JP5990830B2 - Polishing pad and manufacturing method thereof - Google Patents

Description

  The present invention relates to a polishing pad and a method for manufacturing the same. In particular, the present invention relates to a polishing pad for polishing a compound semiconductor for a wafer made of a compound such as SiC, GaN, LT, and LN, and a method for manufacturing the same.

Currently, a power device using a silicon substrate is used. However, due to the material properties of silicon, there is a limit to further improving the performance of power devices by applying fine processing to silicon. There is SiC (silicon carbide) as a material replacing silicon. The forbidden band width of SiC is 3 times that of silicon, the dielectric breakdown electric field is about 10 times that of silicon, and the thermal conductivity is about 3 times that of silicon. SiC has the advantage of being superior in heat dissipation and being easily cooled. Also have. For this reason, the SiC substrate is attracting attention as a semiconductor substrate for power devices that replaces the silicon substrate. However, SiC is a chemically stable and non-reactive substance, and is a hard material next to diamond, and there is a problem that the time required for final polishing that finally eliminates scratches on the polishing surface becomes extremely long. For this reason, many applications have been filed for polishing methods relating to SiC substrates, and non-woven polishing pads have been used for the polishing pads. However, most of the conventionally reported polishing methods for SiC substrates are related to improvement of the slurry for polishing SiC substrates, and although it is described that a non-woven type polishing pad is used, the relationship between the polishing pad and the polishing characteristics There was no mention of (see Patent Documents 1 and 2).
On the other hand, many types of non-woven polishing pads have been filed. For example, a polishing pad using a non-woven fabric with a high basis weight and using a hard resin as an impregnating resin has been reported to improve the flatness of an object to be polished and prevent the occurrence of scratches (see Patent Document 4). It has also been reported that a polishing pad in which a nonwoven fabric is impregnated with a resin and pores containing a surfactant are provided inside the resin improves the flatness of the object to be polished and reduces the occurrence of scratches (patent document) 3).

JP2007-021703 JP2007-027663 JP 2002-283221 A Patent 3655252

  An object of the present invention is to provide a polishing pad capable of erasing scratches on the surface of an object after polishing in a short time in polishing compound semiconductors such as silicon carbide (SiC).

As a result of intensive investigations on a polishing pad using a nonwoven fabric in particular, the present inventors have made a compound by adding a specific amount of conductive fine particles in a polishing pad prepared by impregnating a resin into a nonwoven fabric. The present inventors have found that a polishing pad capable of erasing scratches in a short time in semiconductor polishing can be obtained.
That is, the present invention provides the following.
1. A polishing pad comprising a polishing cloth substrate impregnated with a resin, wherein the resin contains 0.5 to 18% by mass of conductive fine particles with respect to the total mass of the resin after drying. pad.
2. 2. The polishing pad according to 1 above, wherein the polishing cloth substrate is a non-woven fabric.
3. 3. The polishing pad according to 1 or 2 above, which is used for a compound semiconductor.
4). 1 to 3 above, wherein the impregnating resin contains a primary impregnating resin and a secondary impregnating resin, and the conductive fine particles are contained only in the secondary impregnating resin or in both the primary impregnating resin and the secondary impregnating resin. The polishing pad as described in any one.
5. The polishing pad according to any one of 1 to 4, wherein the conductive fine particles are selected from the group consisting of carbon black and nanodiamond.
6). The polishing pad according to any one of 1 to 5, wherein the resin is selected from the group consisting of a thermoplastic resin, a thermosetting resin, an elastomer, and raw rubber.
7). A method for producing a polishing pad, comprising preparing a polishing cloth substrate and impregnating the substrate with a resin solution containing 0.5 to 18% by mass of conductive fine particles based on the total mass of the resin after drying.
8). The step of forming a resin by impregnating a polishing cloth substrate with a resin solution includes the step of forming a resin by impregnating the polishing cloth substrate with a primary impregnation resin solution and the step of impregnating the polishing cloth substrate with a secondary impregnation resin solution. The polishing according to 7 above, wherein the conductive fine particles are contained only in the secondary impregnation resin solution or in both the primary impregnation resin solution and the secondary impregnation resin solution. A method for manufacturing a pad.
9. The method for producing a polishing pad as described in 8 above, wherein the secondary impregnating resin is formed by a dry solidification method.
10. The method for producing a polishing pad according to 8 or 9, wherein the 10.1 impregnating resin is formed by a wet coagulation method.
11. The polishing cloth base is a non-woven fabric, and the step of impregnating the resin solution with the polishing cloth base to form a resin includes immersing the non-woven cloth in the resin before impregnating the non-woven cloth with the resin solution containing conductive fine particles. The method for producing a polishing pad according to any one of 8 to 10, further comprising a stopping step.

