JP2013515379A - Polishing pad and method of manufacturing the same - Google Patents

Abstract

The present disclosure relates to a polishing pad having a porous polishing layer, a method of manufacturing such a pad, and a method of using such a pad in a polishing process. The polishing pad includes a flexible layer having first and second surfaces facing each other, and a porous polishing layer disposed on the first surface of the flexible layer. The porous polishing layer includes a crosslinked network including a thermosetting component and a radiation curable component, and the radioactive curable component and the thermosetting component are covalently bonded in the crosslinked network. The porous abrasive layer also includes polymer particles dispersed in the crosslinked network, the polymer particles including at least one of thermoplastic polymers or thermosetting polymers. The porous polishing layer typically also includes closed cell pores dispersed in the crosslinked network.
[Selection] Figure 4

Description

(Cross-reference of related applications)
This application claims the benefit of US provisional application 61 / 288,982 filed on December 22, 2009 and 61 / 422,442 filed on December 13, 2010. The disclosures of which are incorporated herein by reference in their entirety.

  During the manufacture of semiconductor devices and integrated circuits, silicon wafers are iteratively processed through a series of deposition and etching steps to form overlapping material layers and device structures. In order to obtain a smooth wafer surface with high uniformity across the wafer surface, without scratches or dents (known as dishing), surface irregularities remaining after the deposition and etching steps (protruding, uneven) A polishing technique known as chemical mechanical planarization (CMP) may be used to remove height, dents, grooves, etc.).

  In a typical CMP polishing process, a substrate, such as a wafer, is exposed to a polishing pad in the presence of a processing liquid and / or an etching chemistry that typically has a slurry of abrasive particles in water. Press and move relatively. Various CMP polishing pads used with polishing slurries are described, for example, in U.S. Pat. Nos. 5,257,478 (Hyde et al.); 5,921,855 (Osterheld et al.); 6,126,532. (Sevilla et al.); 6,899,598 (Prasad); and 7,267,610 (Elmufdi et al.). Fixed polishing pads are also known, and those exemplified in U.S. Pat. No. 6,908,366 (Gagliadi) often have abrasive particles that are precisely shaped particles. It extends from the pad surface in the form of a composite and is secured to the entire surface of the pad. Recently, a polishing pad having a number of polishing elements extending from a compressible underlayer has been described in International Patent Application Publication No. WO / 2006605714 (Bajaj).

  Although various types of polishing pads are known and used, the art still has a CMP process in which relatively large diameter dies are used, or a relatively high level of wafer surface flatness and uniformity. Particularly in the required CMP process, there is a need for new and improved CMP polishing pads.

  The present disclosure provides a porous polishing pad comprising a polishing layer having a thermally cured component and a radiation cured component, and a method for manufacturing such a polishing pad. Through the use of polymer particles, pores are incorporated into the polishing layer. The pores in the porous polishing pad disclosed herein are closed cell pores that generally have lower pore size non-uniformities and pore sizes that are smaller than those of conventional heat-cured polishing pads. Control of pore size and pore distribution can be advantageous, for example, in the polishing performance of the polishing pad.

In one aspect, the present disclosure provides a polishing pad, the polishing pad comprising
A flexible layer having opposing first and second surfaces;
A porous polishing layer disposed on the first surface of the flexible layer, the porous polishing layer comprising:
A crosslinked network comprising a thermosetting component and a radiation curable component, wherein the radiation curable component and the thermosetting component are covalently bonded in the crosslinked network; and
Polymer particles dispersed in a crosslinked network;
Closed cell pores dispersed in the crosslinked network. In some embodiments, the polishing pad further comprises a support layer interposed between the flexible layer and the porous polishing layer.

In another aspect, the present disclosure provides a method of manufacturing a polishing pad, the method comprising:
Providing a thermosetting resin composition, a radiation curable resin composition, and a composition comprising polymer particles;
Forming pores in the composition; and
Placing the composition on a support layer;
By exposing the composition to radiation to at least partially cure the radiation curable resin composition and heating the composition to at least partially cure the thermosetting resin composition on the support layer Forming a porous polishing layer. In some embodiments, the method further comprises adhesively bonding a flexible layer to the support layer surface opposite the porous polishing layer.

In a further aspect, the present disclosure provides a polishing method comprising:
Contacting the substrate surface with a porous polishing layer of a polishing pad according to the present disclosure;
Moving the polishing pad relative to the substrate to reduce the surface of the substrate.

  Exemplary embodiments of polishing pads according to the present disclosure have a variety of features and characteristics that allow them to be used in a variety of polishing applications. In some embodiments, the polishing pads of the present disclosure may be particularly suitable for chemical mechanical planarization (CMP) of wafers used in the manufacture of integrated circuits and semiconductor devices. In some embodiments, the polishing pad described in this disclosure may provide some or all of the following advantages.

  For example, in some embodiments, a polishing pad according to the present disclosure improves retention of a working fluid used in a CMP process at the interface between the pad polishing surface and the substrate polished surface. By acting on, it is possible to improve the effect of the processing liquid in the enhanced polishing. In another exemplary embodiment, a polishing pad according to the present disclosure can reduce or eliminate dishing and / or edge erosion of the wafer surface during polishing. In some exemplary embodiments, using a polishing pad according to the present disclosure in a CMP process may improve polishing uniformity within the wafer, improve wafer surface flatness after polishing, edge die yield from the wafer. As well as improved CMP process operating conditions and consistency. In a further embodiment, the use of a polishing pad according to the present disclosure allows processing of larger diameter wafers while maintaining the degree of surface uniformity necessary to obtain a high chip yield, or It may be possible to process more wafers before pad surface conditioning is required to maintain polishing uniformity on the wafer surface, or to reduce the process time and wear of the pad conditioner.

In this disclosure,
“Pore diameter non-uniformity” refers to the average standard deviation of the pore diameters divided by the average pore diameter and multiplied by 100.

  The term “polyurethane” refers to two or more urethane bonds (—NH—C (O) —O—), urea bonds (—NH—C (O) —NH— or —NH—C (O) —N (R )-, Where R may be hydrogen, aliphatic, cycloaliphatic, or aromatic groups), biuret, allophanate, uretdione, or a polymer having an isocyanurate bond in any combination.

  The term “(meth) acrylate” refers to acrylates and methacrylates, which can include urethane acrylates, methacrylates, and combinations of acrylates and methacrylates.

  The term “polymer” refers to a molecule having a structure comprising a plurality of repeating units derived from a molecule of low relative molecular weight. The term “polymer” includes “oligomers”.

  Terms such as “a”, “an”, and “the” are not intended to refer to only one entity, but include a general classification that can be used for illustration purposes. The terms “a”, “an”, and “the” are used interchangeably with the term “at least one”.

  The phrases “at least one of” and “comprising at least one of” are followed by any one of the items in the list and two or more items in the list. Refers to a combination of

  All numerical ranges include the endpoints and non-integer values between the endpoints unless otherwise specified.

  A summary of various aspects and advantages of exemplary embodiments of the present disclosure has been compiled. The above summary is not intended to describe each illustrated embodiment or every implementation of the present disclosure. In the following figures and detailed description, several embodiments of the present disclosure are illustrated in more detail.

Exemplary embodiments of the present disclosure will be further described with reference to the accompanying drawings.
Sectional drawing and the top view micrograph of the porous polishing pad by a prior art. Sectional drawing and the top view micrograph of the porous polishing pad by a prior art. 1 is a schematic side view of a polishing pad according to the present disclosure. FIG. 4 is a side view of a polishing pad having protruding polishing elements according to another embodiment of the present disclosure. FIG. 4 is a side view of a polishing pad having protruding polishing elements according to yet another embodiment of the present disclosure. FIG. FIG. 3 is a micrograph of a cross-sectional view and a top view of the cured composition of Example 2 useful for forming an abrasive layer according to the present disclosure. FIG. 3 is a micrograph of a cross-sectional view and a top view of the cured composition of Example 2 useful for forming an abrasive layer according to the present disclosure. The microscope picture of sectional drawing and the top view of the hardening composition of the comparative example 3. FIG. The microscope picture of sectional drawing and the top view of the hardening composition of the comparative example 3. FIG. 16 is a cross-sectional and top view micrograph of the cured composition of Example 15 useful for forming an abrasive layer according to the present disclosure. 16 is a cross-sectional and top view micrograph of the cured composition of Example 15 useful for forming an abrasive layer according to the present disclosure. FIG. 5 is a photomicrograph of a cross-sectional view of the cured composition of Example 11 useful for forming an abrasive layer according to the present disclosure.

  In the figures, the same reference numbers refer to similar elements. The figures included herein are not to scale, in which the components of the polishing pad are sized to highlight selected features.

  A typical CMP pad is constructed from a thermoset (eg, polyurethane) material with holes. The pores can be generated using a variety of methods such as microballoons, soluble fibers, gas confinement (eg, in situ or ex situ generation), and physical air confinement. When using these methods, the temperature gradient generated during the polymerization, the skin / core effect resulting from the molding operation, the fiber distribution, the dissolution rate of the soluble fiber, and the polishing chemistry, It can be difficult to control the volume and distribution of the pores.

  Some commercially available CMP pads have an open cell pad structure generated during thermal curing of the isocyanate resin. FIG. 1 shows a cross-sectional and top view of an open-cell CMP pad commercially available from PPG Industries (Pittsburgh, Pa.) Available under the trade name “S7”. As shown in FIG. 1, the hole diameter, hole shape, and distribution in the pad are not controlled.

  The present disclosure generally relates to an improved porous polishing pad in which closed cell pores with controlled pore size and uniformity are formed. Various representative embodiments of the present disclosure will now be described. Various modifications and changes can be made to the exemplary embodiments of the present disclosure without departing from the spirit and scope of the disclosure. Therefore, it should be understood that the embodiments of the present invention are not limited to the representative embodiments described below, but are governed by the limitations set forth in the claims and any equivalents thereto.

  Referring to FIG. 2 below, the porous polishing pad 2a includes a flexible layer 10a and a porous polishing layer 12a disposed on one side (that is, one main surface) of the flexible layer. Between the porous polishing layer 12a and the flexible layer 10a is an optional support layer 8a useful for some embodiments of the porous polishing pad and method of the present disclosure. The porous polishing layer includes a crosslinked network, polymer particles dispersed in the crosslinked network, and closed cell pores dispersed in the crosslinked network. In contrast to polishing pads and methods where polishing pad components are removed during polishing to form voids (eg, by erosion or dissolution), polishing pads according to the present disclosure are porous prior to initiating the polishing process. is there.

