KR100429691B1 - Polishing pad and forming methode of the same - Google Patents

Abstract

The present invention relates to an improved microporous-containing polishing pad and a method for manufacturing the same, and to inorganic particles having a relatively high specific gravity and nonuniformity in density and hardness caused by using an organic polymer hollow sphere having a relatively low specific gravity compared to a matrix. By using a hollow coated sphere to minimize specific gravity deviation between the matrix resin and the curing agent to uniformly distribute the micropores to increase the density and hardness uniformity of the polishing pad, and to reduce the use of abrasive slurries as the inorganic powder functions as an abrasive. And it can provide a microporous-containing polishing pad that can increase the polishing effect.

In addition, in order to increase the flow and distribution effect of the polishing slurry during the polishing process, it is composed of a macro groove that prevents and distributes the slurry as a main flow passage and a micro groove that increases the continuous flow and distribution effect of the slurry to increase the polishing efficiency. Provide a groove shape.

Description

Polishing pad containing micropores and manufacturing method thereof {Polishing pad and forming methode of the same}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microporous-containing polishing pad and a method for manufacturing the same, and more particularly, to a polishing pad used in a planarization process by chemical mechanical polishing (hereinafter referred to as CMP) of a semiconductor wafer. Inorganic hollow spheres coated with an inorganic powder having a uniform specific gravity and high specific gravity, and / or a polishing pad in which micropores are formed by using an organic hollow sphere which is in an unfoamed state before curing and is foamed by thermal expansion during curing, and It relates to a manufacturing method.

In recent years, as semiconductor devices are rapidly becoming highly integrated, wiring patterns become denser, and there is a limit to achieving finer patterns due to densification only by improving the exposure technique at the time of pattern formation. In addition, the unevenness of the surface of the semiconductor wafer is amplified by high integration, and it is difficult to form the wirings densely. Therefore, there is an urgent need for a technology for planarizing the wafer surface.

In addition, the rapid integration of semiconductor devices requires smaller wiring patterns or interconnects that connect the active regions, resulting in smaller tolerances to the flatness of semiconductor wafers used in these processes. .

A CMP apparatus of a general semiconductor wafer is composed of a rotary turntable equipped with a polishing pad, a wafer carrier, a polishing slurry supply device and a diamond dresser. Such a CMP apparatus places a semiconductor wafer mounted on a carrier on an upper portion of the polishing pad, rotates the turntable while applying a load to the wafer carrier, and continuously supplies polishing slurry to provide friction between the polishing pad and the semiconductor wafer. Polishing efficiency can be increased by simultaneously performing mechanical polishing and chemical polishing due to the chemical composition of the slurry.

Here, the wafer carrier serves to transfer the wafer, and the slurry supply device supplies the polishing slurry. For example, the polishing slurry for the oxide film CMP generally includes colloidal silica or fumed silica 10 to 10. It is a high alkali solution adjusted to pH 10 ~ 12 by adding 20% to potassium hydroxide (KOH) or ammonium hydroxide (NH ₄ OH), and the silica particles help mechanical polishing, and the high alkali solution performs chemical polishing. . In addition, if the diamond dresser is clogged by the polishing residues of the semiconductor wafer during the polishing operation process, which consists of continuous pressure and rotation, the pores lose the function of storing the slurry liquid. In this case, the surface of the polishing pad is conditioned to remove the non-uniform wear layer to provide a uniform polishing surface.

Polishing pads used in the above CMP apparatus include a porous nonwoven type prepared by impregnating polyurethane into a nonwoven fabric, and a type derived from expanded polyurethane prepared by a wet coagulation method of a polyurethane solution. All of these have a structure in which the matrix itself has pores therein, and serves to hold the polishing slurry supplied during the polishing process.

As the nonwoven fabric type, a polishing pad of Japanese Patent Laid-Open No. 2-250776 is known. It is manufactured by impregnating a polyurethane / DMF solution into a nonwoven fabric and then solidifying it in a DMF aqueous solution to form micropores. When polishing, the contact with the semiconductor wafer and the retention of the polishing slurry are good, but the surface hardness is low. There is a problem in that deformation easily occurs to lower the flatness of the semiconductor wafer.

In addition, the polishing pad described in WO 9404599 is a polyurethane-derived type, which is an isocyanate-terminated urethane prepolymer as the main component of the matrix, and 4.4-methylene-bis- (2-chloroaniline as a curing agent (active hydrogen compound). After mixing and stirring (hereinafter referred to as MOCA), an expanded organic hollow sphere made of organic polymer (trade name Expancel 551 DE (Dry Expanded)) is added and mixed to cut the mold sheet cured to a certain thickness. Because of its high surface hardness, it has less compression set and improved polishing speed and flatness than nonwoven type.

1 is a cross-sectional view of a microporous-containing polishing pad manufactured using the foamed organic hollow spheres before curing, and the expanded organic hollow spheres 14 are impregnated in the polymeric matrix 12 constituting the polishing pad 10. have.

However, the polishing pad derived from the polyurethane according to the prior art has the following problems. In other words, the conventional polishing pad uses a pre-expanded organic hollow spheres, because the expanded organic hollow spheres have a small specific gravity, and when mixed with the matrix resin, the viscosity of the resin is significantly increased, when the foam is mixed with a curing agent This results in non-uniform bubbles remaining in the molding. In addition, the expanded organic hollow spheres have a specific gravity of about 0.042 g / cm 3 and have a large specific gravity difference with the matrix resin, so that their mixtures (compounds) are easily separated, and the organic hollow spheres are scattered during mixing with the matrix resin or the curing agent. There is a disadvantage in that the working environment is poor, and accurate mixing ratio adjustment is difficult.

Therefore, in the case of molding the urethane formed with micropores with a two-component molding machine, the injection liquid discharged from the molding machine tends to have a batch production method, and thus there is a problem in that the productivity of the batch is reduced. In addition, when the resin composition liquid mixed and stirred with the matrix resin, the expanded organic hollow sphere, and the curing agent is injected into the mold, the expanded hollow sphere rises upwards before the resin is cured, and a phenomenon in which the expanded resin is ubiquitous in the upper direction of the molding As a result, the polishing pad of a certain thickness obtained by slicing the molding in the horizontal direction has a density difference and hardness difference between the upper side and the lower side, resulting in inconsistent material, resulting in variations in polishing characteristics of the polishing pads between wafer lots. There is a problem that occurs.

In addition, when the CMP process is performed, polishing is performed by injecting a slurry containing an abrasive between the semiconductor wafer and the polishing pad, and the slurry is made of chemicals such as expensive abrasives. Due to the nature of the process, there is a problem that the amount is more than the amount used in the process, and the actual efficiency is low and the excess supply is increased to increase the manufacturing cost.

The present invention is to solve the above problems, an object of the present invention is to improve the productivity by uniformly adjusting the dispersion state of the hollow spheres present in the polishing pad matrix, polishing the polishing pad by minimizing density and hardness deviation The present invention provides a polishing pad and a method for manufacturing the same, which can improve polishing characteristics by stabilizing the characteristics, thereby preventing variation in the polishing characteristics between lots of the polishing pads.

1 is a cross-sectional view of a polishing pad according to the prior art.

2 is a cross-sectional view of the polishing pad according to the embodiment of the present invention.

3 is a cross-sectional view of a polishing pad according to another embodiment of the present invention.

Figure 4 is a plan view of a polishing pad formed with a square macro groove according to the present invention.

5 is a plan view of a polishing pad having a rectangular macro and an X-Y type micro groove according to the present invention;

6 is a plan view of a polishing pad formed with an X-Y type macro and a micro groove according to the present invention.

<Description of Symbols for Major Parts of Drawings>

10,20,30,40,50 Polishing pads 12,22,32,42 Matrix

14,34: expanded organic hollow spheres 24,34: inorganic hollow spheres

42,52: Macro groove 44,54: Micro groove

Characteristics of the polishing pad according to the present invention for achieving the above object, (i) an inorganic hollow sphere coated with an inorganic powder on the outside of the organic endothelial, the hollow is formed inside the organic endothelial, and ( ii) a polymeric matrix in which said inorganic hollow sphere is incorporated.