In a polishing pad manufactured by impregnating a non-woven fabric substrate with a resin, a certain amount of conductive fine particles such as carbon black is added to the resin so that the surface of the substrate can be scratched more quickly than before when polishing a substrate such as SiC. It is possible to remove.
In particular, when the nonwoven fabric substrate is impregnated with resin, conductive fine particles are added to both the primary impregnated resin and the secondary impregnated resin to increase the conductive fine particle content of the entire nonwoven fabric, and the entire polishing pad is electrically conductive. The fine particles can be uniformly dispersed, and the ability to remove scratches on the substrate can be further enhanced when the SiC substrate is polished.

It is a microscope picture (50 times) of the cross section of the polishing pad of this invention. It is a microscope picture (50 times) of the surface of the polishing pad of this invention.

1. Polishing pad The polishing pad of the present invention is a polishing pad formed by impregnating a polishing cloth substrate with a resin, and the resin is 0.5 to 18% by mass of conductive fine particles with respect to the total mass of the resin after drying. It is characterized by including.
The polishing pad of the present invention is produced by impregnating a polishing cloth substrate with a resin. Examples of the abrasive cloth substrate include non-woven fabric, woven fabric, knitted fabric, felt, porous membrane, film, and particles. From the viewpoint of easy physical property adjustment, a nonwoven fabric is preferable.
There is no limitation in particular as a fiber, What is necessary is just a nonwoven fabric manufactured from a natural fiber (a modified fiber is included), a synthetic fiber, etc. For example, resin fibers such as polyester fibers, polyamide fibers, and acrylic fibers, and natural fibers such as cotton and hemp may be used. However, raw fibers produced by absorbing an organic solvent such as DMF or a cleaning liquid such as water during the manufacturing process. In view of preventing swelling of the fiber and mass production of the raw material fibers, it is preferable to use resin fibers such as polyester fibers that do not have water absorption (liquid) properties. As the raw fiber, it is preferable to use a fiber having a fineness of 1 to 50 dtex and a fiber length of 20 to 100 mm.

The density of the nonwoven fabric base material is less likely to adhere to the outflow fiber polyurethane resin be impregnated in the polyurethane resin solution through the fiber gap is less than 0.1 g / cm ^3, the polyurethane resin exceeds 0.2 g / cm ³ Since the amount of adhesion increases and closes the gap between the fibers, the range of 0.1 to 0.2 g / cm ³ is preferable.
The thickness of the polishing cloth substrate varies depending on the purpose, but if it is less than 1.5 mm, polyurethane resin migration (resin migration) occurs in the thickness direction during drying after impregnation of the polyurethane resin solution, and the polyurethane resin coating thickness tends to be uneven. If the thickness exceeds 5.0 mm, the polyurethane resin solution cannot penetrate into the nonwoven fabric base material, and thus it is preferably in the range of 1.5 to 5.0 mm.

The polishing pad of the present invention is manufactured by impregnating the polishing cloth substrate with a resin. The present invention is characterized in that the resin contains 0.5 to 18% by mass of conductive fine particles with respect to the total mass of the resin.
By adding the conductive fine particles, the number of scratches existing on the surface of the object to be polished can be reduced without reducing the polishing rate. The amount of the conductive fine particles is preferably 0.9 to 17% by mass, more preferably 2.5 to 15% by mass, and further preferably 4 to 10% by mass with respect to the total mass of the resin. If the amount is less than 0.5% by mass, the number of scratches cannot be sufficiently reduced. On the other hand, if it exceeds 18% by mass, the polishing rate is gradually lowered and the effect of reducing the number of scratches is lost.