  Exemplary polymer particles in the polishing layer can include thermoplastic polymer particles, thermosetting polymer particles, and mixtures thereof. The term “thermoplastic polymer” refers to a polymeric material that is essentially not cross-linked and essentially does not form a three-dimensional network. The term “thermoset” refers to a polymer that is at least substantially cross-linked, the polymer having an essentially three-dimensional network. In some embodiments, the polymer particles have minimal sintering of the particles upon heating (ie, there is minimal plastic flow at the interface of the polymer particles in the polishing pad of the present disclosure, and the polymer particles May be selected such that there is little or no interparticle fusion. In some embodiments, if the pad polymer particles comprise a particulate thermoplastic polymer, the polishing pad can be prepared below the melting point or sintering point of the particulate thermoplastic polymer. In another embodiment, the polymer particles comprise a thermosetting polymer.

  Polymer particles useful in the practice of the present disclosure can be prepared by a variety of methods, such as condensation reactions, free radical initiation reactions, or combinations thereof. In yet another embodiment, the polymer may comprise an interpenetrating polymer network formed by stepwise or simultaneous condensation and free radical polymerization reactions. In this disclosure, the term “interpenetrating polymer network” (IPN) refers to a combination of two polymers, both in network form, at least one of which is in the other existing polymer, It is synthesized or cross-linked. Typically in IPN, there is no induced covalent bond between the two polymers. Thus, in addition to mechanical blending and copolymerization, IPN represents another mechanism by which different polymers can be physically combined.

  The polymer particles can be prepared by various methods. In some embodiments, the bulk polymer may be cryomilled and classified to the desired particle size range. The shape of the polymer particles may be regular or irregular, and may include the following shapes. Spheres, fibers, disks, flakes, and combinations or mixtures thereof. In some embodiments, the polymer particles are substantially spherical. The term “substantially spherical” is at least 0.75 (in some embodiments, at least 0.8, 0.85, 0.9, 0.95, 0.96, 0.97, or 0.98). ). In some embodiments, the polymer particles are fibers. Fibers useful in the practice of this disclosure are typically at least 1.5: 1, such as at least 2: 1, 3: 1, 4: 1, 5: 1, 10: 1, 25: 1, 50 :. 1. Aspect ratio (ie, ratio of longest dimension to shortest dimension) of 1, 75: 1, 100: 1 or greater. Fibers useful in the practice of the present disclosure may have an aspect ratio in the range of 2: 1 to 100: 1, 5: 1 to 75: 1, or 10: 1 to 50: 1.

  In some embodiments, the polymer particles may have an average particle size of at least 5 (in some embodiments, at least 7, 10, 15, 20, 25, 30, 40, or 50) micrometers. Good. In some embodiments, the polymer particles may have an average particle size of up to 500 (in some embodiments, up to 400, 300, 200, or 100) micrometers. Particle size generally refers to the diameter of the particle, but in embodiments where the particle is not spherical (eg, a fiber), it may refer to the largest dimension of the particle. The average particle diameter of the polymer particles can be measured by a conventional method. For example, the average particle size of the polymer particles can be measured using light scattering techniques such as a Coulter LS particle size analyzer manufactured and marketed by Beckman Coulter Incorporated. “Particle size” as used herein and in the claims refers to the diameter or maximum dimension of a particle based on volume percent measured by light scattering using a Coulter Counter LS particle size analyzer. In this light scattering technique, the particle size is measured from the hydrodynamic radius of gyration, regardless of the actual shape of the particle. The “average” particle size is the average diameter of the particles based on volume percent. In some embodiments, particularly those in which the particles are fibers, the fibers may be up to about 600, 500, or 450 micrometers (30, 35, or 40 US Mesh) as measured by conventional sieving techniques. ) Maximum particle size. For example, in some embodiments, at least 97, 98, or 99 percent of the fiber passes through a sieve having an opening of 600, 500, or 400 micrometers (30, 35, or 40 US Mesh). To do.

  In some embodiments, the polymer particles have a high degree of uniformity. In some embodiments, the non-uniformity in the particle size of the polymer particles is up to 75 (in some embodiments, up to 70, 65, 60, 65, or 50) percent. Particle size non-uniformity refers to the standard deviation of particle size divided by the average particle size multiplied by 100.

  In some embodiments, the polymer particles are substantially solid. The term “substantially solid” as used herein means that the particulate polymer is not hollow, for example, the polymer particles are not in the form of hollow microcapsules. However, in some embodiments, the substantially solid polymer particles may contain trapped bubbles.

  Suitable polymer particles include polyvinyl chloride, polyvinyl fluoride, polyethylene, polypropylene, nylon, polycarbonate, polyester, poly (meth) acrylate, polyether, polyamide, polyurethane, polyepoxide, polystyrene, polyimide (eg, polyetherimide). , Polysulfones and mixtures thereof. In some embodiments, the polymer particles may be selected from poly (meth) acrylates, polyurethanes, polyepoxides, and mixtures thereof.

  In some embodiments, the polymer particles include water soluble particles. Typical useful water-soluble particles include sugars (eg, polysaccharides such as dextrin, cyclodextrin, starch, mannitol, and lactose), celluloses (eg, hydroxypropylcelluloses and methylcelluloses), proteins, polyvinyl alcohol. , Polyvinyl pyrrolidone, polyacrylic acid, polyethylene oxide, water-soluble photosensitive resin, sulfonated polyisoprene, sulfonated polyisoprene copolymer, and any combination thereof. In some embodiments, the polymer particles comprise cellulose. In some of these embodiments, the polymer particles comprise methylcellulose. In these embodiments, the polymer particles include water-soluble particles, but the polymer particles can form pores in the polishing layer when the polishing layer is formed. A working fluid capable of dissolving the particles during polishing is not necessary for the formation of the holes.

  In some embodiments, the polymer particles comprise a polyurethane, the polyurethane comprising, for example, a resin comprising an end-protected isocyanate reactant having at least two isocyanate groups and / or at least two end-protected isocyanate groups; And a second resin having at least two groups reactive with the group.

  In some embodiments, the first and second resins may be mixed together and polymerized or cured to form a bulk polyurethane, which may then be ground (eg, cryogenic ground) and optionally classified. May be. In some embodiments, the polymer particles mix the first and second resins together and slowly pour the mixture under stirring into heated deionized water (optionally organic co-solvent and / or interface). May be formed by isolating the formed particulate material (in the presence of an activator) (eg, by filtration), drying the isolated particulate material, and optionally classifying the dried particulate polyurethane. . In another embodiment, the isocyanate and hydrogen materials are present in the presence of an organic solvent (eg, alcohols, water-insoluble ethers, branched and straight chain hydrocarbons, ketones, toluene, xylene, and mixtures thereof). May be mixed together.

  In some embodiments, the first resin comprising at least two isocyanate groups may be selected from isocyanate functional monomers, isocyanate functional prepolymers, and combinations thereof. Typical suitable isocyanate monomers include: aliphatic polyisocyanates; ethylenically unsaturated polyisocyanates; alicyclic polyisocyanates; aromatic polyisocyanates in which the isocyanate group is not directly bonded to an aromatic ring Such as α, α′-xylene diisocyanate; aromatic polyisocyanates in which the isocyanate group is directly bonded to an aromatic ring, such as benzene diisocyanate; halogenation, alkylation, alkoxylation, nitration, carbodiimide of these polyisocyanates Modified, urea-modified, and biuret-modified derivatives; and dimerization and trimerization products of these polyisocyanates.

  Typical aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethyl. Hexane diisocyanate, decamethylene diisocyanate, 2,4,4, -trimethylhexamethylene diisocyanate, 1,6,1-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4- (isocyanate Natomethyl) octane, 2,5,7-trimethyl-1,8-diisocyanato-5- (isocyanatomethyl) octane, bis (isocyanatoethyl) -ca Boneto, bis (isocyanatoethyl) ether, 2-isocyanatopropyl-2,6-diisocyanato hexanoate, lysine diisocyanate methyl ester, ricin triisocyanate methyl ester and mixtures thereof.

  Representative suitable ethylenically unsaturated polyisocyanates include butene diisocyanate and 1,3-butadiene-1,4-diisocyanate. Typical suitable alicyclic polyisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatocyclohexyl) -2,2 -Propane, bis (isocyanatocyclohexyl) -1,2-ethane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2 -Isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5 Isocyanatomethyl-bicyclo [2. .1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3- Isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) ) -Bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane and These mixtures are mentioned.

  Typical aromatic polyisocyanates in which the isocyanate group is not directly bonded to the aromatic ring include bis (isocyanatoethyl) benzene, α, α, α ′, α′-tetramethylxylene diisocyanate, 1,3 -Bis (1-isocyanato-1-methylethyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylene triisocyanate, 2,5-di (isocyanatomethyl) furan and mixtures thereof.

  Representative suitable aromatic polyisocyanates having an isocyanate group directly bonded to an aromatic ring include phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene tris. Isocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, ortho-tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, bis (3-methyl-4-isocyanatophenyl) methane, bis (isocyanatophenyl) ethylene 3,3′-dimethoxy-biphenyl -4,4'-diisocyanate, triphenylmethane triisocyanate, polymer 4,4'-diphenylmethane diisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 4-methyldiphenylmethane-3,5,2 ', 4', 6'-pentaisocyanate, diphenyl ether diisocyanate, bis (isocyanatophenyl ether) ethylene glycol, bis (isocyanatophenyl ether) -1,3-propylene glycol, benzophenone diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichloro Examples include carbazole diisocyanate and mixtures thereof.

  In some embodiments, the first resin comprising at least two isocyanate groups is α, α′-xylene diisocyanate, α, α, α ′, α′-tetramethylxylene diisocyanate, isophorone diisocyanate, bis (isocyanato). (Cyclohexyl) methane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and mixtures thereof.

  In some embodiments, the first resin having at least two isocyanate groups may comprise an isocyanate functional polyurethane prepolymer. Isocyanate functional polyurethane prepolymers can be prepared by a variety of conventional techniques. In some embodiments, at least one polyol such as a diol and at least one isocyanate functional monomer such as a diisocyanate monomer may be reacted with each other to form a polyurethane prepolymer having at least two isocyanate groups. . Representative suitable isocyanate functional monomers include the isocyanate functional monomers described above.

  Suitable isocyanate functional polyurethane prepolymers useful in the practice of the present disclosure may have various molecular weights within a wide range. In some embodiments, the isocyanate functional polyurethane prepolymer has a number average molecular weight (Mn) of 500-15,000, or 500-5000, as measured by gel permeation chromatography (GPC) using polystyrene standards. You may have.

