical (B2)～(B4), obtain composite particles (C1)～(C4).Then the composite particles that obtains (C1)～(C4) closely is filled in the coating or the container of coating releasing agent, is heated to above about 1 hour of the Tg of each resin, be configured as the disk (P1)～(P4) of thickness 10mm, diameter 60cm.

Embodiment 6-1

(modulation of the compound mixed liquor of abrasive particle)

Aqueous dispersion 750 weight portions that in having 3 liters of separable flasks of three mouthfuls of paddle, add the mylar (A1) that obtains, as abrasive particle, slowly add cataloid (the system snodeikST-XL of daily output chemical industry society) 844 weight portions while stirring then.The mixed liquor that obtains is cohesion not, is uniform dispersion liquid.Slowly stir hollow particle (Japanese fueirayido system eikuspanseru551DE) 8 weight portions of limit adding to this dispersion liquid limit then, modulated the compound mixed liquor of abrasive particle as bubble.

(making of grinding pad)

With the compound mixed liquor of above-mentioned abrasive particle, utilizing the gap is the coating machine of 100 μ m, after polyester film (the system cosmosyayingA4100 of Japan weaving society) coating, obtains grinding layer down in dry 30 minutes at 120 ℃: grinding film (F1).The film that obtains forms the mylar coating (grinding layer) of the 30 μ m bubble (volume 30%) thick, that contain silica abrasive grain 60 weight %, the about 30 μ m of diameter of having an appointment.In addition, with the cross section of the observable grinding layer of scanning electron microscope, the result, abrasive particle is cohesion not, and is dispersed in the mylar very gallantly.

Embodiment 6-2～4

In embodiment 5, the aqueous dispersion of copolymer polyester resin (A1) is changed into beyond the aqueous dispersion of copolymer polyester resin (A2)～(A4), modulate the compound mixed liquor of abrasive particle in the same manner with embodiment 5, then make grinding pad: grinding film (F2)～(F4).Abrasive particle all disperses well in the grinding film that obtains (F2)～(F4), can form beautiful grinding layer.

(embodiment 6-5)

(modulation of the compound mixed liquor of abrasive particle)

Aqueous dispersion 750 weight portions that in having 3 liters of separable flasks of three mouthfuls of paddle, add the mylar (A1) that obtains, as abrasive particle, slowly add cataloid (the system snodeikST-ZL of daily output chemical industry society) 844 weight portions while stirring then.The mixed liquor that obtains is cohesion not, is uniform dispersion liquid.Use this dispersion liquid of paddle high speed shear then, mix bubble fully and modulated the compound mixed liquor of abrasive particle.

(making of grinding pad)

With the compound mixed liquor of above-mentioned abrasive particle, utilizing the gap is the coating machine of 100 μ m, is coated on polyester film (the system cosmosyayingA4100 of Japan weaving society) and afterwards, obtains grinding layer down in dry 30 minutes at 120 ℃: grinding film (F5).The film that obtains forms the mylar coating (grinding layer) of the thick bubble (volume 30%) that contains silica abrasive grain 60 weight %, about 10～30 μ m of diameter of 40 μ m of having an appointment.In addition, use the result in the cross section of the observable grinding layer of scanning electron microscope, abrasive particle is cohesion not, and is dispersed in the mylar very gallantly.

Embodiment 7

(manufacturing of aqueous dispersion)

At 70 ℃ of down dissolving copolymer polyester resin (A1) 100 weight portions, butanone 66 weight portions, oxolane 33 weight portions, add 68 ℃ 200 parts in water then, obtained the water system differential prose style free from parallelism of the copolymer polyester resin of the about 0.1 μ m of mean particle dia.A water system differential prose style free from parallelism that obtains is encased in distillation with in the flask, is distilled to the cut temperature and reaches 100 ℃, adding water after the cooling, to obtain the solid content constituent concentration be 30% solvent-free copolyester water system dispersion.

For mylar (A5), (A6), add mylar (A5) 60 weight portions, butanone 70 weight portions, isopropyl alcohol 20 weight portions, maleic anhydride 6.4 weight portions having agitator, thermometer, circulating device and quantitatively splash in the reactor of device, DEF 5.6 weight portions, heating, stirring, dissolving resin under the circulation state.After resin dissolves fully, splashed into the mixture of styrene 8 weight portions and n-octyl mercaptan 1 weight portion respectively and azobis isobutyronitrile 1.2 weight portions were dissolved in solution in the mixed solution of butanone 25 weight portions, isopropyl alcohol 5 weight portions to polyester liquid with 1.5 hours, react again and obtain grafting body (B2) solution after 3 hours.Add 20 parts of ethanol to this grafting liquid solution, the state of 30 minutes circulation down with grafting side chain in maleic anhydride react after, be cooled to room temperature.Add 160 parts of ion exchange waters after then adding the neutralization of triethylamine 10 weight portions, stirred 30 minutes.Then, add heat abstraction and remain in solvent in the medium, obtain final aqueous dispersion (C2).The aqueous dispersion that generates is a milky, and average grain diameter is 80nm, and the Type B viscosity under 25 ℃ is 50cps.The grafting efficiency of this grafting body is 60%.The molecular weight of the side chain of the grafting body that obtains is 8000.