  As will be described later, when the resin is impregnated into a primary impregnation resin and a secondary impregnation resin, conductive particles may be added to either one or both resins. It is preferable to add such that it is contained in at least the secondary impregnating resin. That is, it is preferable to add only the secondary impregnation resin or both the primary impregnation resin and the secondary impregnation resin. Furthermore, it is more preferable to add to both primary impregnation resin and secondary impregnation resin. The reason is not clear, but the effect of reducing the number of scratches is enhanced. When added to both, the amount of the conductive fine particles is 50% by mass or more in the secondary impregnated resin with respect to the total amount of the conductive fine particles in the primary impregnated resin and the secondary impregnated resin of the conductive fine particles. It is preferable that it is contained in.

  Although the present invention is not bound by theory, the following points are considered for the effect of using the conductive fine particles of the present invention. Carbon black and nano diamond are known to emit electrons. It is considered that the emitted electrons enter the conductive single crystal or polycrystalline substrate material, and the substrate material into which the electrons have entered becomes fragile. For this reason, it is considered that the polished surface can be efficiently polished and the surface scratches are reduced.

  In the present invention, examples of the conductive fine particles include carbon black and nanodiamond, and carbon black is preferable from the viewpoint of the effects of the present invention, in particular, the reduction of scratches. The type of carbon black to be added is not particularly limited, and any of channel black, furnace black, acetylene black, and the like can be used. The shape of the particles is not particularly limited, but the particle size (average diameter) is preferably about 10 to 100 nm, and more preferably 10 to 30 nm.

The size of the structure is indirectly represented by the oil absorption amount of Japanese Industrial Standards (JISK6217-4, carbon black for rubber-basic characteristics-Chapter 4: Determination of oil absorption amount (including compressed sample)). In the structure, the porosity and size have a positive correlation. That is, as the number of carbon black particles constituting the structure increases, the voids between the particles increase, so the amount of oil absorbed in the voids in the structure (oil absorption amount) also increases. An absorption meter is used to measure the oil absorption, and dibutyl phthalate (hereinafter abbreviated as DBP) or paraffin oil is used as the oil.
In the present invention, it is preferred that structure of the carbon black DBP oil absorption amount is about 40~200cm ³ / 100g, and more preferably 50~90cm ³ / 100g.

  In the present invention, examples of the resin include thermoplastic resins, thermosetting resins, elastomers, raw rubbers, and the like, and more specifically, thermoplastics such as polyamide, polyacryl, polyolefin, polyvinyl, polycarbonate, polyacetal, polyurethane, and polyimide resin. Examples thereof include thermosetting resins such as resin, polyurethane, epoxy, phenol, melamine, urea, and polyimide. Examples of the elastomer or raw rubber include diene elastomers (for example, 1,2-polybutadiene), olefin elastomers (for example, those obtained by dynamically cross-linking ethylene-propylene rubber and polypropylene resin, etc.), urethane elastomers, urethane rubbers (for example, Urethane rubber, etc.), styrene elastomer (eg, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer), conjugated diene rubber (eg, high cis butadiene rubber, low cis butadiene) Rubber, isoprene rubber, styrene-butadiene rubber, styrene-isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, etc.), ethylene-α-olefin rubber (for example, ethylene-propylene rubber, ethylene-propylene rubber) Down - non-conjugated diene rubber) include butyl rubber, other rubbers (e.g. silicone rubber, fluorine rubber, nitrile rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, etc.) and the like. Further, these resins may be mixed and used.

  In the present invention, the resin is preferably formed by impregnating at least twice. This is because the impregnation in two steps makes it easy to impregnate a sufficient amount of resin, and the conductive fine particles are stably supported in the resin. Depending on the type of resin and the size and properties of the conductive fine particles, the impregnation may be performed three or more times.

Also, before impregnating the resin containing conductive fine particles, in order to maintain the voids formed between the fibers, a dry resin (resin formed by dry coagulation method) is impregnated in advance to temporarily fix the fibers May be. As a result, voids formed between the fibers are maintained, so that the resin containing conductive fine particles can be sufficiently impregnated. In the present specification, the “total resin mass” means the total total mass of the resin impregnated in a plurality of times.
The adhesion amount of the dry resin used for temporary fixing is preferably 10% by mass or less of the mass of the fiber aggregate (non-impregnated resin). The adhesion amount of the primary impregnating resin is preferably 50 to 80% by mass of the mass of the fiber assembly. The adhesion amount of the secondary impregnating resin is preferably 50 to 80% by mass of the mass of the fiber assembly.