  Representative polyols useful for the preparation of isocyanate functional polyurethane prepolymers include 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1, Linear or branched alkane polyols such as 3-butanediol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, di-trimethylolpropane, erythritol, pentaerythritol and di-pentaerythritol; -And tetraethylene glycol, and polyalkylene glycols such as di-, tri- and tetrapropylene glycol; cyclopentanediol, cyclohexanediol, cyclohexanetriol, cyclohexanedimethanol, hydroxypropyl Cyclic alkane polyols such as pyrcyclohexanol and cyclohexanediethanol; aromatic polyols such as dihydroxybenzene, benzenetriol, hydroxybenzyl alcohol and dihydroxytoluene; 4,4′-isopropylidenediphenol (bisphenol A), 4,4 ′ -Oxybisphenol, 4,4'-dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein, bis (4-hydroxyphenyl) methane (bisphenol F), 4,4 '-(1,2-ethenediyl) bisphenol And bisphenols such as 4,4′-sulfonylbisphenol; 4,4′-isopropylidenebis (2,6-dibromophenol), 4,4′-isopropylidenebis (2,6-dichloropheno) And halogenated bisphenols such as 4,4′-isopropylidenebis (2,3,5,6-tetrachlorophenol); one or more alkoxy such as ethoxy, propoxy, α-butoxy and β-butoxy groups Alkoxylated bisphenols such as alkoxylated 4,4'-isopropylidenediphenol having a group; and 4,4'-isopropylidene-biscyclohexanol, 4,4'-oxybiscyclohexanol, 4,4'-thio Biscyclohexanols that can be prepared by hydrogenating the corresponding bisphenols, such as biscyclohexanol and bis (4-hydroxycyclohexanol) methane.

  Further examples of suitable polyols useful for the preparation of isocyanate functional polyurethane prepolymers include higher order polyalkylene glycols such as polyethylene glycol having a number average molecular weight (Mn) of 200 to 2000 grams / mole. Hydroxyl-supported acrylic resins such as those formed by copolymerization of (meth) acrylates and hydroxy-functional (meth) acrylates, such as copolymers of methyl methacrylate and hydroxyethyl methacrylate; and diols such as butanediol And hydroxy-functional polyesters such as those formed by reaction of diacids such as adipic acid or diethyl adipate or diesters. In some embodiments, polyols useful in the practice of the present disclosure may have a number average molecular weight (Mn) of 200 to 2000 grams / mole.

  In some embodiments, an isocyanate functional polyurethane prepolymer may be prepared by reacting a diisocyanate such as toluene diisocyanate with a polyalkylene glycol such as poly (tetrahydrofuran).

  In some embodiments, the isocyanate functional polyurethane prepolymer may be prepared in the presence of a catalyst. In some embodiments, the amount of catalyst used may be less than 5 weight percent, or less than 3 weight percent, or less than 1 weight percent, based on the total weight of polyol and isocyanate functional monomer. In some embodiments, representative suitable catalysts include tin addition of organic acids such as tin oxalate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, dibutyltin dimaleate, dimethyltin diacetate, dimethyltin dilaurate, etc. , 1,4-diazabicyclo [2.2.2] octane, and mixtures thereof. In another embodiment, the catalyst may be zinc oxalate, bismuth, or ferric acetylacetonate. Further representative suitable catalysts include tertiary amines such as triethylamine, triisopropylamine and N, N-dimethylbenzylamine.

  In polyurethane embodiments useful for making polymer particles, the first resin having at least two isocyanate groups includes a terminal protected isocyanate compound having at least two terminal protected isocyanate groups. The term “terminally protected isocyanate compound” refers to a monomer or prepolymer having a terminally protected (ie, free) isocyanate group and a terminal and / or pendant terminally protected isocyanate group that may be converted to a separate or free terminal protecting group. . Any of the aforementioned examples of suitable isocyanate compounds can be end-protected. Representative nonfugitive terminal protecting groups for isocyanate include 1H-imidazole, 1H-pyrazole, 3,5-dimethyl-1H-pyrazole, 1H-1,2,3-triazole, 1H-1, 1H-azoles such as 2,3-benzotriazole, 1H-1,2,4-triazole, 1H-5-methyl-1,2,4-triazole and 1H-3-amino-1,2,4-triazole Lactams such as e-caprolactam and 2-pyrrolidinone; morpholines such as 3-aminopropylmorpholine; and N-hydroxyphthalimide. Typical fugitive terminal protecting groups for terminally protected isocyanate compounds include alcohols such as propanol, isopropanol, butanol, isobutanol, tert-butanol and hexanol; ethylene glycol monoalkyl ethers (eg, ethylene glycol) Monobutyl ethers and ethylene glycol monohexyl ethers) and alkylene glycol monoalkyl ethers such as propylene glycol monoalkyl ethers (for example, propylene glycol monomethyl ether); and ketoximes such as methyl ethyl ketoxime.

  Without being bound by any theory, by including in the first resin an end-protected isocyanate material having at least two isocyanate groups, (a) between at least a portion of the particulate polyurethane particles; and / or (B) It is believed that a covalent bond can be formed between at least a portion of the particulate polyurethane and at least a portion of the crosslinked network. In some embodiments, the end-protected isocyanate compound is such that the end-protected isocyanate group of the first resin is at least 5 mole percent, or at least 10 mole percent, based on the total molar equivalents of free isocyanate and end-protected isocyanate groups. Or it may be present to be present in an amount of less than 40 mole percent, or less than 50 mole percent.

  The second resin having at least two groups reactive with isocyanate groups can be selected from a wide variety of materials. In some embodiments, the second resin has a functional group selected from hydroxyl, mercapto, primary amine, secondary amine, and combinations thereof. Exemplary suitable second resins include the aforementioned polyols.

  In some embodiments, the second resin that may have at least two groups reactive with isocyanate groups includes polyamines. Typical polyamines include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), piperazine, diethylenediamine (DEDA), and 2 -Ethyleneamines such as amino-1-ethylpiperazine. Further representative suitable polyamines include 3,5-dimethyl-2,4-toluenediamine, 3,5-dimethyl-2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine. , 3,5-diethyl-2,6-toluenediamine, 3,5-diisopropyl-2,4-toluenediamine, 3,5-diisopropyl-2,6-toluenediamine, and mixtures thereof. One or more isomers may be mentioned. In some embodiments, the polyamine may be selected from methylene dianiline, trimethylene glycol di (para-aminobenzoate), and amine-terminated oligomers and prepolymers.

  In some embodiments, suitable polyamines are based on 4,4′-methylene-bis (dialkylaniline) (eg, 4,4′-methylene-bis (2,6-dimethylaniline), 4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-ethyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline) 4,4′-methylene-bis (2-isopropyl-6-methylaniline), 4,4′-methylene-bis (2,6-diethyl-3-chloroaniline), and mixtures thereof. .

  In some embodiments, the preparation of the particulate polyurethane from a first resin comprising at least two isocyanate groups and a second resin comprising at least two groups reactive with isocyanate is carried out in the presence of a catalyst. It may be done. Suitable catalysts include those listed above in the preparation of the isocyanate functional polyurethane prepolymer.

  In some embodiments, the molar equivalent ratio of isocyanate groups and optional end-protected isocyanate groups to isocyanate-reactive groups useful for the preparation of particulate polyurethanes is 0.5: 1.0 to 1.5: 1. 0, for example 0.7: 1.0 to 1.3: 1.0 or 0.8: 1.0 to 1.2: 1.0. In some embodiments, the crosslinked polyurethane may be prepared by using less than the stoichiometrically required amount of the second resin so that the urethane or urea linkages react with the remaining isocyanate. In another embodiment, partial replacement of a bifunctional compound with a trifunctional compound will result in a more thermally stable chemical crosslink.

  Some useful microparticulate polyurethanes are commercially available, see, for example, Dainichiseika Color & Chemicals Mfg. Co. , Ltd., Ltd. It is commercially available from Advanced Polymers Group (Tokyo, Japan) under the trade names “DAIMIC-BEAZ” under the grades “UCN-5350D”, “UCN-5150D”, and “UCN-5070D”, and also from Negami Chemical Ind. , Ltd., Ltd. Polyurethane particles available under the trade name “ART PEARL” from (Nomi-city, Japan); and, for example, aliphatic polyether-based thermoplastic polyurethanes available under the trade name “TEXIN” from Bayer Corporation.

  In some embodiments, suitable polymer particles useful in the practice of the present disclosure include particulate polyepoxides. The particulate polyepoxide may be prepared, for example, from the reaction product of a first resin having at least two epoxide groups and a second resin having at least two groups reactive with the epoxide groups of the epoxide.

  In some embodiments, a first resin containing at least two epoxide groups and a second resin are mixed together and polymerized or cured to form a bulk polyepoxide, which is then ground (eg, cold milled). ) And may be classified according to circumstances. In some embodiments, the particulate polyepoxide mixes the epoxide functional material and the hydrogen functional material together and slowly pours the mixture into heated deionized water under agitation to remove the particulate material formed. It may be formed by isolation (eg, by filtration), drying the isolated particulate material, and optionally classifying the dried particulate polyepoxide.

  In some embodiments, suitable epoxide functional materials useful in the practice of the present disclosure include epoxide functional monomers, epoxide functional prepolymers, and combinations thereof. Representative suitable epoxide functional monomers include aliphatic polyepoxides such as 1,2,3,4-diepoxybutane, 1,2,7,8-diepoxyoctane; 1,2,4,5 -Diepoxycyclohexane, 1,2,5,6-diepoxycyclooctane, 7-oxa-bicyclo [4.1.0] heptane-3-carboxylic acid 7-oxa-bicyclo [4.1.0] hepta Cycloaliphatic polyepoxides such as 3-ylmethyl ester, 1,2-epoxy-4-oxiranyl-cyclohexane and 2,3- (epoxypropyl) cyclohexane; Fragrance such as bis (4-hydroxyphenyl) methane diglycidyl ether Mention may be made of the group polyepoxides; hydrogenated bisphenol A diepoxides and mixtures thereof. Epoxide functional monomers that may be useful in the present disclosure are typically prepared by reaction of a polyol with an epihalohydrin, such as epichlorohydrin. Polyols that can be used in the preparation of epoxide functional monomers include those previously cited herein in connection with the preparation of isocyanate functional prepolymers. A useful class of epoxide functional monomers includes those prepared by reaction of bisphenol with epichlorohydrin (eg, reacting 4,4′-isopropylidenediphenol with epichlorohydrin. 4,4′-isopropylidenediphenol diglycidyl ether).

  In some embodiments, epoxide functional prepolymers useful for the preparation of certain epoxides may be prepared by reacting a polymeric polyol with epichlorohydrin. Representative suitable polymeric polyols include polyalkylene glycols such as polyethylene glycol and polytetrahydrofuran; polyester polyols; polyurethane polyols; poly ((meth) acrylate) polyols; and mixtures thereof. it can.

  In some embodiments of the present disclosure, the epoxide functional prepolymer can be prepared from a (meth) acrylate monomer and a radical polymerizable epoxide functional monomer (eg, glycidyl (meth) acrylate). Poly ((meth) acrylate) polymers may be included. Suitable epoxide functional prepolymers can have a wide range of molecular weights. In some embodiments, the molecular weight of the epoxide functional prepolymer is determined, for example, by 500-15,000 grams / mole, or 500-5000 grams / mole, as measured by gel permeation chromatography (GPC) using polystyrene standards. Mole may be sufficient.