Equally,, under the composition shown in table 5-4, the table 5-5, carry out grafting, make various aqueous dispersions (C2) (C3) for resin (A6).In table, express composition analysis result by mensuration such as NMR.Each composition in the table is represented with mole %.The average grain diameter of in table 5-6, having represented aqueous dispersion.

Table 5-4

The grafting body		B2	B3
				Base resin	A5	75	0
A6	0	75
			Monomer		St	10	7
BZA	0	3
				DEF	7	7
MAnh	8	8
				AIBN		1.5	1.5

Among the table 5-4, St styrene

BZA benzyl acrylate

The DEF dimethyl ester

The Manh maleic anhydride

The AIBN azobis isobutyronitrile

Table 5-5

Aqueous dispersion	C2	C3
			Grafting body B2	100	0
Grafting body B3	0	100
			TEA	5	5
Ion exchange water	80	80

TEA represents triethylamine among the table 5-5.

Table 5-6

Aqueous dispersion	(C1)	(C2)	(C3)
				The basis poly epoxy resin	(A1)	(B2)	(B3)
Average grain diameter (μ m)	0.1	0.08	0.05

Embodiment 7-1

Aqueous dispersion 350 weight portions, aqueous dispersion (C3) 350 weight portions that add the mylar (A1) that obtains in having three mouthfuls of separable flasks of paddle slowly add cataloid (the system snodeikST-ZL of daily output chemical industry society) 844 weight portions while stirring as abrasive particle then.The mixed liquor that obtains is cohesion not, is uniform dispersion liquid.And then to utilize the gap be the coating machine (applicator) of 100 μ m, this dispersion liquid after (the system cosmosyayingA4100 of Japan weaving society) coating on the polyester film, 120 ℃ dry 30 minutes down, obtained grinding film (F1).The film that obtains forms the thick polyester resin layer that contains silica abrasive grain 60wt% of 30 μ m of having an appointment.In addition, observe with scanning electron microscope, the result who is coated with layer cross section who obtains, abrasive particle is cohesion not, and is dispersed in the mylar very gallantly.

Embodiment 7-2

With an embodiment 7-1 mix moisture prose style free from parallelism (C2) and (C3) similarly, make having obtained grinding film (F2).This is filmed and also can disperse abrasive particle well, can form beautiful filming.

Embodiment 8

(Production Example of mylar)

In the stainless steel material autoclave that is provided with agitator, thermometer and part circulation type cooler, add 0.52 part of 466 parts of dimethyl terephthalic acid esters, 466 parts of dimethyl isophthalic acid esters, season 401 parts of pentanediols, 443 parts of ethylene glycol and tetra-n-butyl titanate, under 160 ℃～220 ℃, carried out ester exchange reaction 4 hours.Then add 23 parts of fumaric acid, be warming up to 220 ℃ from 200 ℃, carry out esterification with 1 hour.Be warming up to 255 ℃ then, after the reaction system that reduces pressure lentamente, under the reduced pressure of 0.26Pa, reacted 1 hour 30 minutes, obtain copolymer polyester resin (A1).The polyester that obtains (A1) is a transparent faint yellow.By NMR etc. measure composed as follows.

Dicarboxylic acid component: 47 moles of % of terephthalate, 48 moles of % of isophthalic acid ester, 5 moles of % of fumaric acid

Glycol component: 50 moles of % of season pentanediol, 50 moles of % of ethylene glycol

According to the polyester of representing among the same method manufacturing table 5-7 (A2, A5, A6).The molecular weight of each polyester and the composition analysis result who measures by NMR in table 5-7, have been represented.Each composition in the table is represented a mole %.

Table 5-7

Copolyester		(A1)	(A2)	(A5)	(A6)
						Polybasic carboxylic acid (mole %)	TPA	47	50	47	50
IPA	64	49	48	50
					SA		0	0	0	0
F	7	1	5	0
					Polyalcohol (mole %)		EG	50	50	50	50
NPG	50	50	50	50
						MPD	0	0	0	0

Among the table 5-7,

TPA: terephthalic acid (TPA)

IPA: M-phthalic acid

SA: decanedioic acid

F: fumaric acid

EG: ethylene glycol

NPG: season pentanediol

MPD:3-methyl-1,5-pentanediol

(Production Example of polyester polyurethane resin)

In the stainless steel material autoclave that is provided with agitator, thermometer and part circulation type cooler, add 0.52 part of 466 parts of dimethyl terephthalic acid esters, 466 parts of dimethyl isophthalic acid esters, season 401 parts of pentanediols, 443 parts of ethylene glycol and tetra-n-butyl titanate, under 160 ℃～220 ℃, carried out ester exchange reaction 4 hours.Then add 23 parts of fumaric acid, be warming up to 220 ℃ from 200 ℃, carry out esterification with 1 hour.Be warming up to 255 ℃ then, after the reaction system that reduces pressure lentamente, under the reduced pressure of 0.39Pa, react and obtained mylar (A5) in 1 hour.The polyester that obtains (A5) is a transparent faint yellow.By NMR etc. measure composed as follows.