  The primary impregnation resin and the secondary impregnation resin can be arbitrarily selected from the resins described above, but a resin formed by dry coagulation is preferable as the secondary impregnation resin. Examples of such resins include polyurethane, epoxy, phenol, melamine, urea, polyimide, and the like.

Further, the primary impregnating resin is preferably a resin formed by wet coagulation. Examples of such resins include polyurethanes such as polyurethane and polyurethane polyurea, acrylics such as polyacrylate and polyacrylonitrile, vinyls such as polyvinyl chloride, polyvinyl acetate, and polyvinylidene fluoride, polysulfone, and polyethersulfone. And polysulfone type such as acetylated cellulose, acylated cellulose type such as butyrylated cellulose, polyamide type and polystyrene type.
The amount of the primary impregnation resin and the amount of the secondary impregnation resin is preferably about 1: 1 to 1: 5 by mass ratio.

The resin of the present invention may further contain a crosslinking agent, an additive and the like.
Examples of the crosslinking agent include polyvalent isocyanate compounds and organic diamine compounds. The amount of the crosslinking agent is preferably about 1 to 20% by mass relative to the resin to be crosslinked (primary impregnation resin or secondary impregnation resin).
As the additive, a hydrophilic active agent that promotes foaming, a hydrophobic active agent that stabilizes the coagulation regeneration of the polyurethane resin, and the like can be used. As the hydrophilic additive, for example, an anionic surfactant such as carboxylate, sulfonate, sulfate ester salt, phosphate ester salt or the like is used. Examples of the hydrophobic surfactant include nonions such as polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, perfluoroalkylethylene oxide adduct, glycerin fatty acid ester, and propylene glycol fatty acid ester. An anionic surfactant such as an alkyl surfactant or an alkyl carboxylic acid can be used. The addition amount varies depending on the type of additive and the type of resin, and is not particularly limited. For example, the addition amount is 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin solution.

  A compound semiconductor means a substrate made of a substance that exhibits properties of a semiconductor by combining two or more elements of Group II-VI, Group III-V, and Group IV-IV. For example, a SiC (silicon carbide) substrate GaN (gallium nitride) substrate and the like.

A manufacturing method will be briefly described by taking a SiC single crystal as an example.
The SiC single crystal is manufactured by a crystal growth method called a sublimation recombination method. The SiC powder is sublimated in a crucible having a high temperature of 2400 ° C., and the vapor is recombined on the seed crystal to obtain a SiC ingot. The completed ingot is cut with a diamond electrodeposited wire saw to obtain a single crystal substrate.
The surface scratches of the obtained single crystal substrate are removed by lapping. However, since the surface scratches cannot be completely removed, the scratches are removed by performing a final polishing process.
A SiC wafer is manufactured by performing epitaxial growth in which single crystal layers having different conductivity types and predetermined resistivities are continuously grown on the crystal structure of the substrate on the obtained substrate single crystal. If so, defects will appear in the epitaxially grown single crystal layer. For this reason, it is necessary to remove the substrate defects by finish polishing before the epitaxial growth.

The polishing pad of the present invention is particularly suitable for the polishing of a compound semiconductor, particularly the above-described finish polishing treatment, which has taken a very long time to reduce the number of scratches in the conventional polishing pad. This is because the number of scratches can be reduced with a sufficient polishing rate.
It should be noted that the polishing surface of the polishing pad of the present invention may be appropriately grooved as necessary.

2. Method for Producing Polishing Pad The method for producing a polishing pad of the present invention comprises preparing a polishing cloth substrate and applying the substrate to a resin solution containing 0.5 to 18% by mass of conductive fine particles based on the total mass of the resin after drying. Impregnating.
In the method of the present invention, the resin solution is prepared by dissolving the above resin containing conductive fine particles in a solvent. In the case of wet coagulation, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetone, acetonitrile, N- Examples include methylpyrrolidone (NMP) and a mixture thereof. Among these, DMF is particularly preferable. In the case of dry coagulation, DMF, MEK and a mixture thereof can be mentioned.
The amount of the solvent is not particularly limited, but may be added so that the resin solid content concentration is, for example, 10 to 50 (v / w)%.

A polishing cloth substrate is immersed in the resin solution. What is necessary is just to immerse for about 1 to 30 minutes at about 5-40 degreeC. After immersion, the solvent is removed by drying.
Thereafter, a thermosetting treatment or the like is optionally performed depending on the type of resin used.