  The second resin having at least two groups reactive with epoxides may comprise at least one of hydroxyl, mercapto, carboxylic acid, primary amine, or secondary amine. In some embodiments, the second resin may include polyols previously cited herein. In another embodiment, the second resin may include polyamines previously cited herein. In some embodiments, suitable polyamines may include polyamide prepolymers having at least two amine groups selected from primary amines, secondary amines, and combinations thereof. Suitable representative polyamide prepolymers include, for example, those available from Cognis Corporation, Coating & Inks Division (Monheim, Germany) under the trade name “VERSAMID”.

  In some embodiments, the preparation of the particulate epoxide from a first resin comprising at least two epoxide groups and a second resin comprising at least two groups reactive with the epoxide is carried out in the presence of a catalyst. It may be done. Representative suitable catalysts include tertiary amines such as triethylamine, triisopropylamine, tri-tert-butylamine, tetrafluoroboric acid and N, N-dimethylbenzylamine. In some embodiments, the catalyst may be incorporated into the second resin before the second resin is combined with the epoxide functional material. In some embodiments, the amount of catalyst used is less than 5 weight percent, or less than 3 weight percent, or less than 1 weight percent, based on the combined weight of the first and second resins combined. Also good.

  The molar equivalent ratio of epoxide groups to epoxide reactive groups of the reactants used in the preparation of the microparticulate cross-linked polyepoxide is typically 0.5: 1.0 to 2.0: 1.0, for example 0.8. 7: 1.0-1.3: 1.0 or 0.8: 1.0-1.2: 1.0.

  In some embodiments, the first resin having at least two isocyanate groups or at least two epoxide groups, and / or the second resin may optionally include known conventional additives. Examples of such additives include softening agents such as heat stabilizers, antioxidants, mold release agents, static dyes, pigments, alkoxylated phenol benzoates and poly (alkylene glycol) dibenzoates. Examples include additives and surfactants such as ethylene oxide / propylene oxide block copolymer surfactants. In some embodiments, such additives are in a total amount of up to 10 weight percent, or up to 5 weight percent, or up to 3 weight percent, based on the combined weight of the first and second resins combined. May be present.

  Other polymer particles useful in the practice of the present disclosure include, for example, the trade name “RODADON” from ROHM America, Incorporated (Lawrenceville, Georgia) and also from Negami Chemical Industrial Co., Ltd. , Ltd., Ltd. Thermoplastic poly (meth) acrylates commercially available under the trade name "ART PEARL". Still other polymer particles useful in the practice of the present disclosure include, for example, cellulose particles commercially available from Dow Chemical Company (Midland, Michigan) under the trade name “METHOCEL”.

  The amount of polymer particles present in the polishing pad according to the present disclosure may vary. Interestingly, in some embodiments, the amount of polymer particles mixed using a given technique has been found to unexpectedly affect the porosity of the resulting abrasive layer. For example, when using a mixer that combines swirling and rotation, it has been found that a particle level of up to 20 weight percent provides fewer pores than a particle level of up to 15 weight percent. However, other mixing techniques can provide different results. In some embodiments, the polymer particles are present in an amount of at least 1 weight percent, or at least 2.5 weight percent, or at least 5 weight percent, based on the total weight of the particulate polymer and the crosslinked network. In some embodiments, the polymer particles may be present in an amount up to 25 weight percent, or up to 20 weight percent, or less than 20 weight percent, based on the total weight of the polymer particles and the crosslinked network.

  In some embodiments, including embodiments where the polymer particles are fibers, the polymer particles are up to 10 weight percent, or up to 5 weight percent, or less than 5 weight percent, based on the total weight of the polymer particles and the crosslinked network May be present in an amount of. Advantageously, the polymer particles in fiber form can provide useful levels of porosity, even at levels up to 2 weight percent, based on the total weight of the polymer particles and the crosslinked network. In some of these embodiments, the polymer particles are water soluble fibers (eg, methylcellulose fibers). As shown in Tables 1 and 2 of the Examples, when the methylcellulose fiber is used, a higher level of porosity can be obtained as compared with the case where equal weight spherical polyurethane particles are used. By visual comparison between FIG. 8 which is a micrograph of a cross-sectional view of the cured composition of Example 12, and FIGS. 7A and 7B which are micrographs of the cross-sectional view and top view of the cured composition of Example 15, respectively, 2 It is shown that a weight percent fiber (FIG. 8) can achieve a porosity level approximately the same as 10 weight percent particles (FIGS. 7A and 7B).

  Incorporating lower levels of particles to obtain the same porosity can be useful, for example, to improve the uniformity of particle distribution across the cross-linked network and to maintain the hardness of the pad surface during polishing. .

  A polishing pad according to the present disclosure comprises a polishing layer comprising polymer particles and a crosslinked network comprising a thermosetting component and a radiation curable component. A wide variety of suitable polymers can be useful in forming a crosslinked network. In some embodiments, the thermosetting component comprises at least one of polyurethane, polyepoxide, or urethane-modified polyepoxide.

  Typically, the crosslinked network of the present disclosure is formed in the presence of polymer particles. In some embodiments, the thermosetting resin composition and the radiation curable resin composition can react to form a crosslinked network while the curable resin composition is present between the polymer particles.

  In some embodiments, the abrasive layer disclosed herein comprises at least 75 weight percent, or at least 80 weight percent, or at least 85 weight percent crosslinked network, based on the total weight of the polymer particles and crosslinked network. May be included. In some embodiments, the crosslinked network is present in the polishing layer in an amount of up to 99 weight percent, or up to 95 weight percent, or up to 90 weight percent, based on the total weight of the polymer particles and the crosslinked network. May be.

  The crosslinked network may be prepared by methods of conventional polymerization techniques. In some embodiments, the crosslinked network may be formed by a condensation reaction, a free radical initiation reaction, or a combination thereof. In some embodiments, the thermosetting component may comprise a polyurethane formed by condensing a thermosetting resin composition containing a polyurethane prepolymer with a polyamine. In some embodiments, the radiation curable component may comprise a urethane-polyacrylate or urethane-polymethacrylate formed by polymerization of urethane-diacrylate or urethane-dimethacrylate in the presence of a photoinitiator. In some embodiments, the crosslinked network is an interpenetrating polymer network formed by stepwise or simultaneous thermosetting and radiation curable polymerization. In some embodiments, the radiation curable component (polyacrylate or polymethacrylate in some embodiments) is covalently bonded to the heat curable component, for example, via a urethane or urea linking group.

  Suitable thermosetting resin compositions useful in the practice of the present disclosure may contain monomers, prepolymers, and mixtures thereof. In some embodiments, the thermosetting resin composition may contain a catalyst, a crosslinking agent, a curing agent, a solvent, and other conventional additives known in the art.

  In some embodiments, the thermosetting resin composition comprises a first resin having at least two isocyanate groups, which may be terminal protected isocyanate groups, or at least two epoxide groups, and isocyanates and / or epoxides. And a second resin having at least two groups reactive with the class (eg, hydroxyl, amino, carboxy, or mercaptan groups).

  Representative suitable first and second resins that can be used in the preparation of the thermosetting component are the isocyanates (including prepolymers), end protections previously described herein for particulate polyurethanes, respectively. It may be selected from isocyanates, polyols and polyamines. The use of terminally protected isocyanates can delay the onset of gelation when, for example, the first resin and the second resin are combined, which is different from the first resin and the second resin. Longer times of mixing with the polymer particles may be possible.

  Some isocyanate prepolymers useful as the first resin are commercially available, see, eg, Air Products and Chemicals, Inc. There is an isocyanate prepolymer available from (Allentown, Pa.) Under the trade name “AIRTHANE PHP-75D”. Some diamines useful as the second resin are commercially available, see, eg, Air Products and Chemicals, Inc. There are oligomeric diamines available under the trade names "VERSALINK P250" and "VERSALINK P650".

  In some embodiments, radiation curable resins and thermosetting resins comprising: a first resin having at least two isocyanate groups; and a second resin having at least two groups reactive with isocyanate groups. The composition containing may further comprise a catalyst. Representative suitable catalysts include those previously cited herein in connection with the preparation of particulate polyurethanes (eg, tertiary amines such as triethylamine, and organometallic compounds such as dibutyltin dilaurate). it can. In some embodiments, the catalyst may be incorporated into the second resin before combining the first resin and the second resin. In some embodiments, the catalyst may be present in an amount less than 5 weight percent, or less than 3 weight percent, or less than 1 weight percent, based on the combined weight of the first and second resins combined. . The molar equivalent ratios of the isocyanate groups in the first resin and the second resin and any terminally protected isocyanate groups and isocyanate-reactive groups are 0.5: 1.0 to 2.0: 1, respectively. 0.0, or 0.7: 1.0 to 1.3: 1.0, or 0.8: 1.0 to 1.2: 1.0.

  In some embodiments, the thermosetting component has a first resin having at least two epoxide groups; and at least two groups reactive with the epoxide groups (eg, hydroxyl, amino, carboxy, or mercaptan groups) It may be prepared by reacting with a second resin. Exemplary suitable first and second resins having at least two epoxide groups include any of the epoxides, polyamines, and polyols used in the preparation of the particulate polyepoxide previously described herein. Can be mentioned.

  In some embodiments, the composition containing a radiation curable resin and a thermosetting resin, comprising a first resin and a second resin used in the preparation of the thermally cured component of the polyepoxide, An epoxide ring-opening catalyst may further be included. Representative catalysts suitable for ring opening of epoxides include any of those described above (eg, tertiary amines such as tri-tert-butylamine) and tetrafluoroboric acid. In some embodiments, the catalyst may be added to the second resin before mixing the first resin and the second resin. In some embodiments, the epoxide ring-opening catalyst may be present in an amount less than 5 weight percent, or less than 3 weight percent or less than 1 weight percent, based on the total weight of the first and second resins. The molar equivalent ratio between the epoxide group and the epoxide-reactive group in the first and second resins is 0.5: 1.0 to 2.0: 1.0, or 0.7: 1.0 to respectively. It may be 1.3: 1.0, or 0.8: 1.0 to 1.2: 1.0.

  In some embodiments, the thermosetting resin may include conventional additives. Typical suitable conventional additives include any additions such as mold release agents, dyes, and softeners previously described herein in connection with the preparation of particulate polyurethanes and particulate polyepoxides. Agents. In some embodiments, the additive may be present in an amount of less than 10 weight percent, or less than 5 weight percent, or less than 3 weight percent, based on the total weight of the crosslinked network. A conventional additive may be added to either the first or second resin, for example.