The organic endothelial thermoplastic resin is, for example, polyvinyl alcohol, pectin, polyvinyl pyrrolidone, ethyl cellulose, methyl cellulose, propyl methyl cellulose, carboxymethyl cellulose, carboxypropyl cellulose, polyacrylic acid, polyacrylamide, polyethylene Resins consisting of glycols, polyhydroxyetheracrylites, styrene, urethanes, derivatives thereof, copolymers, kraft polymers or combinations thereof are used. In particular, an acrylonitrile copolymer, an acrylonitrile-vinylidene chloride copolymer or a styrene-acrylonitrile copolymer is preferable, and the inorganic powder is calcium carbonate, titanium oxide, silicon oxide, cerium oxide, aluminum oxide, It is composed of barium oxide, ceramics, etc.

The inorganic hollow sphere has a particle diameter of 10 ~ 150㎛ preferably 15-50㎛, specific gravity is 0.05 ~ 0.50 ± 0.05g / cm ³ preferably 0.10 ~ 0.40 ± 0.05g / cm ³ , the inorganic hollow sphere It is contained in 0.5-20 weight part with respect to 100 weight part of polymeric matrices, More preferably, 2 or more inorganic hollow spheres from which a particle size differs are mixed, For example, a particle diameter is 10-50 micrometers and 60-150 micrometers mutually. The hollow spheres of different particle diameters are mixed, and the mixing ratio may be about 2-8ː2-8 based on the weight ratio.

The polymeric matrix may be formed of various polymeric materials such as urethanes, melamines, polyesters, polysulfones, polyvinyl acetates, fluorinated hydrocarbons, derivatives thereof, copolymers, graft polymers or mixtures thereof, and the like. . Polyurethane derivatives are particularly preferred, and for example, isocyanate terminated urethane prepolymers, urethane-modified epoxy resins and styrene-acrylonitrile copolymers or mixtures thereof may be used. For example, the hollow containing the hydrocarbon gas whose boiling point is 70-120 degreeC is formed.

The matrix may further include an organic hollow sphere formed of a single layer of an organic coating together with an inorganic hollow sphere and having a hollow formed therein. At this time, the organic hollow sphere is a conventional organic hollow sphere (hereinafter referred to as the first organic hollow sphere) in which the hydrocarbon gas is contained in the hollow portion by foaming the low-boiling hydrocarbon in the hollow portion before curing, or liquefied hydrocarbon inside the organic coating before curing molding It may be another organic hollow sphere (hereinafter referred to as a second organic hollow sphere) or a mixture thereof, which is contained and is hollowed out by foaming by vaporization of the liquefied hydrocarbon at the time of curing molding. In addition, other types of hollow spheres or pores may be further included as necessary.

In addition, the matrix impregnated with the hollow sphere may have a density of 0.5 to 1.0 g / cm ³ , a hardness of shore D = 50 to 70, and further include a lower pad having different physical properties such as hardness under the matrix. For example, it is preferable to use a nonwoven fabric or urethane foam having a compression ratio of 5 to 15%, a compression modulus of 55 to 75%, and a hardness of 60 to 75 shore A.

In addition, it is preferable that a groove pattern is formed on the polishing surface of the polishing pad so that distribution and retention of slurry can be efficiently performed during the polishing operation, and in particular, an XY orthogonal macro groove showing XY axis orientation ( It is preferable to form an XY orthogonal micro groove together with the macro groove and the macro grooves, or to form a rectangular macro groove alone or together with the XY orthogonal micro grooves. In this case, the rectangular macro grooves are formed with a depth of 0.3-1.5 mm, a width of 0.1-1.0 mm, a pitch of 1.0-8.0 mm, and the XY-type micro grooves have a depth of 0.2-1.0 mm, a width of 0.1-0.5 mm, a pitch. It can be formed in 0.8-5.0 mm.

In the polishing pad according to the present invention, the specific gravity of the inorganic hollow sphere is relatively different from that of the polymeric matrix resin, thereby obtaining a polishing pad cake having an evenly distributed inorganic hollow sphere in the curing molding process, that is, obtaining a cylindrical polishing pad mass before the slicing process. The polishing pad cake may include (i) an inorganic hollow sphere coated with an inorganic powder on the outside of the organic endothelial and a hollow formed therein, and (ii) the inorganic hollow sphere is impregnated. It consists of a matrix cake.

In addition, the polishing pad manufacturing method according to the invention is characterized in that (a) an inorganic powder is coated on the outside of the organic inner shell (organic inner shell), the inside of the organic endothelial inorganic hollow sphere is formed (void) Preparing a mixture by mixing with a polymeric matrix resin, (b) adding and stirring a curing agent to the mixture, and (c) injecting the resultant into a mold to cure and demolding. . When the polishing pad cake obtained after demolding is sliced, a plate-shaped polishing pad is obtained.

The curing agent is an active hydrogen compound, in particular a polyamine or a mixture of polyols and polyamines, the inorganic hollow spheres are mixed at 0.5 to 20 parts by weight based on 100 parts by weight of the matrix resin, and the curing agent is 100 parts by weight of the polymeric matrix resin. It is preferably added at 15-50 parts by weight.

In the step (b), the mixing process may be performed by using a two-liquid component molding machine including a first tank filled with the inorganic hollow sphere and a matrix resin mixture, and a second tank filled with the curing agent. It is preferable to maintain one tank at 60-90 degreeC, and a 2nd tank at 80-120 degreeC.

Hereinafter, a polishing pad and a method of manufacturing the same according to the present invention will be described in detail.

In the polishing pad according to the present invention, an inorganic hollow sphere coated with an inorganic powder is uniformly impregnated in the inside of the polymeric matrix formed by curing the polymeric matrix resin with a hardening material. Hollow spheres or expanded organic hollow spheres.

First, as the polymeric matrix according to the present invention, urethane derivatives such as isocyanate terminated urethane prepolymers are preferred. Isocyanate terminated urethane prepolymers are reactants of isocyanates with polyols and chain extenders, with isocyanates mainly using 2.4-triene diisocyanate. Moreover, it is also possible to use diisocyanate together in the range which does not impair the effect of this invention. Preferred diisocyanate compounds include 2.6-triene diisocyanate, 4.4-diphenylmethane diisocyanate, paraphenylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and the like.

The polyol may be a polyether polyol such as poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, polycarbonate art polyol, polyester polyol, or the like.

Further, as the chain extender, low molecular weight polyols are used, for example, ethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol, 1.4-butanediol, neopentin glycol, 1.5-pentanediol, 1.6-hexanediol, diethylene glycol Etc. can be used.

In addition, the toluene diisocyanate ( TDI) monomer content of the isocyanate terminated urethane prepolymer used in the present invention is 0.1% or less, which is lower than the TDI monomer content of the urethane prepolymer generally used, which is 0.2 to 0.5%. It is efficient in terms of improvement of working environment, easy to control process conditions due to long pot life, and has excellent properties such as durability and mechanical properties.

On the other hand, an active hydrogen compound may be used as the curing agent. For example, a polyamine (MOCA) in a solid state at room temperature may be used alone, or a mixture of a polyamine in a solid state and a polyol in a liquid state may be used. In particular, 3.3-dichloro 4.4-diamino diphenylmethane, chloroaniline modified-chlorodiaminophenylmethane, 3.5-bis (methylthio) 2.4-toluene diamine, 3.5- (methylthio) 2.6-toluenediamine, amino ethyl piperazine And diamines such as metaxylene diamine are preferable.

Such diamines may be used alone, or may be used in combination with polyether polyols such as poly (oxytetramethylene) glycol and poly (oxypropylene) glycol, polycarbonate polyols, polyester polyols, and the like, as necessary. The polyol used in combination with the amine is low in molecular weight, and particularly preferably poly (oxytetramethylene) glycol or polycarbonate glycol in the weight average molecular weight range of 500 to 3,000.

2 is a cross-sectional view of the polishing pad according to the embodiment of the present invention, which shows the polishing pad 20 uniformly impregnated with the inorganic hollow spheres 24 in the polymeric matrix 22. The inorganic hollow sphere 24 is a structure in which the inorganic powder is coated on the outer wall of the organic hollow sphere having a hollow portion therein,

The organic hollow sphere is a thermoplastic resin, which is an acrylonitrile copolymer, an acrylonitrile-vinylidene chloride copolymer or a styrene-acrylonitrile copolymer, and the hollow portion has a low boiling point such as isobutane, pentane, isopentane, and the like. Hydrogen gas is contained, and the inorganic powder contains titanium oxide (TiO ₂ ), calcium carbonate (CaCO ₃ ), silicon oxide, cerium oxide, aluminum oxide, barium oxide, ceramics, talc (TALC), etc. Preferably, the inorganic hollow spheres have a particle diameter of 10 to 150 µm, and a particle diameter of 10 to 50 µm and a particle diameter of 60 to 150 µm may be mixed and used in a ratio of 2 to 8: 8 to 2.