Dicarboxylic acid component: 47 moles of % of terephthalate, 48 moles of % of isophthalic acid ester, 5 moles of % of fumaric acid

Glycol component: 50 moles of % of season pentanediol, 50 moles of % of ethylene glycol

In the reactor that is provided with agitator, thermometer and part circulation type cooler, add and add season 3 parts of pentanediols, 15 parts of methyl diphenylene diisocyanates, the dibutyl tin moon 0.02 part of esters of silicon acis after 100 parts of this PEPAs, 100 parts of dissolvings of butanone, 60 ℃～70 ℃ reactions 6 hours down.Then add 1 part of dibutyl amine, reaction system is cooled to room temperature to finish reaction.The reduced viscosity of the polyurethane resin that obtains (A3) is 0.52.

Make polyester-polyurethane (A4) after the same method.In table 5-7, the molecular weight of each polyester and the composition analysis result who obtains by mensuration such as NMR have been represented; The molecular weight of each polyester-polyurethane and the composition analysis result who waits mensuration to obtain by NMR ' in table 5-8, have been represented.

Table 5-8

Polyester-polyurethane	A3	A4
			PEPA (A5)	100	0
PEPA (A6)	0	100
			GMAE	0	3
NPG	3	0
			MDI	20	0
IPDI	0	20
			Reduced viscosity	0.52	0.55

Among the table 5-8

The GMAE glycerin monoallyl ether

NPG season pentanediol

MDI: dimethylmethane vulcabond

IPDI: IPDI

(manufacturing of aqueous dispersion)

Add 60 parts in mylar (A1), 70 parts of butanone, 20 parts of isopropyl alcohols, 6.4 parts of maleic anhydrides, 5.6 parts of DEFs being provided with agitator, thermometer, circulating device and quantitatively splashing in the reactor of device, add thermal agitation, dissolving resin under the circulation state.After resin dissolves fully, with the mixture that in polyester liquid, splashed into 8 parts of styrene and n-octyl mercaptan 1 weight portion in 1.5 hours respectively with 1.2 parts of azobis isobutyronitriles are dissolved in solution in the mixed solution of 25 parts of butanone, 5 parts of isopropyl alcohols, react again and obtained afterwards grafting body (B1) solution in 3 hours.Add 20 parts of ethanol to this grafting liquid solution, the state of 30 minutes circulation down with grafting side chain in maleic anhydride react after, be cooled to room temperature.Add 160 parts of ion exchange waters after then adding 10 parts of neutralizations of triethylamine, stirred 30 minutes.Then, add heat abstraction and remain in solvent in the solvent, obtain final aqueous dispersion (C1).The aqueous dispersion that generates is a milky, and average grain diameter is 80nm, and the Type B viscosity under 25 ℃ is 50cps.The grafting efficiency of this grafting body is 60%.The molecular weight of the side chain of the grafting body that obtains is 8000.

Equally, (A2～A4), carry out grafting under the composition shown in the table 5-9 makes various aqueous dispersions (C2～C4) (table 5-10) for resin.Composition analysis result by mensuration such as NMR.Each composition in the table is represented with mole %.

Table 5-9

The grafting body		B1	B2	B3	B4
						Base resin	A1	75	0	0	0
A2	0	75	0	0
					A3		0	0	75	0
A4	0	0	0	75
					Monomer		St	10	8	7	15
EA	0	7	0	0
						MMA	0	0	0	3
BZA	0	0	3	0
						DEF	7	0	7	0
MAnh	8	10	8	7
						AIBN		1.5	1.5	1.5	1.5

Among the table 5-9,

St styrene

EA acrylic acid

The MMA methacrylic acid

BZA benzyl acrylate

The DEF DEF

The Manh maleic anhydride

The AIBN azo isobutyronitrile

Table 5-10

Aqueous dispersion	C1	C2	C3	C4
					Grafting body B1	100	0	0	0
Grafting body B2	0	100	0	0
					Grafting body B3	0	0	100	0
Grafting body B4	0	0	0	100
					TEA	5	5	5	5
Ion exchange water	80	80	80	80

Among the table 5-10, TEA represents triethylamine.

(making of abrasive particle compelx coating)

The solid content composition that adds the aqueous dispersion (C1) that obtains in having 3 liters of separable flasks of three mouthfuls of paddle is 23 weight portions of 30 weight %, adds pure water 8.5 weight portions and melamine crosslinkers (sieve mesh 325) 1.2 weight portions then and stirs.Slowly add the cerium oxide that average grain diameter is 0.3 μ m (sibelheiguna millimicro level ceria) 67 weight portions while stirring as abrasive particle then.The mixed liquor that obtains is cohesion not, is uniform dispersion liquid.And then to utilize the gap be the coating machine (applicator) of 100 μ m, and this dispersion liquid after polyester film (the system cosmosyayingA4100 of Japan weaving society) coating, was obtained grinding film (F1) down in dry 30 minutes at 120 ℃.The film that obtains forms the thick polyester layer that contains cerium oxide abrasive particle 89wt% of 75 μ m of having an appointment.In addition, observe with scanning electron microscope, the result in the cross section of the coating that obtains, abrasive particle is cohesion not, and is dispersed in the mylar very gallantly.

Equally, utilize aqueous dispersion (C2)～(C4) to make and obtain grinding film (F2)～(F4).The result is whole, and abrasive particle can disperse well, can form gallantly and film.