  The porous polishing pad according to the present disclosure includes a polishing layer having a radiation curable component. The radiation curable component includes at least one of polyacrylate, polymethacrylate, poly (vinyl ether), polyvinyl, or polyepoxide. In some embodiments, the radiation curable component comprises at least one of polyacrylate or polymethacrylate. The radiation curable component may be prepared from a radiation curable resin containing at least two acrylate, methacrylate, vinyl (eg, vinyl, allyl, or styryl groups), or epoxide groups. In some embodiments, the radiation curable resin comprises at least two acrylate or methacrylate groups.

  In some embodiments, the radiation curable resin may comprise a (meth) acrylate modified polyfunctional isocyanate material having at least two (meth) acrylate modified isocyanate groups, which may be, for example, terminal and / or pendant isocyanate. -Based polyurethane prepolymers (eg, polyurethane prepolymers described above in connection with the preparation of particulate polyurethanes) and (meth) acrylates having isocyanate-reactive functional groups (eg, hydroxyl, amino or mercapto groups) It may be a reaction product.

  Representative suitable hydroxy or amino functional (meth) acrylates include hydroxyalkyl acrylates and methacrylates (eg, 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methyl acrylate (HEMA), 2-hydroxy Propyl acrylate, 3-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 1,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate and methacrylate, 2-hydroxyethylacrylamide and methacrylamide 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxyp Pyr (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphates, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, Neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate; N-alkyl-N- Hydroxyethyl acrylamides and methacrylamides, hydroxyethyl-β carboxyethyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl methacrylate, polypropylene Lenglycol monomethacrylate, propylene glycol monomethacrylate, caprolactone acrylate, t-butylaminoethyl methacrylate, and mixtures thereof). Many of these are available from commercial sources, for example, useful hydroxyethyl acrylates and hydroxypropyl acrylates are available from Dow Chemical (Midland, Mich.) And Osaka Organic Chemical Industry Ltd. (Osaka, Japan). Useful hydroxybutyl acrylates are available from Osaka Organic Chemical Ltd. Commercially available. Useful hydroxy polyester acrylates are commercially available from Dow Chemical Company under the trade name “TONE MONOMER M-100” and are also available from Osaka Organic Chemical Industry Ltd. From "VISCOAT 2308". Useful hydroxy polyether acrylates are commercially available from Bayer Chemicals (Pittsburgh, Pa.) Under the trade name "ARCOL R-2733".

  (Meth) acrylate groups may be located on the pendant, terminal, or combinations thereof on the prepolymer. In some embodiments, the prepolymer is end-protected with (meth) acrylate groups. The radiation curable resin may be prepared, for example, by reacting a (meth) acrylate having an isocyanate-reactive functional group with a polyisocyanate prepolymer, typically in the presence of excess isocyanate. In some embodiments, the (meth) acrylate having isocyanate-reactive functional groups is about 10% to about 80%, about 20% to about 70%, or about 30% to about 60% on the isocyanate functional prepolymer. % Isocyanate groups are reacted with the isocyanate functional prepolymer in an amount that reacts with the (meth) acrylate having an isocyanate reactive functional group.

  Some (meth) acrylate-modified polyfunctional isocyanate materials having at least two (meth) acrylate-modified isocyanate groups are commercially available, for example, from Bayer Materials Science (Pittsburgh, PA) under the trade names “DESMOLUX D100”, “ There are isocyanate urethane acrylates available under "DESMOLUX VPLS 2396" and "DESMOLUX XP2510".

  Compositions containing radiation curable compositions and thermosetting compositions typically also contain a photoinitiator or a combination of photoinitiators. Useful photoinitiators include, for example, benzoin, benzoin acetals (eg, benzyldimethyl ketal), benzoin ethers (eg, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether), hydroxyalkyl phenyl ketones (eg, 1 -Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one), benzoylcyclohexanol, Dialkoxyacetophenone derivatives (eg, 2,2-diethoxyacetophenone), acylphosphine oxides (eg, bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxy Bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide and 2,4,4-trimethylbenzoyldiphenylphosphine oxide), methylthiophenylmorpholinoketones (for example, 2-methyl-1 -4 (methylthio) and phenyl-2-morpholino-1-propanone) and morpholinophenylaminoketones, such as “α-cleavage” photoinitiators; benzophenones, thioxanthones, benzyls, camphorquinones and And hydrogen abstracting photoinitiators including photoinitiators and coinitiators based on ketocoumarins; and combinations thereof. In some embodiments, the photoinitiator is an acylphosphine oxide (eg, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4). -Trimethylpentyl) phosphine oxide and 2,4,4-trimethylbenzoyldiphenylphosphine oxide).

  Representative useful commercially available photoinitiators are trade names “IRGACURE 369”, “IRGACURE 819”, “IRGACURE CGI403”, “IRGACURE 651”, “IRGACURE 1841”, “IRGACURE 29594”, “DAROCUR 1173”, “ DAROCUR 4265 "and" CGI 1700 ", all of which are available from Ciba Specialty Chemicals (Ardsley, NY). The photoinitiator is preferably present in an amount sufficient to provide the desired rate of photopolymerization. The amount will depend in part on the light source, the thickness of the layer exposed to the radiant energy, and the extinction coefficient of the photoinitiator at the wavelength. Typically, the photoinitiator component is in an amount of at least about 0.01 wt%, at least about 0.1 wt%, at least about 0.2 wt%, up to about 10 wt%, or up to about 5 wt%. Will exist.

  The radiation curable composition and the thermosetting composition can be intimately mixed in the composition to make the porous polishing pad disclosed herein. In some embodiments, the composition is radiation curable at least about 10 (in some embodiments, at least about 15, 20, 25, 30, or 40) weight percent, based on the total weight of the composition. Containing the composition and up to 85 (in some embodiments, up to about 80, 75, 70, 65, 60, 55, or 50) weight percent radiation curable composition. In some embodiments, the composition is at least about 15 (in some embodiments, 60 at least about 20, 25, 30, 35, 40, 45, 50, 55, based on the total weight of the composition). ) Weight percent of the thermosetting composition, and up to about 90 (in some embodiments, up to about 85, 80, or 75) weight percent of the thermosetting composition.

  In some embodiments, the thermosetting resin composition, the radiation curable resin composition, and the composition containing polymer particles further comprise a surfactant. Similarly, in some embodiments, a crosslinked network comprising a thermosetting component and a radiation curable component, polymer particles dispersed in the crosslinked network, and closed cell pores dispersed in the crosslinked network. The porous polishing layer containing further includes a surfactant dispersed in the crosslinked network. Examples of surfactants that may be useful in the practice of the present disclosure include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants (eg, zwitterionic surfactants) , And combinations thereof. Each of these types of surfactants can include fluorine-based, silicone-based, and hydrocarbon-based surfactants.

  Representative useful cationic surfactants include aliphatic ammonium salts. Representative useful anionic surfactants include carboxylates (eg, fatty acid salts and alkyl ether carboxylates), sulfonates (eg, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and α-olefins). Sulfonates), sulfates (eg, higher alcohol sulfates and alkyl ether sulfates), and phosphates (eg, alkyl phosphates). Typical useful nonionic surfactants include polyoxyethylene alkyl ethers, ether esters (eg, polyoxyethylene ethers of glycerin esters), esters (eg, polyethylene glycol fatty acid esters, glycerin). Esters, sorbitan esters), and silicone glycol copolymers such as those available under the trade name “DABCO” from Air Products (Allentown, Pennsylvania). The surfactant can be, for example, up to 10 weight percent (in some embodiments, up to 4, 3, or 2 weights) based on the total weight of the composition or porous polishing layer in the composition or polishing layer. Percent). In some embodiments, the surfactant is present in an amount of at least 1 percent, based on the total weight of the composition or porous polishing layer. The present disclosure provides a method of manufacturing the polishing pad described herein. The method includes the step of forming pores in the thermosetting resin composition, the radiation curable resin composition, and the composition containing polymer particles. In some embodiments, the formation of pores in the composition is performed by mixing the composition. Mixing may be performed by a variety of techniques, for example, using a mechanical mixer or hand mixing. In some embodiments, the mixing process (and mechanical mixer) may include both rotation and swirl. The particle size and load of the polymer particles can affect the porosity of the resulting polishing layer, as described above.

  In some embodiments, the thermosetting resin composition, the radiation curable resin composition, and the composition containing the polymer particles may be mixed together and disposed on the support layer. An open mold on the top of the support layer (eg, a mold without a top or lid) can be useful in forming the desired shape of the polishing layer. The mixture can be distributed into the mold by mechanical means to fill the mold uniformly. Suitable mechanical means may include the use of low pressure or compression rollers.

  The method of manufacturing a polishing pad disclosed herein includes exposing a composition to radiation to at least partially cure the radiation curable composition and heating the composition to at least partially cure the thermosetting resin. The process of forming a grinding | polishing layer is also included. The radiation is typically ultraviolet radiation (ie, radiation in the range of about 200 nm to about 400 nm). The amount of radiation required to at least partially cure the composition includes, for example, the angle of exposure to radiation, the thickness of the composition, the amount of polymerizable groups in the composition, and the type and amount of photoinitiator. It will depend on a variety of factors. Typically, a UV light source having a wavelength of about 200 nm to about 400 nm is directed to the composition being transported on a conveyor system that provides a speed through the UV source that is appropriate for the radiation absorption profile of the composition. The Useful UV light sources include, for example, ultra high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low intensity fluorescent lamps, metal halide lamps, microwave output lamps, xenon lamps such as excimer lasers and argon ion lasers. Including laser light sources, as well as combinations thereof. The composition is then, for example, up to about 180 ° C., or up to about 150 ° C., or up to about 135 ° C., or up to about 120 ° C. (eg, 80 ° C. to 120 ° C., or 80 ° C. to 110 ° C., or 90 ° C. You may arrange | position for a fixed time (for example, 30 minutes-24 hours) in the high temperature furnace of the range of 100 degreeC. Exposure to radiation and heating may be performed in any order or simultaneously. In some embodiments, exposure to radiation occurs before heating.

  The polishing pads of the present disclosure may have one or more working surfaces, and “working surface” as used herein refers to the surface of the polishing pad that can be contacted with the surface of the article to be polished. . In some embodiments, the article to be polished may be a silicon wafer. In some embodiments, the working surface of the polishing pad may have a surface structure such as channels, grooves, perforations and combinations thereof. These surface structures can improve one or more of the following properties. (1) movement of the polishing slurry between the working surface of the pad and the surface of the article to be polished; (2) removal and transport of material worn away from the surface of the article to be polished; or (3) of the polishing pad Polishing efficiency or planarization efficiency.

  The surface structure can be incorporated into the work surface of the polishing pad by a variety of methods. In some embodiments, the working surface of the pad may be mechanically altered, for example, by scraping or cutting. In another embodiment, the surface structure is a work of the pad during the molding process, for example by providing a raised structure on at least one inner surface of the mold that can be imprinted in the work surface of the pad during the formation of the pad. It may be incorporated into the surface. The surface structure may be distributed in an irregular or uniform pattern throughout the work surface of the polishing pad. Typical surface structure patterns include spirals, circles, squares, crossed parallel lines and waffle-like patterns.