The specific gravity of the inorganic hollow spheres 24 is 0.05 to 0.50 ± 0.05 g / cm 3, and is usually 0.1 to 0.50 ± 0.05 g / cm 3, and is a conventional pre-cured expanded organic hollow sphere, that is, a first organic hollow sphere. Since the specific gravity of Expancel 551DE (trade name, Rhodel Co., Ltd.) is significantly larger than 0.04 ± 0.04 g / cm 3, the separation phenomenon due to the specific gravity deviation of the mixture is suppressed when mixed with matrix resin such as isocyanate-terminated urethane prepolymer or urethane-modified epoxy. This can solve the problem of particles scattering. In addition, since the outer part of the hollow sphere is coated with inorganic powder in nanometers, they participate in the polishing process to perform a polishing function, thereby reducing the amount of abrasive used, improving the polishing rate, and reducing the process cost. The inorganic hollow sphere is preferably contained in 0.5 to 20 parts by weight, preferably 1.0 to 10 parts by weight with respect to 100 parts by weight of the matrix resin.

3 is a cross-sectional view of a polishing pad according to another embodiment of the present invention, wherein the inorganic hollow sphere 34 and the unfoamed organic hollow sphere 36 before curing, that is, the second organic hollow sphere are formed in the matrix 32. A uniformly impregnated polishing pad is shown.

The second organic hollow sphere 36 has a structure in which a low boiling point hydrocarbon gas such as isobutane, pentane, isopentane or the like is contained in an organic coating made of thermoplastic resin. The thermoplastic resin may be an acrylonitrile copolymer, an acrylonitrile-vinylidene chloride copolymer or a styrene-acrylonitrile copolymer, and the softening temperature of the thermoplastic resin is preferably higher than the boiling point of the internal hydrocarbon. . Therefore, when heat is applied to the softening temperature of the thermoplastic resin in the step of mixing and curing the matrix resin and the second organic hollow sphere with a two-component molding machine, the thermoplastic resin softens and at the same time volume expansion of the contained low boiling hydrocarbon occurs. The organic hollow sphere is expanded, and a hollow portion containing a hydrocarbon gas is formed therein.

At this time, the softening temperature of the thermoplastic resin is preferably in the range of 70 ~ 120 ℃, especially 80 ~ 110 ℃. In addition, the particle size of the organic hollow sphere in the unfoamed state is 5 ~ 30㎛ preferably 8 ~ 15㎛, particle size after expansion is 10 ~ 70㎛, preferably 20 ~ 50㎛.

The specific gravity of the second organic hollow sphere in the unfoamed state is 1.0 to 1.1, which is similar to the specific gravity of the matrix resin, for example, the isocyanate-terminated urethane prepolymer, so that it is not separated during stirring and mixing and can maintain a uniform dispersion state. The degree of dispersion of the hollow spheres in the resulting polishing pad cake is constant, and the disk-shaped polishing pad obtained after the slice also has uniform physical properties.

The second organic hollow sphere in the unfoamed state before curing is expanded mainly by the heat of reaction released during curing after mixing and stirring the matrix resin and the curing agent. Therefore, the curing temperature in the two-liquid reaction curing process should be adjusted to a temperature range in which the organic hollow spheres are expandable. For example, the expansion temperature of the organic hollow spheres is in the range of 60 to 120 ° C., and the optimum expansion temperature is 90 to 130 ° C. In the case of, the curing temperature is maintained at about 90 to 130 ° C, or more preferably, the curing temperature is in the range of 100 to 120 ° C to obtain a matrix having a more uniform micropore distribution.

In addition, in order to improve the expansion efficiency, the curing reaction may be performed after a predetermined expansion at 70-90 ° C., which is near the heating expansion start temperature, before the curing reaction.

Further, the first organic hollow spheres foamed in advance before curing may also be added, wherein the amount of the first and second organic hollow spheres added is appropriate in a range in which their mixed solution does not lose fluidity when added to the matrix resin or the curing agent. Is adjusted. For example, when using a two-liquid component casting machine, the inorganic hollow spheres, the first and the second organic hollow spheres are first mixed with the matrix resin in the first tank and then injected into the mold and the curing agent in the second tank. And secondary mixing and stirring, wherein the addition amount of the first and second organic hollow spheres can be appropriately adjusted within a range in which the primary mixed mixture composition does not lose fluidity. The same applies to the case where the first and second organic hollow spheres are first mixed with the curing agent and then mixed and stirred with the matrix resin at the time of mold injection.

The total amount of the inorganic hollow spheres and the first and second organic hollow spheres is preferably in the range of 0.5 to 20, preferably 1.0 to 10 parts by weight. When used in this range, the polishing pad can be handled in a relatively low viscosity region and at the same time contains fine pores.

Hereinafter, a method of manufacturing a polishing pad according to the present invention using a two-component molding machine will be described.

First, a first liquid containing a mixture of a matrix resin, such as a polyurene derivative, and an inorganic hollow sphere as a main component is stored in a first tank of a two-liquid component casting machine, and optionally a first or second organic hollow sphere is further added. Add. Moreover, after preparing the 2nd liquid which has a hardening | curing agent as a main component in a 2nd tank, these are inject | poured in a metal mold | die at a suitable ratio, mixing, stirring, and hardening reaction is advanced. In this case, various additives may be added to the first liquid or the second liquid as necessary.

When an isocyanate-terminated urethane prepolymer is used as a matrix resin and diamine uses a hardening | curing agent, the two-component compounding ratio of a matrix resin and a hardening | curing agent is determined based on the molar ratio of an isocyanate group and an amine group. Preferably in the range of and the mixing ratio of the second liquid such that the NH ₂ /NCO=0.7~1.2 range, more preferably NH ₂ / NCO 0.8 ~ 1.0.

Also, when using a mixture of the polyol and diamine curing agent has an active hydrogen compound to form an amine group by adjusting the molar ratio NH ₂ / NCO of the isocyanate groups in the diamine curing agent for the isocyanate terminated urethane prepolymer.

It is preferable that the matrix resin and the curing agent at the time of performing the curing reaction in the two-liquid component casting machine are maintained at a temperature that does not interfere with the circulation of the two-liquid component molding machine. For example, the matrix resin in the first tank is maintained at a temperature of more preferably from 60 to 100 ° C, preferably from 70 to 90 ° C, and the curing agent in the second tank varies at an appropriate temperature depending on the components, but is usually maintained at 60-130 ° C. Specifically, for example, in the case of using diamines and solid 3.3-dichloro4.4-diamino phenylmethane at room temperature, the temperature is maintained at a temperature of 100 to 120 ° C, and diamines or mixtures of these and polyols at room temperature When using, it is preferable to maintain at the temperature of 60-100 degreeC.

In addition, when the non-foamed organic hollow sphere, that is, the second organic hollow sphere is used together, the tank including the same should be set to a temperature lower than the start temperature of expansion of the second organic hollow sphere.

As such, the composition stored in the two-liquid component molding machine at a predetermined temperature is discharged from the head of the molding machine and injected into the mold to be molded. At this time, the second organic hollow sphere expands mainly by the heat of reaction released during the curing reaction, but also expands by heating from the outside. In the case where the mold temperature is lower than 80 ° C, the resin of the part in contact with the mold loses heat to the outside, and thus foam stain occurs. If the mold temperature exceeds 120 ° C, the hollow sphere at the part in contact with the mold is formed. Foaming stains also occur because the expansion is too fast. Therefore, the mold temperature at the time of curing molding is preferably maintained in the range of 60 ~ 120 ℃, ideally it is preferable to maintain the mold temperature at 90 ~ 110 ℃ according to the exothermic behavior of the two-liquid mixture.