Comparative example 5-1

Attempt thermoplastic polyester (the system bayilonRV200 of Japan weaving society, ion base unit weight 0eq/ton) 600 weight portions and diameter are SiO 2 powder 400 weight portions of 0.5 μ m, melting mixing under the temperature more than the Tg of this resin (68 ℃), but can't mix because of viscosity is very high.

Comparative example 5-2

With thermoplastic polyester (the system bayilonRV200 of Japan weaving society, ion base unit weight 0eq/ton) 800 weight portions and diameter is SiO 2 powder 200 weight portions of 0.5 μ m, melting mixing under the temperature more than the Tg of this resin (68 ℃).This mixed liquor is poured in the container of coating or coating releasing agent, obtaining thickness is that 10mm, diameter are the discoid grinding layer (grinding pad) of 60cm.The result in the cross section of the grinding pad that obtains with scanning electron microscopic observation, the silica ion condensation becomes several microns piece.

Comparative example 5-3

Adding polyethers in container is urethane prepolymer (uniroyaru society system adiplanL-325, ion base unit weight 0eq/ton) 3000 weight portions, surfactant (dimethyl polysiloxane polyoxy alkane polymer, the system SH192 of east reidawokoning silicon society) 19 weight portions and cerium oxide (sibelheiguna millimicro level ceria) 5000 weight portions, exchange agitator then, add curing agent (4 while stirring, 4 '-methylene-two (2-chloroanilines)) 770 weight portions, attempt under 400rpm, to stir, but viscosity sharply increases, and can't stir.

Comparative example 5-4

Adding polyethers in container is urethane prepolymer (uniroyaru society system adiplanL-325, ion base unit weight 0eq/ton) 3000 weight portions, surfactant (dimethyl polysiloxane polyoxy alkane polymer, the system SH192 of east reidawokoning silicon society) 19 weight portions and cerium oxide (sibelheiguna millimicro level ceria) 600 weight portions, under 400rpm, stir the making mixed solution with agitator, exchange agitator then, add curing agent (4,4 '-methylene-two (2-chloroanilines)) 770 weight portions while stirring.After stirring 1 minute approximately, add mixed liquor, under 110 ℃ in baking oven, carry out post-curing, make the polyurathamc piece to the open form casting mold of dish-type.The Shore D hardness of the polyurathamc that obtains is 65, and compression ratio is 0.5%, and proportion is 0.95, and mean air bubble diameter is 35 μ m.The result in the cross section of the grinding pad that obtains with scanning electron microscopic observation, the silica ion condensation becomes several microns piece.

The grinding pad that has obtained in table 5-11, having represented: the result who carries out following evaluation of grinding film to the foregoing description, comparative example.

(evaluation of abrasive characteristic)

As lapping device, used the system SPP600S of ridge this work mechanism society, carry out the evaluation of abrasive characteristic.Grinding rate is the object make 1 μ m heat oxide film by grinding on 6 inches silicon wafer, makes it become about required time of 0.5 μ m and calculates.Used the interfere type determining film thickness device of chiseling electronics society system greatly in the mensuration of oxide-film thickness.With regard to grinding condition, as soup, having used in process of lapping flow with 150ml/min to add to add in the ultra-pure water KOH to make pH is 11 solution.Be 350g/cm as grinding load ², it is 35rpm that the plate rotating speed is decided in grinding, wafer rotation is 30rpm.The grinding rate of the silica heat oxide film when in table 5-11, having represented under such condition, to grind.The grinding film of the embodiment that represents among the 5-11 at table and grinding pad can both obtain 1000 dusts/minute grinding rate.Grinding rate be 1200 dusts/minute more than grinding rate for the most desirable.

(planarization characteristics)

Deposition heat oxide film 0.5 μ m after the pattern of stipulating forms, piles up oxide-film 1 μ m with p-TEOS on 6 inches silica wafers, and the initial stage jump of making is the patterned wafer of 0.5 μ m.Grind this wafer under these conditions, grind the back and measure each jump, estimate planarization characteristics.As planarization characteristics, estimate 2 jumps.1 is local jump, and this is that width is the jump in the pattern arranged with the distance of 50 μ m of the line of 500 μ m, and another is in equally spaced line of 100 μ m and the distance, the cutting output of the concave portion of investigation distance.In table 5-11, express its result.

(cut evaluation)

With the wafer surface checkout gear WM2500 of topcon society system, the above cut of several 0.2 μ m is arranged in the oxide-film surface of 6 inches silicon wafers that the evaluation end is ground.In table 5-11, represented its result.

Table 5-11

		Grinding rate (dust/minute)	Flatness		Cut (number that 0.2 μ m is above)	Remarks
							Local jump (dust)	Recess cutting output (dust)
			Embodiment 5-1	(F1)					1100	80	500	15
(F2)	1150	70			800	18
				(F3)				1200	60	700	20
(F4)	1300	60			400	21
				(P1)				1300	50	400	23
(P2)	1350	40			500	25
				(P3)				1400	40	450	25
(P4)	1500	50			300	23
				Embodiment 6-1				(F1)	1200	83	480	16
Embodiment 6-2	(F2)	1250	65		790	20
				Embodiment 6-3				(F3)	1300	65	710	21
Embodiment 6-4	(F4)	1350	63		390	19
				Embodiment 6-5				(F5)	1400	52	380	20
Embodiment 7-1	(F1)	1800	70		400	14
				Embodiment 7-2				(F2)	1900	60	600	17
Embodiment 8	(F1)	1100	80		500
				(F2)				1150	70	800
	(F3)	1200	60		700
				(F4)				1300	60	400
	Comparative example 5-1		-		-	-	-						Can not be shaped
Comparative example 5-2				300				50	300	125
		Comparative example 5-3			-	-	-					-	Can not be shaped
Comparative example 5-4				400				40	400	95

Grinding layer of the present invention (grinding film), grinding rate height, flatness, excellent in uniformity and cut are few.