  In some embodiments, a polishing pad according to or made in accordance with the present disclosure comprises a separate polishing element that protrudes from a support layer. Referring now to FIG. 3, an embodiment of a polishing pad 2 that includes a plurality of polishing elements 4 is shown, each of the polishing elements 4 being attached to an optional support layer 8. The polishing pad 2 further includes a flexible layer 10. Typically, the polishing layer comprising separate polishing elements is a continuous layer, but is not shown in FIG. Between separate abrasive elements, the film may have a thickness of, for example, a maximum of 0.01, 0.02, or 0.03 mm. In another embodiment, an abrasive layer comprising separate abrasive elements may be discontinuous, for example in a film between separate abrasive elements. In the illustrated embodiment, the polishing element 4 is attached to the support layer between the polishing elements 4 by a thin film layer (not shown), so that the polishing element is associated with one or more other polishing elements 4. Although the lateral movement of the four is limited, the polishing elements 4 typically remain independently movable in an axis perpendicular to the polishing surface 14 of each polishing element 4. As shown, each of the polishing elements 4 generally has a plurality of holes 15 distributed substantially throughout the polishing element 4.

  In the particular embodiment illustrated in FIG. 3, the polishing element 4 is shown attached to the first major side of the support layer 10, for example by direct bonding to the support layer 8. The abrasive element 4 may be molded directly on the support layer 8 and cured. In another embodiment, the abrasive element 4 may be attached to the support layer 8 using an adhesive or directly to the flexible layer 10. In these embodiments, the porous polishing layer is typically a discontinuous layer. In the particular embodiment illustrated in FIG. 3, any pad that can be used to secure the polishing pad 2 to a polishing platen (not shown in FIG. 3) of a CMP polishing apparatus (not shown in FIG. 3). A pressure sensitive adhesive layer 12 is shown adjacent to the flexible layer 10 opposite the support layer 8.

  Referring to FIG. 4, another exemplary embodiment of a polishing pad 2 'is illustrated, the polishing pad 2' having a first main side and a second main side opposite the first main side. A plurality of polishing elements 24 having a land region 25 for each polishing element 24 to adhere to the first major side of the flexible layer 30; An optional guide plate 31 having a first main surface and a second main surface opposite the first main surface, wherein the plurality of polishing elements 24 are on the first main side surface of the flexible layer 30. The guide plate 31 is positioned such that the first major surface of the guide plate 31 is distal to the flexible layer 30.

  As shown in FIG. 4, each polishing element 24 extends from the first major surface of the guide plate 31 along a first direction that is substantially perpendicular to the first major side surface. Yes. In the particular embodiment illustrated in FIG. 4, each of the porous polishing elements 24 is also shown as having a plurality of holes 15 distributed over substantially the entire polishing element 24. In addition, in the particular embodiment illustrated in FIG. 4, three polishing elements 24 are illustrated, all of which are distributed over the porous polishing surface 23 and substantially the entire polishing element 24. It is illustrated as a porous abrasive element that includes both pores 15. However, any number of polishing elements 24 may be used, and the number of porous polishing elements may vary from at least one polishing element to many equal to the number of all polishing elements, or any in between. It should be understood that the number may be chosen.

  An optional polishing composition distribution layer 28 is additionally illustrated in FIG. During the polishing process, the optional polishing composition distribution layer 28 assists in the distribution of the working fluid and / or polishing slurry to the individual polishing elements 24. Also, as shown in FIG. 4, a plurality of openings 26 extending through at least the guide plate 31 and the optional polishing composition distribution layer 28 can be provided. In some embodiments, the guide plate 31 may also serve as a polishing composition distribution layer.

  As shown in FIG. 4, in some embodiments, each polishing element 24 has a land area 25, and each polishing element 24 passes a corresponding land area 25 to the second main portion of the guide plate 31. It is attached to the first major side of the flexible layer 30 by engaging the surface. At least a portion of each polishing element 24 extends into a corresponding opening 26, and each polishing element 24 also extends outwardly from the first major surface of the guide plate 31 through the corresponding opening 26. Thus, the plurality of openings 26 in the guide plate 31 serve to guide the lateral arrangement of the polishing elements 24 on the support layer 30 while engaging with the respective land areas 25 to each corresponding polishing element. It also serves to attach 24 to the support layer 30.

  As a result, during the polishing process, the polishing element 24 is freely and independently displaced in a direction substantially perpendicular to the first major side of the flexible layer 30, while the support plate 30 is supported by the guide plate 31. It will be kept attached. In some embodiments, this may allow the use of non-flexible abrasive elements, eg, porous abrasive elements having pores distributed only at or near the abrasive surface.

  In the particular embodiment illustrated in FIG. 4, the polishing element 24 uses a first adhesive layer 34 that uses an optional adhesive layer 34 positioned at the interface between the flexible layer 30 and the guide plate 31. It is additionally attached to the main side surface. However, other bonding methods may be used including, for example, directly bonding the polishing element 24 to the flexible layer 30 using heat and pressure.

  In an exemplary related embodiment not shown in FIG. 4, the plurality of openings may be arranged as an array of openings in which at least a portion of the openings 26 comprises an undercut region of the main cylinder and the guide plate 31. The cut area forms a shoulder that engages the corresponding abrasive element land area 25 to hold the abrasive element 24 without the need for adhesive between the abrasive element 24 and the flexible layer 30.

  Furthermore, as illustrated in FIG. 4, an optional second adhesive layer 36 can be used to adhere an optional polishing composition distribution layer 28 to the first major surface of the guide plate 31. In addition, in the particular embodiment illustrated in FIG. 4, the polishing pad 2 ′ can be used to secure a polishing platen (not shown in FIG. 4) of a CMP polishing apparatus (not shown in FIG. 4). An optional pressure sensitive adhesive layer 32 is shown adjacent to the support layer 30 opposite the guide plate 31.

  Guide plates and / or distribution layers may also be used in connection with the embodiment shown in FIG. 3 in which the porous polishing element 4 does not have land areas. In the presence of the guide plate, the support layer 8 may be eliminated and the porous abrasive element may be attached to the flexible layer 10 using, for example, an adhesive.

  The cross-sectional shape of the polishing elements 4 and 24 passing through the polishing elements 4 and 24 in a direction generally parallel to the polishing surfaces 14 and 23 can vary widely depending on the intended application. Although FIGS. 3 and 4 show generally cylindrical polishing elements 4 and 24 having a generally circular cross-section, other cross-sectional shapes are possible and may be desirable in some embodiments. For example, circular, elliptical, triangular, square, rectangular, and hexagonal cross-sectional shapes may be useful.

  For cylindrical polishing elements 4 and 24 having a circular cross section, the diameter of the cross section of the polishing elements 4 and 24 may be from about 50 μm to about 20 mm in a direction generally parallel to the polishing surfaces 14 and 23, in some implementations. In form, the cross-sectional diameter is from about 1 mm to about 15 mm, and in another embodiment, the cross-sectional diameter is from about 5 mm to about 15 mm (or even from about 5 mm to about 10 mm). For non-cylindrical polishing elements having a non-circular cross-section, characteristic dimensions at a particular height, width, and length can be used to characterize the size of the polishing element. In some exemplary embodiments, a characteristic dimension of about 0.1 mm to about 30 mm may be selected.

In another exemplary embodiment, the cross-sectional area of each polishing element 4 and 24, in a direction generally parallel to the polishing surface 14 and 23, about 1 mm ² ~ about 1,000mm ^2, in another embodiment about 10 mm ² ~ about 500 mm ^2, in another embodiment further it may be about 20 mm ² ~ about 250 mm ^2.

  Abrasive elements (4 in FIG. 3, 24 in FIG. 4) are distributed in very diverse patterns on the main side of the flexible layer (10 in FIG. 3, 30 in FIG. 4) depending on the intended application And their patterns may be regular or irregular. The abrasive element may be on substantially the entire surface of the flexible layer, or there may be a region of the support layer that does not include the abrasive element. In some embodiments, the polishing element comprises a total of the major surfaces of the flexible layer as an average surface coverage of the flexible layer determined by the number of polishing elements and the cross-sectional area of each polishing element and the cross-sectional area of the polishing pad. Having from about 30 to about 95 percent of the area.

The cross-sectional area of the polishing pad in a direction generally parallel to the major surface of the polishing pad may be from about 100 cm ² to about 300,000 cm ² in some exemplary embodiments, and in another embodiment about it may be 1,000 cm ² ~ about 100,000 ^2, in another embodiment further it may be about 2,000 cm ² ~ about 50,000 cm ^2.

  Prior to the first use of the polishing pad (2 in FIG. 3, 2 ′ in FIG. 4) in the polishing operation, in some exemplary embodiments, each polishing element (4 in FIG. 3, 24 in FIG. 4). ) Extends along a first direction substantially perpendicular to the first major side of the flexible layer (10 in FIG. 3 and 30 in FIG. 4). In another exemplary embodiment, each polishing element extends along a first direction at least about 0.25 mm above the plane containing the guide plate (31 in FIG. 4). In a further exemplary embodiment, each polishing element extends along the first direction at least about 0.25 mm above the plane containing the support layer (10 in FIG. 3). In an additional exemplary embodiment, the height of the polishing surface (14 in FIG. 3, 23 in FIG. 4) on the base or bottom of the polishing element (2 in FIG. 3, 2 ′ in FIG. 4) is used. 0.25 mm, 0.5 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 5.0 mm, 10 mm or more depending on the polishing composition and the material selected for the polishing element It may be.

  Referring again to FIG. 4, the depth and spacing of the polishing composition distribution layer (28 and the entire aperture 26 across the guide plate 31 may vary as needed for a particular CMP process. , Each maintaining a planar orientation with respect to each other and with respect to the polishing composition distribution layer 28 and the guide plate 31 and projecting above the surfaces of the polishing composition distribution layer 28 and the guide plate 31.

  In some exemplary embodiments, the polishing element (4 in FIG. 3, 4 in FIG. 4) above the guide plate 31 and optional polishing composition distribution layer (28 in FIG. 4) or support layer (8 in FIG. 3). The volume created by the extension of 24) may provide room for the distribution of the polishing composition on the surface of the polishing composition distribution layer (28 in FIG. 4) or the support layer (8 in FIG. 3). it can. The polishing element (4 in FIG. 3, 24 in FIG. 4) is made up of the material properties of the polishing element and the polishing composition (working fluid) on the surface of the polishing composition distribution layer (28 in FIG. 4) or support layer (8 in FIG. 3). And / or protrude above the polishing composition distribution layer (28 in FIG. 4) or the support layer (8 in FIG. 3) depending on an amount that depends at least in part on the flow desired in the polishing slurry.