At this time, the specific gravity of the second organic hollow sphere changes as the foam is formed by the reaction heat and external heating during the two-liquid reaction curing process, but the organic hollow sphere has a change in specific gravity gradually in a system of increasing the surrounding viscosity. Uneven distribution of the hollow spheres does not occur in the molding, so that the dispersed state of the pores in the molding is uniform. Therefore, when the polishing pad cake after demolding is sliced in the horizontal direction to produce a thin plate-shaped polishing pad, it is possible to obtain a uniform polishing pad without any density difference and hardness difference even if it is cut off at any part.

On the other hand, it is preferable to form grooves of a predetermined shape on the sliced thin plate polishing pad surface obtained in the present invention for efficient retention and uniform distribution of the slurry. It is also possible to adhere a flexible porous sheet such as a nonwoven fabric to the same. In addition, the mold may be formed into a plate shape to obtain a final pad-shaped polishing pad immediately without slicing after forming.

Hollow sphere-containing polishing pad according to the present invention is 0.5 ~ 1.0g / ㎠, More preferably, it has a density of 0.7 to 0.9 g / cm 3, and the hardness varies depending on the type and amount of the matrix resin, the curing agent or the hollow sphere, but in general, the range of shore D = 50 to 70 is particularly good. The range of D = 52-65 is preferable. In the polishing process, polishing characteristics such as polishing efficiency, surface characteristics and flatness of the wafer are greatly influenced by the hardness of the polishing pad. If the hardness of the pad is large, the polishing efficiency increases but the surface state and flatness decrease, and the hardness Low increases surface condition and flatness but decreases polishing efficiency. Therefore, by using the characteristics according to the hardness of the polishing pad, a high hardness polishing pad upper layer part is manufactured according to the present invention, the upper pad is supported on the lower portion of the upper layer pad, the lower pad to act as a buffer used to attach The lower pad may include a nonwoven fabric or a polyurethane foam. Preferably, the non-woven fabric may have a compression ratio of 5 to 15%, a compression modulus of 55 to 75%, and a hardness of 60 to 75 shore A.

In addition, the polishing efficiency and flatness are affected not only by the material properties of the polishing pad but also by the surface shape of the pad. The polishing pad according to the present invention forms grooves on the polishing surface after slicing to improve slurry retention and distribution and improve polishing efficiency. It can increase. As shown in FIG. 4, the groove is provided with a macro groove 42 formed in a square shape on the polishing surface of the polishing pad 40 that grows at a predetermined interval from the center, or as shown in FIG. 5. The micro grooves 44 formed in the XY direction may be formed between the macro grooves 42, and as shown in FIG. 6 as another shape, at a predetermined interval from the center on the polishing surface of the polishing pad 50. FIG. The macro grooves 52 formed so that the grooves extending in the XY direction become larger orthogonal to each other and the micro grooves 54 formed in the XY direction between the macro grooves 52 may be provided together.

As described above, in the polishing pad having macro and micro grooves, when the slurry supplied to the upper surface of the polishing pad flows to the edge by the rotational force during the wafer polishing process, the macro grooves become the main flow passages, and the micro grooves become the secondary passages. By uniformly flowing and dispersing the slurry on the entire surface of the polishing pad, the non-uniform distribution of the slurry does not occur, thereby preventing the non-uniformity of the polishing surface and increasing the manufacturing cost due to the oversupply of the slurry.

Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to this. The weight part of an Example and a comparative example shows a weight% unless there is particular notice.

Example Group I

(1) Polishing speed measurement method

Abrasion test is carried out for 1 minute to measure the thickness of the polished material before and after the test, and 50 positions are determined in advance in the polishing surface. The polishing rate of one polishing pad is calculated by calculating the average value of the thickness difference before and after the polishing test of 50 measuring positions.

In addition, the average value A and the dispersion value B of the polishing rate of 10 polishing pads sliced resin moldings containing the same type of hollow spheres are expressed as A ± B to evaluate polishing characteristics and lot-to-lot variation. A is related to the polishing rate, the higher the value, the better the polishing efficiency, and B is related to the variation between lots, and the smaller the value, the more uniform the polishing property.

(2) Polishing flatness measuring method

The polishing test is carried out for 1 minute and the thickness of the polished object before and after the test is measured. The measurement positions are determined in advance at 50 positions in the polishing surface. From the maximum, minimum, and average values of the thickness difference before and after the 50 polishing tests at the measurement positions, the flatness of one polishing pad is calculated using the following equation.

Flatness = 100X (Max-Min) / Average

The average value C and the dispersion value D of the flatness values for 10 polishing pads in which the same hollow sphere-containing matrix was sliced are expressed as C ± D to evaluate polishing characteristics and lot-to-lot variation. C refers to the polishing characteristics, the smaller the value, the more excellent the flatness of the polished surface, and D is the variation between lots, the smaller the value, the more stable the polishing property.

In the polishing test method, 10 polishing pads were mounted in a polishing apparatus to measure polishing characteristics of a silicon oxide film (SiO ₂ ), with a wafer load of 5.0 psi and a table and head (wafer carrier) rotation speed of 300 rpm in the same direction. Rotate, and the rotation speed difference is about ± 30%, and the polishing test is carried out under polishing conditions having a polishing time of 60 seconds.

(3) Comparative Example

A mixture obtained by adding 2.3 parts by weight of a conventional first organic hollow sphere (trade name Expencel-551 DE) to 100 parts by weight of isocyanate terminated urethane prepolymer-A (TDI / PTMG / DEG system, product name NCOeq = 450) with a polymeric matrix resin was mixed. At 70 ° C, as a curing agent, 25 parts by weight of MOCA was heated at 120 ° C in a two-liquid component type molding machine, respectively.

Thereafter, a mixture of these two liquid components is poured into a mold having a molding temperature of 100 ° C., and then heated to 110 ° C. for 30 minutes in an oven to cure first. Thereafter, the molded product was demolded and then cured at 120 ° C. for 5 hours, and then cooled to 25 ° C. to obtain a polishing pad cake molded product, which was sliced to 1.5 mm thickness and ground again to prepare a 1.35 mm thickness polishing pad. A nonwoven fabric is bonded to the back surface of the polishing pad to prepare a laminated pad. The first organic hollow sphere product name Expencel-551 DE is manufactured by Akzo Nobel and uses isobutane gas as a non-bottom hydrocarbon gas, and is a vinyldene fluoride acrylonitrile copolymer material having a particle diameter of about 20 to 50 μm. Specific gravity of 0.04 ± 0.004 g / cm 3 It is enough.

Ten polishing pads prepared according to the above method were tested by the above experimental method, and the polishing rate was 1870 ± 50 / min, and the flatness was 9 ± 2%.

(4) Example 1

A mixture of 3 parts by weight of a second organic hollow sphere (trade name F-20D, Matsumoto Oils & Pharmaceuticals) was added to 100 parts by weight of an isocyanate-terminated urethane prepolymer-A (TDI / PTMG / DEG-based, NCOeq = 450) which is a polymeric matrix resin. And 25 parts by weight of the curing agent MOCA were placed in the liquid A tank and the liquid B tank of the elastomer casting machine, respectively, and the liquid A system was adjusted to 70 ° C. and the liquid B system was 120 ° C.

Thereafter, the resin mixed with two liquids in the mixing head is poured into a mold having a molding temperature of 100 ° C., and then molded at a temperature of 110 ° C. for 30 minutes in an oven to cure first. Thereafter, the molded product was demolded, secondary cured at 120 ° C. for 5 hours, and the molded product was cooled to 25 ° C., and then a polishing pad was produced by the above-described method. The second organic hollow sphere (brand name F-20D) uses isobutane gas as the low boiling point gas in the hollow portion, and the organic coating constituting the hollow sphere is made of vinyldene fluoride acrylonitrile copolymer, and the particle size is foamed. It is about 10-15 micrometers before, about 20-40 micrometers after foaming, and specific gravity is about 1.0 +/- 0.1 g / cm <3> before foaming expansion.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 1870 ± 40 mW / min and the flatness was 7 ± 2%.

(5) Example 2

To 100 parts by weight of isocyanate-terminated urethane prepolymer-A (TDI / PTMG / DEG system, NCOeq = 450), 3.2 parts by weight of the second organic hollow sphere (trade name F-20D) was added and mixed, and a hardening agent etacure-300 (BMTTDA) 19.3 parts by weight of each of the Elastomeric Molding Machine was placed in the A liquid tank and the B liquid tank, and the temperature of the A liquid system was adjusted to 80 ° C. and the temperature of the B liquid system to 80 ° C. After the resin was injected into a mold having a molding temperature of 100 ° C., a polishing pad was produced in the same manner as in the manufacturing method of the comparative example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 1890 ± 50 Pa / min and the flatness was 7 ± 1%.