  The step of impregnating the substrate with the resin solution to form the resin includes the step of impregnating the substrate with the primary impregnation resin solution to form the resin and the step of impregnating the substrate with the secondary impregnation resin solution to form the resin. It is preferable to include.

(Primary impregnation step)
There is no particular restriction on the impregnation method in each impregnation step, but when the dry resin is impregnated directly into the sheet fiber substrate by primary impregnation, and solvent drying and resin curing are simultaneously performed in a drying furnace, until dry curing During this period, resin migration may occur in the thickness direction of the fiber base material, and the amount of resin may become non-uniform in the thickness direction of the polishing cloth. For this reason, the resin impregnated in the next impregnation step may become non-uniform, resulting in variations in physical properties. Therefore, it is preferable to use a wet coagulation method in the primary impregnation.

  The wet coagulation method impregnates a resin solution by impregnating a substrate such as a nonwoven fabric into a resin solution, and immersing the nonwoven fabric after impregnation in an aqueous coagulation liquid mainly composed of water, which is a poor solvent for the resin. It is a method performed by making it. In the coagulation liquid, the resin is coagulated and regenerated on the surface of the fiber by the progress of substitution of the resin solution solvent (for example, DMF) and the coagulation liquid on the surface of the resin solution adhering to the fibers of the nonwoven fabric. In the method of the present invention, conductive fine particles are added in advance to the resin solution.

  In the washing / drying step, the nonwoven fabric base material on which the resin has been coagulated and regenerated is washed in a washing liquid such as water to remove the solvent such as DMF remaining in the nonwoven fabric base material. After washing, the nonwoven fabric substrate is pulled up from the washing liquid, and excess washing liquid is squeezed out using a mangle roller or the like. Then, you may dry a nonwoven fabric base material in the dryer of 100 to 150 degreeC (for example, about 120 degreeC).

A cross-linking agent such as a polyvalent isocyanate compound is previously contained in a resin solution such as a polyurethane resin, and after the drying, a cross-linking reaction by the cross-linking agent is advanced by heat treatment or the like to further create a cross-linked resin layer. May be.
In the heat treatment step, for example, the non-woven fabric substrate after drying is heated for about 12 to 36 hours (for example, 17 hours) in a heater set to 100 to 130 ° C. (for example, about 110 ° C.). By this heat treatment, a cross-linking bond is formed between the coagulated and regenerated resin molecules by a cross-linking agent such as a polyvalent isocyanate compound previously contained in the resin solution. A crosslinked resin layer is formed on the surface of the polyester fiber by a crosslinked resin.

You may perform a buff process or a slice process process after the said drying or bridge | crosslinking.
In the buffing step, buffing may be performed on both sides of the nonwoven fabric substrate after the first layer is formed (after the primary impregnation). In a nonwoven fabric base material with a thermosetting coating layer formed on the surface of the fiber, the amount of resin on both sides is large, and the gap between fibers is narrowed, so the gap is narrowed by buffing on both sides. Remove the part. At this time, in order to remove a portion having a large amount of resin, both surfaces need to be buffed with a thickness of 0.1 to 0.7 mm.

(Secondary impregnation step)
The step of forming the resin by impregnating the substrate with the secondary impregnating resin solution is preferably performed by a dry solidification method. The dry coagulation method means that a substrate such as a nonwoven fabric is immersed in a solvent solution containing a monomer or prepolymer or a solvent solution containing a polymer (resin), and the monomer is cured by heating, and then the solvent is removed. Do.
In the present specification, when the “step of forming a resin by impregnating the substrate with a resin solution”, the “resin solution” includes a solution such as a solvent solution containing a monomer or a prepolymer.