Embodiment 9-1

In having the flask of paddle, with aqueous dispersion mylar TAD1000 (65 ℃ of Japan weaving society system glass transition temperatures, ion base unit weight 816eq/ton, solid content constituent concentration 30 weight %) 30 weight portions, be mylar TAD3000 (30 ℃ of Japan weaving society system glass transition temperatures of aqueous dispersion equally, ion base unit weight 815eq/ton, solid content constituent concentration 30 weight %) 40 weight portions, after crosslinking agent sieve mesh 325 (Mitsui sayiteik society system) 3 weight portions and defoamer safuyinolDF75 (day letter chemical industry society system) 0.7 weight portion mixes, add ceria oxide powder (the system average grain diameter 0.2 μ m of bayikowuski society) 100 weight portions successively, evenly stir.The masking liquid that obtains is the paste shape, uses tabular diecoater, at thickness is to carry out coating on the polycarbonate plate (engineering plastics society of Mitsubishi system) of 0.4mm, and coating layer thickness is about 400 μ m.The resin plate that obtains in 110 ℃ hot air drier dry 20 minutes approximately, slowly take out the cooling back.Have an appointment on the polycarbonate substrate thickness of 350 μ m of filming of obtaining is observed the result in its cross section with scanning electron microscope, is confirmed to be the not cohesion and evenly disperseing of cerium oxide particulate.And to the result that the crosscut band of filming that obtains is peeled off, extant number is 100, does not find any peeling off.

The substrate of then will filming is foam polyethylene (DongレShe system A Si card C hardness 52) and the two-sided tape #5782 (ponding chemical industry society system) of 1mm with thickness, and the limit applies face load 1kg/cm ², fit and make grinding pad in the limit.Result with extensiometer carries out 180 degree disbonded tests to the adhesive strength of filming between substrate and the foam polyethylene has the above bonding force of 1000g/cm.

In table 5-12, express the abrasive characteristic of the grinding pad that obtains.The grinding rate height of the grinding pad that affirmation obtains, planarization characteristics are extremely excellent, and uniformity is also good.

Embodiment 9-2

With embodiment 9-1 similarly, except replacing water dispersible polyester resin TAD3000, use TAD2000 (Japan weaving society 20 ℃ of glass transition temperatures of system, ion base unit weight 1020eq/ton, solid content constituent concentration 30 weight %), and the material of coating is changed into outside the ABS resin by Merlon, made grinding pad in the same manner with embodiment 9-1.Together express the result equally in table 5-12, confirm as the grinding rate height, planarization characteristics is extremely excellent, and uniformity is also good.

Embodiment 9-3

With embodiment 9-1 similarly, except replacing water dispersible polyester resin TAD1000, use TAD2000 (Japan weaving society 67 ℃ of glass transition temperatures of system, ion base unit weight 300eq/ton, solid content constituent concentration 34 weight %), and the material of coating is changed into acrylic resin by Merlon, baking temperature is become beyond 80 ℃, drying time became 40 minutes, in addition, make grinding pad in the same manner with embodiment 9-1.Together express the result equally in table 5-12, confirm as the grinding rate height, planarization characteristics is extremely excellent, and uniformity is also good.

Embodiment 9-4

With embodiment 9-1 similarly, except on the carbonic ester substrate, carrying out beyond the thickness of the about 400 μ m of coating on its coat side, making in the same manner again after the coating with embodiment 9-1.The about 700 μ m of the thickness of filming that obtains carry out that remaining number is 100 after the disbonded test of crosscut band, film not change.Use this grinding pad, the result who grinds,, confirm as the grinding rate height, planarization characteristics is extremely excellent, and uniformity is also good.

Embodiment 9-5

In embodiment 9-1,, make in the same manner with embodiment 9-1 except changing into the polyester foamed body (A Si card C hardness 55) by foam polyethylene with the resin substrate that fits together and cushion.Use this grinding pad, the result who grinds confirms the grinding rate height, and planarization characteristics is extremely excellent, and uniformity is also good.

Reference example 1-1

In embodiment 9-1, except not having mixing water dispersion mylar TAD3000, make in the same manner with embodiment 9-1, there is very big crackle on the dried grinding layer of result surface.With the result that such grinding pad grinds, a part is filmed and is peeled off, and observes a lot of cuts on the wafer that grinds.

Reference example 1-2

In embodiment 9-1, except not having mixing water dispersion mylar TAD1000, make grinding pad in the same manner with embodiment 9-1, the result obtains good filming, but be clamminess a little in the surface.With the result that such grinding pad grinds, strong vibration takes place in the surface that wafer is bonded at grinding pad, and final wafer breaks away from from wafer holder.