(6) Example 3

Compound mixed with 3.5 parts by weight of the second organic hollow sphere (F-20D) to 100 parts by weight of isocyanate-terminated urethane prepolymer-A (TDI / PTMG / DEG-based, NCOeq = 450), and a curing agent BMTTDA / PTMG (Mw2,000) 35 parts by weight of each of 5/5 mixtures of an elastomer molder were filled, and the temperature of the liquid A system was adjusted to 80 ° C. and the temperature of the liquid B system to 80 ° C. Thereafter, a polishing pad was produced in the same manner as in the manufacturing method of Comparative Example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1880 ± 50 mW / min and the flatness was 6 ± 1%.

(7) Example 4

A compound obtained by adding 3.5 parts by weight of a second organic hollow sphere (F-20D) to 100 parts by weight of an isocyanate-terminated urethane prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450) and BMTTDA 19.3 parts by weight of an elastomer Put the A liquid tank and the B liquid tank of the molding machine, adjust the temperature of the A liquid system to 80 ° C. and the B liquid system to 70 ° C. and inject the resin mixed with two liquids into the mold at a molding temperature of 100 ° C. by molding. In the same manner as in the manufacturing method of Comparative Example, a polishing pad was prepared.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1900 ± 30 Pa / min and the flatness was 7 ± 1%.

(8) Example 5

Isocyanate-terminated urethane prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450) 5 parts of a compound mixed with the addition of 3.2 parts by weight of the second organic hollow sphere F-20D and a curing agent MOCA / PTMG-Mw 2,000 Each of 38 parts by weight of the / 5 mixture was placed in the A liquid tank and the B liquid tank of the elastomer molding machine, and the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C. After the injection into the mold, a polishing pad was produced in the same manner as in the manufacturing method of the comparative example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 1890 ± 40 mW / min and the flatness was 6 ± 2%.

(9) Example 6

5 parts by weight of an isocyanate-terminated urethane prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450) in an inorganic hollow sphere (a hollow sphere coated with an inorganic powder mainly composed of titanium dioxide; trade name MFL-30STI) Add the mixed compound and 25 parts by weight of the curing agent MOCA to the A liquid tank and the B liquid tank of the elastomer molding machine, respectively.The temperature of the A liquid system was adjusted to 70 ° C. and the B liquid system was adjusted to 120 ° C., followed by mixing with two mixing heads with a mixing head. Was injected into a mold having a molding temperature of 100 ° C. and then molded, and a polishing pad was manufactured in the same manner as in the manufacturing method of Comparative Example.

Here, the hollow part of the inorganic hollow sphere (trade name MFL-30STI) is filled with isobutane gas, and the organic endothelial is mainly composed of vinyldene chloride acrylonitrile copolymer, and the inorganic powder is mainly composed of titanium oxide. The diameter is 20 μm and the specific gravity is about 0.2 ± 0.05 g / cm ³ .

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1900 ± 50 Pa / min and the flatness was 6 ± 2%.

(10) Example 7

Compound which added 5 parts by weight of inorganic hollow sphere (coated powder coated with calcium carbonate: trade name MFL-80GCA) to 100 parts by weight of isocyanate-terminated urethane prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450), and a hardening agent 25 parts by weight of MOCA are placed in the A and B liquid tanks of the elastomer molder, respectively. The temperature of the liquid A system was adjusted to 70 ° C. and the liquid B system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad in the same manner as in the comparative example. It was.

Here, the hollow portion of the inorganic hollow sphere (brand name MFL-80GCA) is filled with isobutane or n-pantan gas, and the organic endothelial is composed of acrylonitrile copolymer as a main component, and the inorganic powder is composed of calcium carbonate as a main component. Is 20 μm, and the specific gravity is about 0.2 ± 0.05 g / cm ³ .

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 1890 ± 50 Pa / min, and the flatness was 6 ± 2%.

(11) Example 8

100 parts by weight of isocyanate-terminated urethane prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450) was added and mixed with 3.0 parts by weight of MFL-30STI as an inorganic hollow sphere and 2.0 parts by weight of F-20D as a second organic hollow sphere. The mixture and 19.3 parts by weight of the curing agent BMTTDA are placed in the liquid A tank and the liquid B tank of the elastomer molder, respectively. The temperature of the A liquid system was adjusted to 70 ° C. and the B liquid system was adjusted to 70 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C. A polishing pad was produced.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1830 ± 20 Pa / min and the flatness was 9 ± 2%.

(12) Example 9

To 100 parts by weight of isocyanate terminated urethane prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450), 3.0 parts by weight of inorganic hollow sphere (MFL-80GCA) and 1.5 parts by weight of the first organic hollow sphere used in the comparative example were added. The mixed mixture and 25 parts by weight of the curing agent MOCA are placed in the A liquid tank and the B liquid tank of the elastomer molding machine, respectively. The temperature of the A liquid system was adjusted to 70 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C. A polishing pad was produced.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1910 ± 20 Pa / min and the flatness was 6 ± 2%.

(13) Example 10

Isocyanate Terminated Urethane Prepolymer-B (TDI / PTMG / PC / DEG-based, NCOeq = 450) to 3.0 parts by weight of inorganic hollow sphere (trade name: MFL-3OSTI) and 1.5 parts by weight of the first organic hollow sphere used in Comparative Example 25 parts by weight of the mixture and the mixture of the hardener MOCA were added to the A liquid tank and the B liquid tank of the elastomer molding machine. The temperature of the liquid A system was adjusted to 70 ° C. and the liquid B system was adjusted to 120 ° C., followed by molding a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then a polishing pad was manufactured in the same manner as in the comparative example. .

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1900 ± 50 Pa / min and the flatness was 6 ± 2%.

(14) Example 11

Compound which mixed 3.5 weight part of 2nd organic hollow spheres F-20D with 100 weight part of urethane modified epoxy (brand name UME-305, Kukdo Chemical), and the hardening | curing agent amino ethyl piperazine (brand name kh-252, Kukdo Chemical) 30 The weight parts are placed in the liquid A tank and the liquid B tank of the elastomer molder, respectively. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C. Produced.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 1890 ± 50 Pa / min and the flatness was 7 ± 1%.

(15) Example 12

The compound which mixed 3.5 weight part of 2nd organic hollow spheres F-20D with 100 weight part of UME-305, 30 weight part of hardening agent metaxylenediamine (brand name h-3808, Kukdo Chemical Co., Ltd.), the A liquid tank of an elastomeric molding machine, and Put in liquid B tank. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad in the same manner as in Comparative Example. .

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 1890 ± 40 mW / min and the flatness was 6 ± 2%.

(16) Example 13

A compound obtained by adding 1.0 parts by weight of a second organic hollow sphere F-20D and 2.0 parts by weight of an inorganic hollow sphere (MFL-30STI) to 100 parts by weight of UME-305, and a curing agent aminoethyl piperazine (trade name KH-252, manufactured by Kukdo Chemical Co., Ltd.). 30 parts by weight are put in the A liquid tank and the B liquid tank of the elastomer molder, respectively. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., followed by molding a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then a polishing pad was manufactured in the same manner as in the comparative example. .

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 1900 ± 40 Pa / min and the flatness was 6 ± 1%.

Table 1 summarizes the results of Examples 1 to 13.