The secondary impregnation step will be described more specifically with an example.
In one example, a substrate such as a nonwoven fabric is immersed in a solvent solution of a resin containing a monomer such as an isocyanate-terminated urethane prepolymer or an organic diamine compound, and the substrate is impregnated with the monomer.
In another example, the solvent solution in which the thermosetting polyurethane resin is dissolved is impregnated at a concentration of at least ½ or less of the concentration of the thermosetting polyurethane resin contained in the solvent solution used in the primary impregnation.
When the former solvent solution is used, in the secondary impregnation step, both surfaces are buffed in a solvent solution in which an isocyanate-terminated urethane prepolymer and an organic diamine compound are dissolved in, for example, methyl ethyl ketone (hereinafter abbreviated as MEK). After immersing the non-woven fabric intermediate, excess solvent solution is squeezed out using a mangle roller in the same manner as in the primary impregnation step, and the non-woven fabric intermediate is uniformly impregnated.
The solid content concentration of the solvent solution is preferably in the range of 30 to 70% by mass, for example. The solid content concentration of the crosslinking agent is preferably 4 to 20% by mass. The secondary impregnation is preferably performed at 5 to 40 ° C, more preferably 20 to 30 ° C. By performing the secondary impregnation within this temperature range, the progress of the crosslinking reaction by the organic diamine compound contained in the solvent solution is suppressed.

  Also, before impregnating the resin containing conductive fine particles (or before the primary impregnation step), in order to maintain the void formed between the fibers, the fibers may be preliminarily impregnated and temporarily fixed. Good. At this time, the dry resin adhesion amount is preferably 10% by mass or less of the mass of the fiber assembly (resin non-impregnated). As a result, voids formed between the fibers are maintained, so that a resin containing conductive fine particles can be sufficiently impregnated between the fibers.

The polishing pad of the present invention is preferably subjected to drying, crosslinking, thermosetting treatment, and the like after the resin impregnation treatment step described above, and then sliced to a thickness of about 0.5 to 2.0 mm.
Further, it is preferable to further buff the surface after slicing. The buffing process can be performed by a buffing machine. The buffing machine is provided with a pressure roller having a substantially flat surface. On the surface layer of the pressure roller, an elastic layer is formed of an elastic material such as rubber. A baffler for buffing the resin-impregnated nonwoven fabric is disposed on the opposite side of the pressure roller so as to face the pressure-contact roller via the resin-impregnated nonwoven fabric. Sandpaper as a buff sheet is attached to the surface of the baflora. At the time of buffing, the back surface of the resin-impregnated nonwoven fabric is pressed against the surface of the pressure roller. In a state where the resin-impregnated nonwoven fabric is supported substantially flat on the surface of the pressure roller, buffing is performed on the opposite surface side with a buffalo. The buff amount is adjusted by appropriately changing the interval (clearance) between the pressure roller and the buffalo. The sandpaper count, buff amount, and processing speed are adjusted as appropriate, but the sandpaper count is # 100 to # 200, the buff amount is 0.05 to 1.0 mm, and the processing speed is 0.5 to 5 m / min. It is preferable.

An example of a method for producing the polishing pad of the present invention is as follows.
(i) A first step of wet-coagulating a thermosetting polyurethane resin impregnated in a non-woven fabric substrate and then drying and crosslinking the thermosetting polyurethane resin wet-coagulated by heat treatment
(ii) Buffing both surfaces of the fiber assembly on which the resin layer is formed in the first step
(iii) A secondary impregnation step of impregnating the buffed fiber aggregate in a solvent solution of an isocyanate-terminated urethane prepolymer and a crosslinking agent, and a crosslinking agent obtained by impregnating the isocyanate-terminated urethane prepolymer impregnated in the secondary impregnation step by a drying heat treatment Cross-linking step
(iv) A step of slicing a fiber aggregate crosslinked with a crosslinking agent after secondary impregnation
(v) Step of buffing the sliced fiber aggregate In the above method, the conductive fine particles are added to the resin in the step (i) and / or (iii).

As another embodiment, a method including a step of temporarily fixing fibers to a nonwoven fabric substrate using a thermosetting polyurethane resin can be given as follows.
(a) A process of temporarily fixing a fiber by impregnating a nonwoven fabric substrate with a dry resin and then curing the resin by drying and heat treatment
(b) A step of slicing the fiber assembly temporarily fixed in step (a)
(i) The first step of impregnating the fiber aggregate and thermosetting polyurethane resin in step (b), wet coagulating and then drying, and crosslinking the thermosetting polyurethane resin wet coagulated by heat treatment
(ii) Buffing both surfaces of the fiber assembly on which the resin layer is formed in the first step
(iii) A secondary impregnation step of impregnating the buffed fiber aggregate in a solvent solution of an isocyanate-terminated urethane prepolymer and a crosslinking agent, and a crosslinking agent obtained by impregnating the isocyanate-terminated urethane prepolymer impregnated in the secondary impregnation step by a drying heat treatment Cross-linking step
(vi) A step of slicing a fiber aggregate crosslinked with a crosslinking agent after secondary impregnation
(v) Step of buffing the sliced fiber aggregate In the above method, the conductive fine particles are added to the resin in the step (i) and / or (iii).