  Useful guide plates for some embodiments can be made of a variety of materials such as polymers, copolymers, polymer blends, polymer composites, or combinations thereof. Non-conductive, liquid-impermeable polymeric materials are generally preferred and polycarbonate has been found to be particularly useful.

  Any polishing composition distribution layer useful in some embodiments can also be made of a wide variety of polymeric materials. The polishing composition distribution layer, in some embodiments, includes at least one hydrophilic polymer. Preferred hydrophilic polymers include polyurethanes, polyacrylates, polyvinyl alcohols, polyoxymethylenes, and combinations thereof. The polymeric material is preferably porous and more preferably comprises a foam to provide a positive pressure towards the substrate when the polishing composition distribution layer is compressed during the polishing operation. In some embodiments, a porous or foam material having closed cells or open cells may be preferred. In some specific embodiments, the polishing composition distribution layer has a porosity of about 10 to about 90 percent. In an alternative embodiment, the polishing composition layer is preferably a hydrogel material, such as a hydrophilic urethane, capable of absorbing water, preferably from about 5 to about 60 to provide a smooth surface during polishing operations. May be provided in weight percent range.

  In some exemplary embodiments, the polishing composition distribution layer can distribute the polishing composition substantially uniformly across the surface of the substrate being polished to provide more uniform polishing. The polishing composition distribution layer may optionally include flow resistance elements such as baffles, grooves (not shown), holes, etc. to adjust the flow rate of the polishing composition during polishing. In a further exemplary embodiment, the polishing composition distribution layer can include a variety of layers of different materials to achieve a desired polishing composition flow rate at different depths from the polishing surface.

  In some exemplary embodiments, one or more polishing elements may include an open core region or cavity defined within the polishing element, but such a configuration is not necessary. In some embodiments, such as those described in International Patent Application Publication No. WO 2006/055720 (Torgerson et al.), The core of the polishing element includes a sensor that detects pressure, conductivity, capacitance, eddy currents, and the like. But you can.

  In some embodiments of the polishing pad and / or method of manufacturing the polishing pad disclosed herein, the support layer comprises a flexible and soft material. The support layer is typically a film that provides a surface onto which a composition containing a thermosetting resin composition and a radiation curable resin composition can be cured. In some exemplary embodiments in which the porous abrasive layer includes an abrasive element, the abrasive element, at least a portion of which includes the porous abrasive element, is combined with the support layer as a single sheet of abrasive element attached to the support layer. Can be formed.

  The support layer also serves to protect the flexible layer from water or other fluids in the polishing composition during use of the polishing pad. The support layer is typically fluid impermeable (however, a permeable material in combination with any barrier may be used to prevent or prevent fluid penetration through the support layer). . In some exemplary embodiments, the support layer comprises a polymeric material selected from silicone, natural rubber, styrene-butadiene rubber, neoprene, polyurethane, polyolefin, and combinations thereof. The support layer may further comprise a wide variety of additional materials such as fillers, particulates, fibers, reinforcing agents and the like. In some embodiments, the support layer is transparent.

  The support layer may be made, for example, by extruding a material (eg, silicone, natural rubber, styrene-butadiene rubber, neoprene, polyurethane, polyolefin, and combinations thereof) into the film. In some embodiments, the material is, for example, Lubrizol Advanced Materials, Inc. (Cleveland, OH), available under the trade name "ESTANE 58887-NAT02" or from Dow Chemical (Midland, MI) under the trade name "PELLETHANE", for example "PELLETHANE 2102-65D". Commercially available films useful as the support layer include, for example, trade names “ST-1882”, “ST-1035”, “SS-3331”, “SS-1495L”, and “ST- 1” from Stevens Urethane (Easthampton, Massachusetts). 1880 ".

  In some embodiments of the polishing pad and / or method of manufacturing the polishing pad disclosed herein, the soft layer comprises a flexible and soft material, such as soft rubber or polymer. The compliant layer is generally compressible to provide a positive pressure towards the polishing surface, and helps provide uniformity of contact between the polishing pad and the surface of the substrate being polished, for example. Can do. In some exemplary embodiments, the flexible layer is formed from a compressible polymeric material (eg, a foamed polymeric material made from natural rubber, synthetic rubber, or a thermoplastic elastomer). Closed cell porous materials may be useful. In some embodiments, the compliant layer comprises polyurethane, and may be, for example, foamed polyurethane or polyurethane impregnated felt. The thickness of the flexible layer may be, for example, in the range of 0.2 to 3 mm. In some exemplary embodiments in which the abrasive layer includes an abrasive element, the abrasive element, at least a portion of which includes a porous abrasive element, is a single abrasive element attached to a flexible layer that may be a porous flexible layer. It may be formed with a flexible layer as one sheet.

  In some exemplary embodiments, the flexible layer comprises a polymeric material selected from silicone, natural rubber, styrene-butadiene rubber, neoprene, polyurethane, polyolefin, and combinations thereof. The support layer may further comprise a wide variety of additional materials such as fillers, particulates, fibers, reinforcing agents and the like. In some embodiments, the compliant layer is fluid impermeable (but a permeable material may be used in combination with the support layer described above).

  Suitable commercially available flexible layers include, for example, product descriptions 4701-60-20062-04, 4701-50-20062-04, 4701-40-20062-04, eg, Rogers Corp. (Rogers, CT) and microcellular polyurethanes available under the trade name “PORON”. Other suitable flexible layers include, for example, a polyurethane-impregnated polyester felt available from Rodel, Incorporated (Newark, DE) under the trade name “SUBA IV”, and Rubber Cypress Sponge Rubber Products, Inc. An adhesive rubber sheet available from (Santa Ana, CA) under the trade name “BONDTEX”.

  In some embodiments of the polishing pad and / or method of manufacturing the polishing pad disclosed herein, the polishing pad is as described in International Patent Application Publication No. WO 2009/140622 (Bajaj et al.) A window extending through the pad in a direction perpendicular to the polishing surface may be included, or a transparent layer and / or a transparent polishing element may be used to allow optical endpoint indication of the polishing process.

  The term “transparent layer” as used above is intended to include a layer containing a transparent region, which can be made of the same or different material as the rest of the layer. In some exemplary embodiments, at least one of the polishing element, the support layer, the flexible layer, or one region of the polishing layer or support layer may be transparent, or heat and It may be made transparent by applying pressure. In some embodiments, a transparent material is poured (eg, using a mold) into place within an aperture that is suitably positioned in the layer to produce a transparent region (eg, a polishing layer, a support layer, or a flexible layer). In the layer). In some embodiments, the polishing layer is cured in the presence of a pre-formed window to form a transparent region in the polishing layer. In some embodiments, the entire support layer and / or flexible layer may be formed of a material that can be transparent or transparent to energy in the wavelength range of interest used in the endpoint detection device. Suitable transparent materials for the transparent element, layer or region include, for example, transparent polyurethane.

  Furthermore, the term “transparent” as used above is intended to include elements, layers, and / or regions that are substantially transparent to energy in the wavelength range of interest used for the endpoint detector. In some exemplary embodiments, the endpoint detector uses one or more electromagnetic energy sources to emit radiation in the form of ultraviolet light, visible light, infrared light, microwaves, radio waves, combinations thereof, and the like. In some embodiments, the term “transparent” means at least about 25% (eg, at least about 35%, at least about 50) of energy at a wavelength of interest that affects the transparent element, layer, or region that is transmitted. %, At least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%).

  In some exemplary embodiments, the support layer is transparent. In some embodiments, the polishing layer is transparent. In some exemplary embodiments, including the embodiment shown in FIG. 3 above, at least one polishing element is transparent. In some embodiments, the support layer is transparent, at least a portion of the polishing layer (eg, the polishing element) is transparent, and holes aligned with the transparent portion of the polishing layer are present in the flexible layer.

  In additional exemplary embodiments, including the embodiment shown in FIG. 4 above, at least one abrasive element is transparent and the adhesive layer and the flexible layer are also transparent. In further exemplary embodiments, the compliant layer, guide plate, polishing composition distribution layer, at least one polishing element, or a combination thereof is transparent.

  The present disclosure further relates to a method of using the polishing pad described above in a polishing process, the method comprising contacting a surface of a substrate with a porous polishing layer of a polishing pad according to the present disclosure; Moving relative to the surface of the substrate to reduce the surface of the substrate. In some embodiments, the porous polishing layer of the polishing pad includes a plurality of polishing elements, and at least some of the polishing elements are porous. In some exemplary embodiments, a working fluid may be provided at the interface between the polishing pad surface and the substrate surface. Suitable processing fluids include, for example, US Pat. Nos. 6,238,592 (Hardy et al.) And 6,491,843 (Srinivasan et al.) And International Patent Application Publication No. WO 2002/33736 (Her et al.). The thing described in is mentioned.

  In some embodiments, the polishing layer in a polishing pad of the present disclosure and / or prepared by the disclosed method has an average pore size of at least 5 micrometers, at least 10 micrometers, or at least 15 micrometers. May be. In some embodiments, the polishing pad may have an average pore size of up to 100, 75, 50, 45, or 40 micrometers. For example, the average pore size may be in the range of 5-100, 5-75, 5-50, 5-40, or 5-30 micrometers. In some embodiments (eg, embodiments in which at least one of the surfactants is included or the polymer particles are fibers), the polishing pad has an average pore size of up to 30, 25, or 20 micrometers. Also good. The hole diameter generally refers to the diameter of the hole. However, in embodiments where the hole is not spherical, the hole diameter may refer to the maximum dimension of the hole. In some embodiments, the pore size non-uniformity is in the range of 40-75 percent, or in the range of 40-60 percent. In some embodiments, the pore size non-uniformity is up to 75, 70, 65, 60, 55, or 50 percent. In contrast, a comparative composition containing a thermosetting composition can have a pore size non-uniformity greater than 80, 90, or 100%. In some embodiments, a polishing layer in a polishing pad according to the present disclosure may have a porosity in the range of 5-60 percent, or in the range of 5-55, 10-50, or 10-40 percent. .

  The differences between controlling the pore size in the polishing layer according to the present disclosure and the pore size in the comparative thermosetting composition are shown in FIGS. 5A, 5B, 6A, and 6B. 5A and 5B are micrographs of a cross-sectional view and a top view, respectively, of the cured composition described in Example 2 in the Examples below. In contrast, FIGS. 6A and 6B are photomicrographs of a cross-sectional view and a top view of the cured composition of Comparative Example 3, respectively. Both Example 2 and Comparative Example 3 were prepared by using 10 weight percent polymer particles and mixing in the same manner. However, Example 2 was cured by both radiation curing and thermal curing, and Comparative Example 3 was cured only by thermal curing. The micrograph shows that the holes of Example 2 are better controlled than the holes of Comparative Example 3. The data in Table 1 in the following examples also supports the presence of a smaller pore size range, lower pore size non-uniformity, and greater hardness in Example 2 compared to Comparative Example 3.