TABLE 1

Matrix resin (% by weight) Hollow sphere (wt%) Curing agent (% by weight) Polishing Speed (Å / min) Flatness Comparative example Isocyanate Terminated Urethane Prepolymer-A 100 First Organic Hollow Sphere 2.3 MOCA 25 1870 ± 50 9 ± 3% Example 1 Isocyanate Terminated Urethane Prepolymer-A 100 Second organic hollow sphere 3 MOCA 25 1870 ± 40 7 ± 2% Example 2 Isocyanate Terminated Urethane Prepolymer-A 100 Second organic hollow sphere 3.2 BMTTDA 19.3 1890 ± 50 7 ± 2% Example 3 Isocyanate Terminated Urethane Prepolymer-A 100 Second organic hollow sphere 3.5 BMTTDA / PTMG (5/5) 35 1880 ± 50 6 ± 1% Example 4 Isocyanate Terminated Urethane Prepolymer-B 100 Second organic hollow sphere 3.5 BMTTDA 19.3 1900 ± 30 7 ± 1% Example 5 Isocyanate Terminated Urethane Prepolymer-B 100 Second organic hollow sphere 3.2 MOCA / PTMG (5/5) 38 1890 ± 40 6 ± 2% Example 6 Isocyanate Terminated Urethane Prepolymer-B 100 Inorganic hollow spheres 5.0 MOCA 25 1900 ± 50 6 ± 2% Example 7 Isocyanate Terminated Urethane Prepolymer-B 100 Inorganic hollow spheres 5.0 MOCA 25 1890 ± 40 7 ± 2% Example 8 Isocyanate Terminated Urethane Prepolymer-B 100 Second organic hollow sphere 1.0 Inorganic hollow sphere 2.2 BMTTDA 19.3 1910 ± 50 6 ± 2% Example 9 Isocyanate Terminated Urethane Prepolymer-B 100 Inorganic hollow spheres 3.0 First organic hollow spheres 1.5 MOCA 25 1910 ± 40 6 ± 2% Example 10 Isocyanate Terminated Urethane Prepolymer-B 100 Inorganic hollow spheres 3.0 First organic hollow spheres 1.5 MOCA 25 1900 ± 50 6 ± 2% Example 11 Urethane Modified Epoxy 100 Second organic hollow sphere 3.5 Amino Piperazine 30 1890 ± 50 7 ± 1% Example 12 Urethane Modified Epoxy 100 Second organic hollow sphere 3.5 Metaxylenediamine 30 1890 ± 40 6 ± 2% Example 13 Urethane Modified Epoxy 100 Second Organic Hollow Sphere 1.0 Inorganic Hollow Sphere 2.0 Aminoethylpiperazine 30 1900 ± 40 6 ± 1%

As can be seen from Table 1, when comparing the flatness of the comparative example using the first organic hollow spheres and the embodiment using the inorganic hollow spheres and / or the second organic hollow spheres in the flatness of 9 ± 2% of the comparative example It can be seen that the flatness of the above embodiments is low, so that the flatness is excellent and the polishing property is stable.

Example Group II

(1) Polishing speed and flatness measuring method

In the same manner as in the method of group I, the measuring position was set to 49, and the test was carried out using 10 polishing pads. This is to determine the effect of the invention on the actual process by selecting the polishing conditions to meet the actual CMP process.

In addition, a nonwoven fabric was attached to the back surface of the polishing pad, and an X-Y orthogonal macro groove having an X-Y axial direction was formed on the surface of the polishing pad at a depth of 0.7 mm, a width of 0.65 mm, and a pitch of 6.35 mm.

(2) Comparative Example

Isocyanate-terminated urethane prepolymer (trade name: Adiprene L-325, TDI / PTMG / DEG system, NCO content 9.0 to 9.3%) to 100 parts by weight of a mixture of 2.3 parts by weight of the first organic hollow sphere (trade name: Expencel-551 DE) Silver was heated to 70 ° C and 25 parts by weight of the curing agent MOCA were each heated to 120 ° C. The mixture of these two liquid components was poured into a mold having a molding temperature of 100 ° C., and then heated in a oven at 110 ° C. for 30 minutes to cure the first time. After cooling, the slice was sliced to a thickness of 1.3 mm, and a macro groove was formed on the polishing surface to prepare a polishing pad.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2870 ± 50 Pa / min and the flatness was 7 ± 3%.

(3) Example 14

A mixture of 3 parts by weight of the second organic hollow sphere (trade name F-20D, Matsumoto Oils & Pharmaceuticals) was added to 100 parts by weight of the matrix resin Adiprene L-325, and 25 parts by weight of the curing agent MOCA was added to the A liquid tank and the B liquid of the elastomer molding machine. Put it in the tank. A liquid tank system was adjusted to 70 ° C. and B liquid tank system was adjusted to 120 ° C., followed by injecting a resin mixture of two liquids as a mixing head into a mold having a molding temperature of 100 ° C., thereby producing a polishing pad having macro grooves as a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2870 ± 40 Pa / min and the flatness was 5 ± 2%.

(4) Example 15

19.3 parts by weight of the mixture of the second organic hollow sphere F-20D 3.2 parts by weight of Adiprene L-325 and 19.3 parts by weight of the curing agent Ethacua-300 (BMTTDA, produced by Ethyl Co., Ltd.) were added. Put it in the liquid tank. The temperature of the A liquid system was adjusted to 80 ° C. The temperature of the B liquid system was adjusted to 80 ° C., and then the resin mixed with two liquids with a mixing head was injected into a mold having a molding temperature of 100 ° C., thereby producing a polishing pad having macro grooves by the comparative example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2890 ± 50 Pa / min and the flatness was 7 ± 1%.

(5) Example 16

The mixture of the mixture of 3.5 parts by weight of the second organic hollow sphere F-20D and 100 parts by weight of Adiprene L-325 and 35 parts by weight of the curing agent BMTTDA / PTMG-Mw2,000 5/5 mixture, respectively, The temperature of 80 degreeC and B liquid system was adjusted to 80 degreeC, the resin mixed with two liquids by the mixing head was inject | poured into the metal mold | die of 100 degreeC, and the polishing pad which has a macro groove was produced by the method of a comparative example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2880 ± 50 Pa / min and the flatness was 6 ± 1%.

(6) Example 17

The compound obtained by mixing 3.5 parts by weight of the second organic hollow sphere F-20D with 100 parts by weight of Adiprene L-325 and 19.3 parts by weight of the curing agent BMTTDA were placed in the A liquid tank and the B liquid tank of the elastomer molding machine, and the temperature of the A liquid system was Was prepared at 80 ° C. and B liquid system at 70 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2900 ± 30 Pa / min and the flatness was 6 ± 1%.

(7) Example 18

The compound obtained by adding 3.2 parts by weight of the second organic hollow sphere F-20D to 100 parts by weight of Adiprene L-325, and 38 parts by weight of the 5/5 mixture of the curing agent MOCA / PTMG-Mw 2,000, each contained an A liquid tank of an elastomeric molding machine, Place B liquid tank, A liquid system at 80 ℃, B liquid system at 120 ℃ and mix two liquids with a mixing head into a mold with a molding temperature of 100 ℃, and then use a polishing pad with macro grooves as a comparative example. Produced.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2890 ± 40 Pa / min and the flatness was 6 ± 2%.

(8) Example 19

Inorganic hollow spheres coated with an inorganic powder mainly composed of titanium dioxide (trade name MFL-30STI, particle size 20 μm, specific gravity 0.2 ± 0.05) in 100 parts by weight of Adiprene L-325, a compound mixed with 5 parts by weight of a hardening agent and MOCA 25 weight Each part is placed in the A liquid tank and the B liquid tank of the elastomer molding machine, the temperature of the A liquid system is adjusted to 80 ° C., and the B liquid system is adjusted to 120 ° C., and the resin obtained by mixing two liquids with a mixing head is injected into a mold having a molding temperature of 100 ° C. After molding, the polishing pad having macro grooves was produced by the method of Comparative Example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2900 ± 50 Pa / min and the flatness was 6 ± 2%.

(9) Example 20

Compound which added 5 parts by weight of an inorganic hollow sphere coated with an inorganic powder mainly composed of calcium carbonate (trade name MFL-80GCA, particle size 20 μm, specific gravity 0.2 ± 0.05) to 100 parts by weight of Adiprene L-325, and 25 parts by weight of a curing agent MOCA Put the A liquid tank and the B liquid tank of the elastomer molding machine, respectively, and adjust the temperature of the A liquid system to 80 ° C. and the B liquid system to 120 ° C. and inject the resin mixed with two liquids into the mold at the molding temperature of 100 ° C. by molding. After that, a polishing pad having macro grooves was produced by the method of Comparative Example.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2890 ± 50 Pa / min and the flatness was 6 ± 2%.