A polishing pad was produced by the following steps.
1) Manufacturing process
(i) Non-woven fabric substrate (fiber name: polyester) (weight: 0.138 g / cm ³ ) (thickness: 3.4 mm) and dry resin Bernock DN950 (manufactured by DIC) (polyisocyanate prepolymer / DMF + MEK, 8% by mass) After the impregnation, the fiber was temporarily fixed by curing the resin by drying (120 ° C.) and heat treatment (110 ° C., 17 hours).
(ii) The nonwoven fabric substrate temporarily fixed in the step (i) was sliced to a thickness of 2.2 to 2.3 mm.
(iii) The non-woven fabric substrate of (ii) is impregnated with a thermosetting polyurethane resin, wet-coagulated and then dried, and the wet-coagulated thermosetting polyurethane resin is crosslinked by heat treatment (110 ° C., 17 hours) ( Primary impregnation step).
(iv) Both surfaces of the fiber assembly on which the resin layer was formed in the step (iii) were buffed to obtain a fiber assembly having a thickness of 1.95 mm.
(v) After impregnating the fiber aggregate buffed in the step (iv) with a solvent solution of an isocyanate-terminated urethane prepolymer and a crosslinking agent, drying (120 ° C.) and heat treatment (110 ° C., 24 hours) The impregnated isocyanate-terminated urethane prepolymer was crosslinked with a crosslinking agent (secondary impregnation step).
(vi) After the step (v), the fiber assembly crosslinked with a crosslinking agent was sliced to a thickness of 1.5 to 1.6 mm.
(vii) The sliced fiber assembly was further buffed to obtain a polishing pad having a final thickness of 1.3 mm.
Carbon black (average diameter 16 nm, oil absorption: 69) is a predetermined carbon black obtained by dispersing carbon black dispersed in an ester urethane resin in both steps (iii) and (v) (one step in Examples 6 and 7). It added to resin so that it might become quantity.
In Comparative Example 3, silica (particle diameter: about 20 nm, specific gravity 1.070 to 1.100) was used instead of carbon black.
The amounts of each resin, carbon black, crosslinking agent and solvent are shown in Tables 1 and 2.
In addition, the adhesion amount of the dry resin in the temporary fixing step was 10% by mass of the fiber aggregate mass (resin non-impregnated). The adhesion amount of the primary impregnation resin was 75% by mass of the mass of the fiber assembly. The adhesion amount of the secondary impregnating resin was 65% by mass of the mass of the fiber assembly. Therefore, the total adhesion amount of the temporary fixing resin, the primary impregnation resin and the secondary impregnation resin was 150% by mass of the mass of the fiber assembly.

The meanings of the abbreviations in Tables 1 and 2 are described below.
MDI: Diphenylmethane-4,4′-diisocyanate MBOCA: 4,4′-methylene-bis [2-chloroaniline]
DMF: Dimethylformamide additive A: Film forming stabilizer, cellulose additive (acetylbutylcellulose)

2) Polishing evaluation method
(i) Polishing method A SiC substrate and a polishing pad were set in a polishing apparatus, and polishing was performed while an abrasive was dropped on the pad intermittently.
As the abrasive, DSC-0901 (manufactured by Fujimi Incorporated) was used, and 12 cc was dropped onto the polishing pad per minute. The rotation speed of the platen was 35 rpm.
The pressure for pressing the SiC substrate against the polishing pad by the pressure head was 0.1 MPa (530 g / cm ² ).
The SiC surface was polished using five SiC substrates of 3 inches (diameter 7.62 cm). The polishing time was 6 hours.

(ii) Physical properties (thickness)
The thickness of the polyurethane sheet was measured according to the thickness measurement method described in Japanese Industrial Standard (JIS K6550). That is, the sheet thickness was measured when a load of 100 g per 1 cm ² was applied (added) to the polyurethane sheet as the initial load in the thickness direction. The sheet is cut into 100 pieces of 10 cm in length and 10 cm in width, and the thickness of the four corners and the center of each piece is read and measured to the minimum scale using a dial gauge (minimum scale 0.01 mm), and the average value of 5 points is 1 It was set as the thickness of the piece. The average thickness of the sheet was the average thickness measured for 100 pieces.