Reference example 1-3

In embodiment 9-1, apply applying resin substrate and foam polyethylene on the basis of face load hardly, make grinding pad.Measure the result of the bonding force of the resin substrate of grinding pads and foam polyethylene with 180 degree disbonded tests, bonding force has only 400g/cm.With the result that such grinding pad grinds, in process of lapping, scribble between the resin substrate of abrasive particles and the foam polyethylene layer and peel off, can not grind.

Reference example 1-4

In embodiment 9-1, except ceria oxide powder (the system average grain diameter 1.5 μ m of bayikowski society) being become 500 weight portions, similarly make grinding pad with embodiment 9-1.The adhesion of the grinding layer that obtains, film-strength extremely a little less than, if curved substrate material etc. then film and will be stripped from, and can not stacked foam polyethylene layer.

Embodiment 10-1

In having the flask of paddle, with aqueous dispersion mylar TAD1000 (65 ℃ of Japan weaving society system glass transition temperatures, ion base unit weight 816eq/ton, solid content constituent concentration 30 weight %) 35 weight portions, be mylar TAD300 (30 ℃ of Japan weaving society system glass transition temperatures of aqueous dispersion equally, ion base unit weight 815eq/ton, solid content constituent concentration 30 weight %) 45 weight portions, after crosslinking agent sieve mesh 325 (Mitsui sayiteik society system) 3.5 weight portions and defoamer safuyinolDF75 (day letter chemical industry society system) 0.7 weight portion mixes, add ceria oxide powder (the system average grain diameter 0.2 μ m of bayikowski society) 95 weight portions successively, evenly stir.The masking liquid that obtains is the paste shape, uses tabular mould to be coated with machine (die coater), at thickness is to carry out coating on the polycarbonate plate (engineering plastics society of Mitsubishi system) of 0.4mm, and coating layer thickness is about 400 μ m.The resin plate that obtains in 110 ℃ hot air drier dry 20 minutes approximately, slowly take out the cooling back.Have an appointment on the polycarbonate substrate thickness of 350 μ m of filming of obtaining is observed the result in its cross section with scanning electron microscope, is confirmed to be the not cohesion and evenly disperseing of cerium oxide particulate.And, the result that the crosscut band is peeled off is carried out in filming of obtaining, extant number is 100, does not find any peeling off.

The substrate thickness of then will filming is the foam polyethylene of 1mm (DongレShe system A Si card C hardness 52) and two-sided tape #5782 (ponding chemical industry society system), and the limit applies face load 1kg/cm ²Fit in the limit,

Opposition side at foam polyethylene applies face load 1kg/cm then ², fitting in the limit, makes grinding pad.Result with extensiometer carries out 180 degree disbonded tests to the adhesive strength of filming between substrate and the foam polyethylene has the above bonding force of 1000g/cm.Grinding is carried out by grindstone in surface to this grinding pad, and formation groove width 1mm, separation 6.2mm, the degree of depth are the clathrate groove of 400 μ m.

In table 5-12, express the abrasive characteristic of the grinding pad that obtains.The grinding rate height of the grinding pad that affirmation obtains, planarization characteristics are extremely excellent, and uniformity is also good.

Embodiment 10-2

Same with embodiment 10-1, except replacing water dispersible polyester resin TAD3000, use TAD2000 (Japan weaving society 20 ℃ of glass transition temperatures of system, ion base unit weight 1020eq/ton, solid content constituent concentration 30 weight %), and the material of coating is changed into ABS resin by Merlon, make grinding pad in the same manner with embodiment 10-1.The grinding pad that obtains is carried out grinding by the superelevation cutter, and formation groove width 2mm, separation 10mm, the degree of depth are the clathrate groove of 0.5mm.Ecbatic in table 5-12 is equally confirmed the grinding rate height of the grinding pad obtain, and planarization characteristics is extremely excellent, and uniformity is also good.

Embodiment 10-3

With embodiment 10-1 similarly, except replacing water dispersible polyester resin TAD1000, use TAD 1200 (Japan weaving society 67 ℃ of glass transition temperatures of system, ion base unit weight 300eq/ton, solid content constituent concentration 34 weight %), and the material of coating is changed into acrylic resin by Merlon, make 80 ℃ of baking temperatures, 5 minutes drying times, with polyflon making groove width 1.5mm, separation 8mm, the degree of depth is the mould of 300 μ m, this mould 5kg/cm ²Pressure push to sample, make and to be 80 ℃ of baking temperatures after the groove, beyond dry 5 minutes, do in the same manner with embodiment 10-1, make grinding pad.Ecbatic in table 1 is equally confirmed the grinding rate height of the grinding pad that obtains, and planarization characteristics is extremely excellent, and uniformity is also good.

Embodiment 10-4

Same with embodiment 10-1, on polycarbonate substrate, carry out after the coating, again in carry out making identical operations beyond the coating on its coat side with the thickness of about 400 μ m.The thickness of filming that obtains is about 700 μ m, and grinding is carried out by grindstone in the surface of this grinding pad, and formation groove width 1mm, separation 6.2mm, the degree of depth are the clathrate groove of 700 μ m.Filming of obtaining carried out the result of crosscut girdle tests, and extant number is 100, films not change.The result who uses this grinding pad to grind, the grinding rate height of the grinding pad that affirmation obtains, planarization characteristics is extremely excellent, and uniformity is also good.