(10) Example 21

A mixture of the mixture of 3.0 parts by weight of the inorganic hollow sphere MFL-30STI and 2.0 parts by weight of the second organic hollow sphere F-20D, and 19.3 parts by weight of the curing agent BMTTDA were added to 100 parts by weight of the Adiprene L-325, respectively. Into the liquid tank, the temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., and the resin obtained by mixing two liquids with a mixing head was injected into a mold having a molding temperature of 100 ° C., and then the macro grooves were formed in the comparative example. The eggplant produced a polishing pad.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2860 ± 20 Pa / min and the flatness was 6 ± 2%.

(11) Example 22

A mixture of 3.0 parts by weight of inorganic hollow sphere (MFL-80GCA) and 1.5 parts by weight of first organic hollow sphere (Expancel 551-DE) was added to 100 parts by weight of Adiprene L-325, and 25 parts by weight of the curing agent MOCA was added to the elastomer molding machine. Put in liquid A tank and liquid B tank. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2890 ± 20 Pa / min and the flatness was 6 ± 2%.

(12) Example 23

100 parts by weight of Adiprene L-325 was added by mixing 3.0 parts by weight of the inorganic hollow spheres MFL-3OSTI and 1.5 parts by weight of the first organic hollow sphere, and 25 parts by weight of the curing agent MOCA were added to the liquid A and tank B of the elastomeric molding machine. Put it in the tank. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2900 ± 50 Pa / min and the flatness was 6 ± 2%.

(13) Example 24

Compound which mixed 3.5 weight part of 2nd organic hollow spheres F-20D with 100 weight part of urethane modified epoxy (brand name UME-305, Kukdo Chemical), and the hardening | curing agent amino ethyl piperazine (brand name KH-252, Kukdo Chemical) 30 The weight parts are placed in the liquid A tank and the liquid B tank of the elastomer molder, respectively. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., and the resin mixed with two liquids with a mixing head was injected into a mold having a molding temperature of 100 ° C. to form a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2890 ± 50 Pa / min and the flatness was 7 ± 1%.

(14) Example 25

Compound A, which was added and mixed with 3.5 parts by weight of the second organic hollow sphere F-20D to 100 parts by weight of UME-305, 30 parts by weight of the curing agent metaxylenediamine (trade name KH-3808, manufactured by Kukdo Chemical Co., Ltd.) Put in liquid B tank. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., and the resin mixed with two liquids with a mixing head was injected into a mold having a molding temperature of 100 ° C. to form a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2890 ± 40 Pa / min and the flatness was 6 ± 2%.

(15) Example 26

A compound in which 1.0 parts by weight of the second organic hollow sphere F-20D and 2.0 parts by weight of the inorganic hollow sphere MFL-30STI were added to 100 parts by weight of UME-305 and aminoethyl piperazine (trade name KH-252) as an active hydrogen compound 30 The weight parts are placed in the liquid A tank and the liquid B tank of the elastomer molder, respectively. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 80 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by the comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2900 ± 40 Pa / min and the flatness was 6 ± 1%.

(16) Example 27

100 parts by weight of an isocyanate-terminated urethane prepolymer (trade name LF-601D, NCO content 7.3%), an mixture of 3.0 parts by weight of an inorganic hollow sphere MFL-80GCA and 1.5 parts by weight of a first organic hollow sphere, and an elastomer of CACA 20 parts by weight, respectively. Place in the A and B liquid tanks of the molding machine. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2890 ± 20 Pa / min and the flatness was 6 ± 2%.

(17) Example 28

A liquid tank of an elastomeric molding machine, a mixture of 2.5 parts by weight of an inorganic hollow sphere (trade name MFL-100CA) and 100 parts by weight of an isocyanate-terminated urethane prepolymer (trade name LF-650D, NCO content 7.6%), and 22 parts by weight of a curing agent MOCA. And B liquid tank. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

The inorganic hollow sphere (MFL-100CA) is filled with isopentane gas in the hollow portion, the organic endothelial is made of acrylonitrile copolymer as a main component, the inorganic powder is made of calcium carbonate as a main component, and the particle diameter is about 100㎛. The specific gravity is about 0.13 ± 0.03 g / cm 3.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2910 ± 30 Pa / min and the flatness was 6 ± 1%.

(18) Example 29

100 parts by weight of an isocyanate-terminated urethane prepolymer (trade name LF-650D, NCO content 7.6%) and a mixture of 1.0 parts by weight of inorganic hollow spheres MFL-100CA and 3 parts by weight of another type of inorganic hollow spheres MFL-80GCA, and a curing agent MOCA / 43.6 parts by weight of the PTMG-2000 5/5 mixture are placed in the A and B liquid tanks of the elastomer molder, respectively. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 70 ° C., and the resin mixed with two liquids with a mixing head was injected into a mold having a molding temperature of 100 ° C. to form a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions, and the polishing rate was 2910 ± 30 Pa / min and the flatness was 6 ± 1%.

(19) Example 30

100 parts by weight of an isocyanate-terminated urethane prepolymer (LF-601D / L-325 = 5/5 mixture), a mixture of 2.0 parts by weight of an inorganic hollow sphere MFL-100CA and 3 parts by weight of MFL-80GCA, and an elastomer of 22.5 parts by weight of a curing agent MOCA. Place in the A and B liquid tanks of the molding machine. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2910 ± 30 Pa / min and the flatness was 5 ± 1%.

(20) Example 31

A mixture of 3.0 parts by weight of the inorganic hollow sphere MFL-80GCA and 1 part by weight of the first organic hollow sphere Expancel 551-DE1.5 with 100 parts by weight of an isocyanate-terminated urethane prepolymer (LF-601D / L-325 = 5/5 mixture); As the active hydrogen compound, 22.5 parts by weight of MOCA is added to the A liquid tank and the B liquid tank of the elastomer molding machine, respectively. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2880 ± 30 Pa / min and the flatness was 6 ± 2%.

(21) Example 32

100 parts by weight of an isocyanate-terminated urethane prepolymer (LF-700D NCO content 8.3%) and a mixture of 2.0 parts by weight of an inorganic hollow sphere MFL-100CA and 3 parts by weight of MFL-80GCA, and 23.8 parts by weight of MOCA, respectively, an A liquid tank of an elastomeric molding machine. And B liquid tank. The temperature of the A liquid system was adjusted to 80 ° C. and the B liquid system was adjusted to 120 ° C., followed by molding by injecting a resin mixed with two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having macro grooves by a comparative example. It was.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 2900 ± 30 Pa / min and the flatness was 5 ± 2%.

(22) Example 33

To 100 parts by weight of isocyanate-terminated urethane prepolymer (trade name LF-601D, NCO content 7.3%), a mixture of 3.5 parts by weight of the inorganic hollow sphere MFL-80GCA and 0.5 parts by weight of the second organic hollow sphere F-20D was mixed, and 20 parts by weight of MOCA. Into the liquid A tank and the liquid B tank of the elastomer molder, respectively. The temperature of the liquid A system was adjusted to 80 ° C. and the liquid B system was adjusted to 120 ° C., followed by molding by injecting a resin mixture of two liquids with a mixing head into a mold having a molding temperature of 100 ° C., and then manufacturing a polishing pad having grooves as a comparative example. A micro groove having a XY axis direction is formed to a depth of 0.7 mm, a width of 0.65 mm, a pitch of 6.35 mm, and a micro groove having a thin line having an XY axis direction between the macro grooves has a depth of 0.35 mm, The width was formed in 0.25 mm and 2.1 mm pitch.

Ten polishing pads prepared by the above method were tested under the above experimental conditions. The polishing rate was 3100 ± 30 Pa / min and the flatness was 4 ± 1%.

Table 2 summarizes the results of Examples 14 to 33.