(A hardness)
A hardness was measured according to JIS K7311.
(Density g / cm ³ )
The weight (g) of the sample cut into a predetermined size was measured, and the volume (g / cm ³ ) was calculated from the size.
(Compression rate%)
The compression rate was measured in accordance with JIS L 1021, and the thickness reduction during compression was measured, and the percentage of thickness reduction during compression relative to the thickness before compression was calculated.
(Compressive modulus%)
The compression rate was calculated according to JIS L 1021.
(Taber wear (mg / 1000 times))
It measured according to the method according to the Taber abrasion test of Japanese Industrial Standard (JIS K 6902).

(iii) Micrograph A micrograph (50 times) of a cross section of the polishing pad of Example 3 is shown in FIG.
The microscope picture (50 times) of the surface (upper surface) of the polishing pad of Example 3 is shown in FIG.

(iv) Evaluation method and rate: The amount of decrease was calculated by measuring the weight before and after polishing (n = 5). The SiC density = 3.22 g / cm ³ was used.
Scratch measurement: The number of scratches per substrate was measured using a confocal microscope.

From Tables 1 and 2, the following is clear.
When carbon black, which is the conductive fine particles of the present invention, was contained in an amount of 0.5 to 18% by mass, the grinding amount and polishing rate were sufficiently large, and the number of scratches could be reduced (Examples 1 to 8). In addition, when carbon black was added only to the primary impregnating resin (Example 6), the polishing rate was almost the same as when it was added to both (Example 3), but the number of scratches was reduced. The effect was weak.
On the other hand, when carbon black is not included at all, the polishing rate is not significantly reduced, but the number of scratches is 1.4 / one substrate (average of 5 times) (there are countless scratches before polishing). , Could not be reduced (Comparative Example 1). Further, when carbon black was added in an amount of more than 18% by mass, the polishing rate was lowered and the scratch could not be sufficiently reduced (Comparative Example 2). When carbon black was changed to silica, there was no scratch reduction effect (Comparative Example 3).

Claims (11)

A polishing pad obtained by impregnating a polishing cloth base not containing polyvinyl alcohol with a resin, wherein the resin contains 0.5 to 18% by mass of conductive fine particles based on the total mass of the resin after drying. A characteristic polishing pad.   The polishing pad according to claim 1, wherein the polishing cloth substrate is a nonwoven fabric.   The polishing pad according to claim 1 or 2, which is used for a compound semiconductor.   The said impregnating resin contains primary impregnation resin and secondary impregnation resin, and electroconductive fine particles are contained only in secondary impregnation resin or in both primary impregnation resin and secondary impregnation resin. The polishing pad as described in any one of these.   The polishing pad according to any one of claims 1 to 4, wherein the conductive fine particles are selected from the group consisting of carbon black and nanodiamond.   The polishing pad according to any one of claims 1 to 5, wherein the resin is selected from the group consisting of a thermoplastic resin, a thermosetting resin, an elastomer, and raw rubber. Providing a polishing cloth base containing no polyvinyl alcohol, and impregnating the base with a resin solution containing 0.5 to 18% by weight of conductive fine particles based on the total weight of the resin after drying. A method of manufacturing a polishing pad.   The step of forming a resin by impregnating a polishing cloth substrate with a resin solution includes the step of forming a resin by impregnating the polishing cloth substrate with a primary impregnation resin solution and the step of impregnating the polishing cloth substrate with a secondary impregnation resin solution. The method according to claim 7, wherein the conductive fine particles are contained only in the secondary impregnation resin solution or in both the primary impregnation resin solution and the secondary impregnation resin solution. Manufacturing method of polishing pad.   The method for producing a polishing pad according to claim 8, wherein the secondary impregnating resin is formed by a dry solidification method.   The method for producing a polishing pad according to claim 8 or 9, wherein the primary impregnation resin is formed by a wet coagulation method.   The polishing cloth base is a non-woven fabric, and the step of impregnating the resin solution with the polishing cloth base to form a resin includes immersing the non-woven cloth in the resin before impregnating the non-woven cloth with the resin solution containing conductive fine particles. The method for producing a polishing pad according to claim 8, further comprising a stopping step.