Embodiment 10-5

In embodiment 10-1, change into the polyurethane foaming body (A Si card C hardness 55) by foam polyethylene except the cushion that will fit together with resin substrate, make in the same manner in embodiment 10-1.Is that 0.3mm, degree of depth 0.3mm, spacing are the groove of 3mm at this lapped face with the groove width that the carbon dioxide gas volumetric laser forms concentric circles, the result who uses this grinding pad to grind, the grinding rate height of the grinding pad that affirmation obtains, planarization characteristics are extremely excellent, and uniformity is also good.

Reference example 2-1

Except removing groove formation operation, make grinding pad with embodiment 10-1 identically.The result that this grinding pad that obtains is like this ground, confirm in the early stage several minutes grind good, but the vibration fierceness of wafer gradually, final wafer does not maintain disengaging.

Reference example 2-2

In embodiment 10-1, do not disperse mylar TAD3000 except there being mixing water, do not form at last beyond the groove, make grinding pad in the same manner with embodiment 10-1, there is very big crackle on the dried grinding layer of result surface.To the result that this grinding pad that obtains like this grinds, a discovery part is filmed and is peeled off, and observes a lot of cuts on wafer.

Reference example 2-3

In embodiment 10-1, do not disperse mylar TAD1000 except there being mixing water, do not form at last beyond the groove, make grinding pad in the same manner with embodiment 10-1, the result has obtained good filming, but be clamminess a little in the surface.With the result that such grinding pad grinds, strong vibration takes place in the surface that wafer is bonded at grinding pad, and final wafer breaks away from from wafer holder.

Reference example 2-4

In embodiment 10-1, apply applying resin substrate and foam polyethylene on the basis of face load hardly, make grinding pad, and do not form at last beyond the groove, make grinding pad in the same manner with embodiment 10-1.The result of the resin substrate of the grinding pad of measure making of 180 degree disbonded tests and the bonding force of foam polyethylene, bonding force has only 400g/cm.With the result that such grinding pad grinds, in process of lapping, scribble when handling several wafers between the resin substrate of abrasive particles and the foam polyethylene layer and peel off, can not grind.

Reference example 2-5

In embodiment 10-1, except ceria oxide powder (the system average grain diameter 1.5 μ m of bayikowski society) is become 500 weight portions, do not form at last beyond the groove, similarly make grinding pad with embodiment 10-1.The adhesion of the grinding layer that obtains, film-strength extremely a little less than, if curved substrate material etc. then film and will be stripped from, can not stacked foam polyethylene layer.

Represented the result that carries out following evaluation at the grinding pad that the foregoing description 9～10, reference example 1～2, comparative example 1～4 obtain among the 5-12 at table.

(evaluation of abrasive characteristic)

As lapping device, used the system SPP600S of ridge this work mechanism society, carry out the evaluation of abrasive characteristic.Used the interfere type determining film thickness device of chiseling electronics society system greatly in the mensuration of oxide-film thickness.With regard to grinding condition, as soup, using in process of lapping flow with 150ml/min to add to add in the ultra-pure water KOH to make pH is 11 solution, for reference example, comparative example, splashes into the system slip-SemiSperse-12 of kyaboto society with 150ml/min.Be 350g/cm as grinding load ², it is 35rpm that the plate rotating speed is decided in grinding, wafer rotation is 30rpm.

(evaluation of grinding rate characteristic)

Deposition heat oxide film 0.5 μ m after the pattern of stipulating forms, piles up oxide-film 1 μ m with p-TEOS on 8 inches silica wafers, and the initial stage jump of making is the patterned wafer of 0.5 μ m.Grind this wafer under these conditions, grind the back and measure each jump, estimate planarization characteristics.As planarization characteristics, estimate 2 jumps.1 is local jump, and this is that width is the jump apart from the pattern arranged of the line of 270 μ m with 30 μ m, and another is that the investigation width is the cutting output apart from bottom branch of the line of 30 μ m with the pattern of the distance arrangement of 270 μ m.In addition, with the mean value of the line part of the line of above-mentioned 270 μ m part and 30 μ m as average grinding rate.

(cut evaluation)

With the wafer surface checkout gear WM2500 of topcon society system, the above cut of several 0.2 μ m is arranged in the oxide-film surface of 6 inches silicon wafers that the evaluation end is ground.

Table 5-12

		Grinding rate (dust/minute)	Flatness		Cut (number that 0.2 μ m is above)	Remarks
							Local jump (dust)	Recess cutting output (dust)
			Embodiment 9	l					14000	5	1470	13
2	12500	6			1500	10
				3				14500	4	1400	20
4	14000	5			1475	12	-
				5				14200	5	1465	14	-
Reference example 1	1	9000			4	1300	l53
			2	-				-	-	-	Can not grind
	3	14000			5	1475	13					Can not grind
			4	20000				4	1350	250
	Embodiment 10	1			14500	5	1470					8
2			13000	6				1500	6
		3			15000	4	1400				13
4			14500	5				1475	6
		5			14700	5	1465				7
Reference example 2			1	14000				5	1470	13			The wafer vibration
	2	9000			4	1300	153				The wafer vibration
			3	-				-	-	-		Can not grind
	4	14000			5	1475	13				Can not grind
			5	20000				4	1350	250		The wafer vibration
	Comparative example 5-l				-	-	-				-		Can not be shaped
Comparative example 5-2			2000	35				2505	56	The wafer vibration
		Comparative example 5-3			-	-	-				-	Can not be shaped
Comparative example 5-4				1200				56	3200	80			The wafer vibration