TABLE 2

Topic weight% Hollow sphere weight% Curing agent weight% Polishing speed Å / min Flatness Comparative example L-325 100 Expancel 2.3 MOCA 25 2870 ± 50 7 ± 3% Example 14 L-325 100 F-20D 3 MOCA 25 2870 ± 40 5 ± 2% Example 15 L-325 100 F-20D 3.2 BMTTDA 19.3 2890 ± 50 7 ± 1% Example 16 L-325 100 F-20D 3.5 BMTTDA / PTMG (5/5) 35 2880 ± 50 6 ± 1% Example 17 L-325 100 F-20D 3.5 BMTTDA 19.3 2900 ± 30 7 ± 1% Example 18 L-325 100 F-20D 3.2 MOCA / PTMG (5/5) 38 2890 ± 40 6 ± 2% Example 19 L-325 100 MFL-30STI 5.0 MOCA 25 2900 ± 50 6 ± 2% Example 20 L-325 100 MFL-80GCA 5.0 MOCA 25 2890 ± 40 7 ± 2% Example 21 L-325 100 MFL-30STI 3.0F-20D 2.0 BMTTDA 19.3 2910 ± 50 6 ± 2% Example 22 L-325 100 MFL-80GCA 3.0Expancel 1.5 MOCA 25 2910 ± 40 6 ± 2% Example 23 L-325 100 MFL-30STI 3.0Expancel 1.5 MOCA 25 2900 ± 50 6 ± 2% Example 24 UME-305 100 F-20D 3.5 KH-252 30 2890 ± 50 7 ± 1% Example 25 UME-305 100 F-20D 3.5 KH-3808 30 2890 ± 40 6 ± 2% Example 26 UME-305 100 F-20D 1.0MFL-30STI 2.0 KH-252 30 2900 ± 40 6 ± 1% Example 27 LF-601D 100 MFL-80GCA 3.0Expancel 1.5 MOCA 20 2890 ± 20 6 ± 2% Example 28 LF-650D 100 MFL-100CA 2.5 MOCA 22 2910 ± 30 6 ± 1% Example 29 LF-650D 100 MFL-100CA 1.0MFL-80GCA 3.0 MOCA / PTMG (5/5) 43.6 2910 ± 40 6 ± 1% Example 30 LF-601D / L-325 (5/5) 100 MFL-100CA 2.0MFL-80GCA 3.0 MOCA 22.5 2910 ± 40 5 ± 1% Example 31 LF-601D / L-325 (5/5) 100 MFL-80GCA 3.0Expancel 1.5 MOCA 22.5 2880 ± 40 6 ± 2% Example 32 LF-700D 100 MFL-100CA 2.0MFL-80GCA 3.0 MOCA 20 2900 ± 30 5 ± 2% Example 33 LF-601D 100 MFL-80GCA 3.5F-20D 0.5 MOCA 20 3100 ± 30 4 ± 1%

As can be seen from the above table, the polishing pad of the present invention comprising inorganic hollow spheres and / or second organic hollow spheres has excellent flatness and polishing as compared to conventional polishing pads prepared using the first organic hollow spheres. It can be seen that the characteristics are stable.

The polishing pad containing the micropores according to the present invention and the polishing pad manufactured by the method for producing the same include an inorganic hollow sphere coated with an inorganic powder having a relatively high specific gravity to uniformly distribute the micropores in the molding, and the inorganic hollow The durability of the sphere is excellent in material stability, and the difference in density and hardness of the vicinity of the upper and lower surfaces of the microporous-containing polishing pad is small, and thus there is an advantage of preventing variation in the polishing properties between lots. Since the inorganic powder of nanometer particle diameter is coated, a part of the inorganic powder participates in the polishing process and functions as an abrasive, thereby reducing the amount of polishing slurry used and improving the polishing efficiency.

Claims (28)

Inorganic powder is coated on the outside of the organic endothelial, and the inorganic hollow sphere is formed hollow inside the organic endothelial, A polishing pad comprising a polymeric matrix impregnated with said inorganic hollow sphere. The method of claim 1, The organic endothelial is a polishing pad comprising a thermoplastic resin as a main component. The method of claim 2, The thermoplastic resin is a polishing pad, characterized in that the acrylonitrile copolymer, acrylonitrile-vinylidene chloride copolymer or styrene-acrylonitrile copolymer. The method of claim 1, The inorganic powder is a polishing pad, characterized in that the main component is selected from the group consisting of calcium carbonate, titanium oxide, silicon oxide, cerium oxide, aluminum oxide, barium oxide, ceramic, talc and combinations thereof. The method of claim 1, The inorganic hollow sphere is impregnated with 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymeric matrix. The method of claim 1, The inorganic hollow sphere has a particle diameter of 10 ~ 150㎛, specific gravity is 0.05 ~ 0.50 ± 0.05g / cm ³ Polishing pad, characterized in that. The method of claim 1, The inorganic hollow sphere is a polishing pad, characterized in that the hollow spheres of different particle diameters are mixed with a particle size of 10 ~ 50㎛ and 60 ~ 150㎛. The method of claim 1, And the polymeric matrix is a polyurethane derivative. The method of claim 8, The polyurethane derivative is an isocyanate terminated urethane prepolymer, urethane modified epoxy resin or a mixture thereof. The method of claim 1, The hollow inside the organic polishing pad, characterized in that the low boiling point hydrocarbon gas is contained. The method of claim 1, And an organic hollow sphere further impregnated in the polymeric matrix. The method of claim 11, The organic hollow sphere is a first organic hollow sphere foamed in advance before the matrix curing, the hydrocarbon gas is present in the hollow, or a liquid hydrocarbon is present in the hollow before the matrix curing and the low-boiling hydrocarbon in the hollow portion in the gas phase at the time of matrix curing A polishing pad, characterized in that the second organic hollow sphere is changed and the organic coating is foamed and expanded, or a mixture thereof. The method of claim 1, The polishing pad has a density of 0.5-1.0 g / cm ³ and a hardness of shore D = 50-70. The method of claim 1, The polishing pad further comprises a lower pad having a different hardness attached to the lower portion of the matrix. The method of claim 14, The lower pad is a non-woven or urethane foam having a compression ratio of 5 to 15%, a compression modulus of 55 to 75%, and a hardness of 60 to 75 shore A. The method of claim 1, And an X-Y-type macro groove showing an X-Y-axis direction on the polishing surface of the polishing pad, and an X-Y-type micro groove formed between the macro grooves. The method of claim 19, The macro groove has a depth of 0.3-1.5 mm, a width of 0.1-1.0 mm, a pitch of 1.0-8.0 mm, a micro groove of 0.2-1.0 mm in depth, a width of 0.1-0.5 mm, and a pitch of 0.8-5.0 mm. Polishing pad, characterized in that formed. The method of claim 1, And the polishing surface of the polishing pad is formed with orthogonal micro grooves having an X-Y-axis direction formed by a rectangular macro groove alone or between rectangular macro grooves. The method of claim 18, The rectangular macro grooves have a depth of 0.3-1.5 mm, a width of 0.1-1.0 mm, a pitch of 1.0-8.0 mm, and an XY-type micro groove has a depth of 0.2-1.0 mm, a width of 0.1-0.5 mm, a pitch of 0.8-5.0 mm. Polishing pad, characterized in that formed. An inorganic hollow sphere coated with an inorganic powder on the outside of the organic endothelial and having a hollow formed therein; A polishing pad cake comprising a matrix cake in which the inorganic hollow sphere is impregnated. (a) preparing a mixture by mixing an inorganic hollow sphere having an inorganic powder coated on the outside of the organic inner shell and a hollow formed therein with a polymeric matrix resin Wow, (b) adding and stirring a curing agent to the mixture; (C) a method of manufacturing a polishing pad comprising the step of demolding the resultant by injecting into the mold. The method of claim 21, The hardening agent manufacturing method of the polishing pad, characterized in that the active hydrogen compound. The method of claim 21, The hardening agent manufacturing method of a polishing pad, characterized in that the polyamine or a mixture of polyol and polyamine. The method of claim 21, The inorganic hollow sphere is a method for manufacturing a polishing pad, characterized in that mixed in 0.5 to 20 parts by weight based on 100 parts by weight of the matrix resin. The method of claim 21, Wherein the curing agent is added in an amount of 15-50 parts by weight based on 100 parts by weight of the polymeric matrix resin. The method of claim 21, A method of manufacturing a polishing pad, further comprising the step of slice-cutting the polishing pad cake obtained after demolding to obtain a plate-shaped polishing pad. The method of claim 21, Step (b) is a polishing pad manufacturing method, characterized in that carried out using a two-liquid component casting machine. A polishing pad comprising a polymeric matrix and microparticles impregnated within the polymeric matrix, wherein the microparticles are Consists of an inorganic powder coated on the outside of the organic endothelial, an inorganic hollow sphere having a hollow formed inside the inorganic, The organic pad is provided with an organic coating, and is an organic hollow sphere which is maintained in an unfoamed state before being mixed with the matrix resin and cured and foamed during curing to form a hollow portion in the organic coating, or a combination thereof. .