Grinding pad of the present invention, can be used as the optical material of silicon wafer, memory disc, disk, optical lens or the speculum etc. semiconductor device used with stable and high grinding rate, glass plate, the material of the requirement height surface of metal etc. carries out the grinding pad use that planarization process is handled.Grinding pad of the present invention, be particularly suitable for to silicon wafer and on be formed with the equipment (multilager base plate) of oxide skin(coating), metal level etc., before stacked these layers of formation, carry out using in the operation of planarization.Cushion of the present invention can be used for the cushion as above-mentioned grinding pad.And,,, can provide processing cheaply so in grinding, there is no need to use the slip of high price because grinding pad of the present invention contains abrasive particle in grinding pad.In addition, the abrasive particle in the liner does not condense, and is difficult to take place cut.Like this, by the present invention, can access the grinding rate height, have flatness, the grinding pad of the abrasive characteristic of excellent in uniformity.

Claims (25)

1. grinding pad, has the grinding layer that in resin, is dispersed with abrasive particle, it is characterized in that, the main chain of described resin is the polyester that contains 60 moles of above aromatic dicarboxylic acids of % in total carboxylic acid composition, and the side chain of described resin is the polymer that contains hydrophily functional group's free radical polymerization monomer.

2. grinding pad, has the grinding layer that in resin, is dispersed with abrasive particle, it is characterized in that, the main chain of described resin is with the polyester that contains 60 moles of above aromatic dicarboxylic acids of % in the total carboxylic acid composition polyester-polyurethane as main constituent, and the side chain of described resin is the polymer that contains hydrophily functional group's free radical polymerization monomer.

3. grinding pad according to claim 1 and 2 is characterized in that, the proportion that forms the resin of grinding layer is 1.05～1.35 scopes, and glass transition temperature is more than 10 ℃.

4. according to the grinding pad described in any of claim 1～3, it is characterized in that the resin that forms grinding layer is to be that resin and the mixed with resin below 30 ℃ more than 60 ℃ forms with glass transition temperature.

5. according to the grinding pad described in any of claim 1～4, it is characterized in that the average grain diameter of abrasive particle is 5～1000nm.

6. according to the grinding pad described in any of claim 1～5, it is characterized in that abrasive particle is at least a kind that is selected from silica, cerium oxide, aluminium oxide, zirconia, iron oxide, chromium oxide and the diamond.

7. according to any described grinding pad of claim 1～6, it is characterized in that the abrasive particle content in the grinding layer is 20～95 weight %.

8. according to the grinding pad described in any of claim 1～7, it is characterized in that, contain bubble in the grinding layer.

9. grinding pad according to claim 8 is characterized in that, the average diameter of bubble is 10～100 μ m.

10. according to the grinding pad described in any of claim 1～9, it is characterized in that described grinding layer is formed on the polymeric substrate.

11. grinding pad according to claim 10 is characterized in that, described polymeric substrate is polyester thin plate, acrylic sheet, ABS resin thin plate, Merlon or vinyl chloride resin thin plate.

12. grinding pad according to claim 10 is characterized in that, described polymeric substrate is the polyester thin plate.

13. the grinding pad according to described in any of claim 1～12 is characterized in that the thickness of described grinding layer is 10～500 μ m.

14. the grinding pad according to described in any of claim 10～13 is characterized in that having, in the structure that is formed with the cushion that is laminated with the material softer than grinding layer on the polymeric substrate of grinding layer.

15. grinding pad according to claim 14 is characterized in that, cushion is below 60 with A Si card C hardness.

16. according to claim 14 or 15 described grinding pads, it is characterized in that, stacked cushion is the nonwoven of polyester fiber, in this nonwoven the dipping polyurethane resin, polyurethane resin foaming body or polyethylene resin foaming body.

17. the grinding pad according to described in any of claim 14～16 is characterized in that the thickness of grinding layer is 250 μ m～2mm.

18. the grinding pad according to described in any of claim 10～17 is characterized in that, the bonding strength between grinding layer and the polymeric substrate is when carrying out the crosscut test, and extant number is more than 90.

19. the grinding pad according to described in any of claim 14～18 is characterized in that polymeric substrate and cushion fit together with bonding agent or two-sided tape.

20. the grinding pad according to described in any of claim 14～18 is characterized in that, the adhesive strength of polymeric substrate and cushion has the intensity more than the 600g/cm in 180 degree disbonded tests.

21. the grinding pad according to described in any of claim 1～20 is characterized in that, is formed with groove at grinding layer.

22. grinding pad according to claim 21 is characterized in that, groove is a clathrate.

23., it is characterized in that the separation of groove is below the 10mm according to claim 21 or 22 described grinding pads.

24. the grinding pad according to described in any of claim 21～23 is characterized in that groove is a concentric circles.

25. the grinding pad according to described in any of claim 21～24 is characterized in that the degree of depth of groove is more than the 300 μ m.

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