  Without being bound by theory, it is believed that the control of pore size and pore size non-uniformity may be related to the hardness of the polishing layer. In some embodiments, the porous abrasive layer has a Shore D hardness of at least 40, 45, or 50. Hardness may be measured, for example, according to Test Method 2 described in the Examples below. In contrast, a comparative composition containing a thermosetting composition can have a Shore D hardness of less than 40.

  Surfactants are useful in the compositions and porous abrasive layers disclosed herein, for example, typically to reduce pore size and pore size range, and in the absence of surfactant. The pore distribution is further improved as compared with the case of using the heavy curing method. In other words, by adding a surfactant, the pore size distribution, pore size, pore density, and pore shape can be better controlled, which in turn provides uniform performance (eg, removal rate and uniformity within the wafer). ) May have a positive impact on key metrics. The micrographs of FIGS. 7A and 7B, which are cross-sectional and top view micrographs of the cured composition described in Example 15 in the following examples, show that the addition of surfactant is positive in the pore size range and pore distribution. It can have an impact. For example, there is a smaller pore size range in Example 15 compared to Example 2 which has the same number of polymer particles and was prepared in the same way but without a surfactant.

Selected Embodiments of the Present Disclosure In a first embodiment, the present disclosure provides a polishing pad, the polishing pad comprising:
A flexible layer having opposing first and second surfaces;
A porous polishing layer disposed on the first surface of the flexible layer, the porous polishing layer comprising:
A crosslinked network comprising a thermosetting component and a radiation curable component, wherein the radiation curable component and the thermosetting component are covalently bonded in the crosslinked network; and
Polymer particles dispersed in a crosslinked network;
Closed cell pores dispersed in the crosslinked network.

  In a second embodiment, the present disclosure provides the polishing pad according to the first embodiment, further comprising a support layer interposed between the flexible layer and the porous polishing layer.

  In a third embodiment, the present disclosure provides that the thermosetting component comprises at least one of polyurethane or polyepoxide, and the radiation curable component is at least one of polyacrylate, polymethacrylate, poly (vinyl ether), polyvinyl, or polyepoxide. A polishing pad according to the first or second embodiment is provided, including one.

  In a fourth embodiment, the present disclosure provides a polishing pad according to the first or second embodiment, wherein the thermosetting component and the polymer particles each independently comprise polyurethane.

  In a fifth embodiment, the present disclosure provides any one of the first to fourth embodiments, wherein the polymer particles are covalently bonded to at least one of a thermosetting component or a radiation curable component in the crosslinked network. A polishing pad is provided.

  In a sixth embodiment, the present disclosure provides a polishing pad according to any one of the first to fifth embodiments, wherein the radiation curable component comprises at least one of polyacrylate or polymethacrylate.

  In a seventh embodiment, the present disclosure provides a polishing pad according to the sixth embodiment, wherein the polyacrylate or polymethacrylate is covalently bonded to the thermosetting component via a urethane or urea linking group.

  In an eighth embodiment, the present disclosure provides a polishing pad according to any one of the first to seventh embodiments, wherein the porous polishing layer has a Shore D hardness of at least 40 as measured by Test Method 2. I will provide a.

  In a ninth embodiment, the present disclosure provides a polishing pad according to any one of the first to eighth embodiments, wherein the polymer particles have an average particle size in the range of 5 micrometers to 500 micrometers.

  In a tenth embodiment, the present disclosure provides a polishing pad according to any one of the first to ninth embodiments, wherein the polymer particles are substantially spherical.

  In an eleventh embodiment, the present disclosure provides a polishing pad according to any one of the first to tenth embodiments, wherein the polymer particles are fibers.

  In a twelfth embodiment, the present disclosure provides a polishing pad according to any one of the first to eleventh embodiments, wherein the polymer particles are present up to 20 weight percent, based on the total weight of the porous polishing layer. provide.

  In a thirteenth embodiment, the present disclosure provides a polishing pad according to any one of the first to twelfth embodiments, wherein the holes have a hole diameter non-uniformity of up to 75 percent.

  In a fourteenth embodiment, the present disclosure provides a polishing pad according to any one of the first to thirteenth embodiments, wherein the holes have an average pore diameter ranging from 5 micrometers to 100 micrometers.

  In a fifteenth embodiment, the present disclosure provides a polishing pad according to any one of the first to fourteenth embodiments, wherein the polishing layer includes a separate polishing element protruding from the support layer or the flexible layer.

  In a sixteenth embodiment, the present disclosure provides that the polishing elements each have a distal end distal from the support layer, the distal end being movable in an axis perpendicular to the polishing surface of the polishing element. A polishing pad according to 15 embodiments is provided.

  In the seventeenth embodiment, the present disclosure further includes a guide plate having a plurality of openings therein, wherein each of the separate polishing elements protrudes through one of the plurality of openings. A polishing pad is provided.

  In an eighteenth embodiment, the present disclosure provides a polishing pad according to any one of the fifteenth to seventeenth embodiments, wherein the polishing element is attached to the flexible layer with an adhesive.

  In a nineteenth embodiment, the present disclosure provides any of the first to eighteenth embodiments, wherein the flexible layer comprises at least one of silicone, natural rubber, styrene-butadiene rubber, neoprene, polyolefin, or polyurethane. A polishing pad according to one is provided.

  In a twentieth embodiment, the present disclosure provides a polishing pad according to any one of the first to nineteenth embodiments, wherein at least a portion of the polishing pad is transparent.

  In a twenty-first embodiment, the present disclosure provides a polishing pad according to any one of the first to twentieth embodiments, wherein the polymer particles are soluble in water.

  In a twenty-second embodiment, the present disclosure provides the polishing pad according to any one of the first to twenty-first embodiments, wherein the porous polishing layer further comprises a surfactant in the crosslinked network.

In a twenty-third embodiment, the present disclosure provides a method for manufacturing a polishing pad, the method comprising:
Providing a thermosetting resin composition, a radiation curable resin composition, and a composition containing polymer particles;
Forming pores in the composition; and
Placing the composition on a support layer;
By exposing the composition to radiation to at least partially cure the radiation curable resin composition and heating the composition to at least partially cure the thermosetting resin composition on the support layer Forming a porous polishing layer.

  In a twenty-fourth embodiment, the present disclosure provides a method according to the twenty-third embodiment, further comprising adhesively bonding a flexible layer to the support layer surface opposite the porous abrasive layer.

  In a twenty-fifth embodiment, the present disclosure provides that the thermosetting resin composition comprises a first resin having at least two isocyanate groups or at least two epoxide groups and at least two hydroxyl, amino, carboxy, or mercaptan groups. And a method according to the 23rd or 24th embodiment, wherein the radiation curable composition comprises at least two acrylate, methacrylate, vinyl, or epoxide groups. .

  In a twenty-sixth embodiment, the present disclosure provides a radiation curable composition wherein the first resin has at least two isocyanate groups and the second resin has at least two hydroxyl groups or at least two amino groups. Provides a method according to the twenty-fifth embodiment, wherein comprises at least two acrylate or methacrylate groups and the radiation curable composition further comprises at least one of an isocyanate group or a hydroxyl group.

  In a twenty-seventh embodiment, this disclosure provides a method according to the twenty-sixth embodiment, wherein the radiation curable composition is an aliphatic, isocyanate-functional urethane acrylate or methacrylate.

  In a twenty-eighth embodiment, the present disclosure further includes a step of placing an open mold in the composition on the support layer prior to forming the porous polishing layer, any of the twenty-third to twenty-seventh embodiments. One of the methods is provided.

  In a twenty-ninth embodiment, this disclosure provides a method according to any one of the twenty-third to twenty-eighth embodiments, wherein the holes are closed cell holes.

  In the thirty embodiment, the present disclosure provides the method according to any one of the twenty-third to twenty-ninth embodiments, wherein the composition further comprises a surfactant.

  In a thirty-first embodiment, the present disclosure provides a method according to any one of the twenty-third to thirtieth embodiments, wherein the porous polishing layer has a Shore D hardness of at least 40 as measured by Test Method 2. provide.

  In the thirty-second embodiment, the present disclosure provides the method according to any one of the twenty-third to thirty-first embodiments, wherein the polymer particles have an average particle size ranging from 5 micrometers to 500 micrometers.

  In a thirty-third embodiment, the present disclosure provides a method according to any one of the twenty-third to thirty-second embodiments, wherein the polymer particles are substantially spherical.

  In a thirty-fourth embodiment, the present disclosure provides the method according to any one of the twenty-third to thirty-third embodiments, wherein the polymer particles are fibers.

  In a thirty-fifth embodiment, the present disclosure provides a method according to any one of the twenty-third to thirty-fourth embodiments, wherein the polymer particles are soluble in water.

  In the thirty sixth embodiment, the present disclosure provides a method according to any one of the twenty-third to thirty fifth embodiments, wherein the polymer particles are present up to 20 weight percent, based on the total weight of the porous abrasive layer. To do.

  In the thirty-seventh embodiment, the present disclosure provides a method according to any one of the twenty-third to thirty-sixth embodiments, wherein the holes have a hole diameter non-uniformity of up to 75 percent.

  In a thirty-eighth embodiment, the present disclosure provides a method according to any one of the twenty-third to thirty-seventh embodiments, wherein the holes have an average pore diameter in the range of 5 micrometers to 100 micrometers.

  In a thirty-ninth embodiment, the present disclosure provides a method according to any one of the twenty-third to thirty-eighth embodiments, wherein the support layer includes a separate polishing element attached to and protruding from the support layer. To do.

  In a fortieth embodiment, the present disclosure provides for a separate polishing element each having an attached end and a distal end distal from the support layer, the distal end being a polishing element of the polishing element. A method according to a thirty-ninth embodiment is provided that is movable in an axis perpendicular to the surface.

  In a forty-first embodiment, the present disclosure includes separate abrasive elements in which the abrasive layer protrudes from the flexible layer, each abrasive element having a distal end distal from the support layer, the distal end being A method according to any one of the twenty-third to thirty-eighth embodiments is provided that is movable in an axis perpendicular to the polishing surface of the polishing element.

  In a forty-second embodiment, the present disclosure further includes a guide plate having a plurality of openings therein, wherein each of the separate polishing elements protrudes through one of the plurality of openings. A method according to any one of the forms is provided.

  In a forty-third embodiment, the present disclosure relates to any of the twenty-third to forty-second embodiments, wherein the support layer comprises at least one of silicone, natural rubber, styrene-butadiene rubber, neoprene, polyolefin, or polyurethane. One of the methods is provided.

  In a forty-fourth embodiment, the present disclosure provides a method according to any one of the twenty-third to forty-third embodiments, wherein at least a portion of the polishing pad is transparent.

In a forty-fifth embodiment, the present disclosure provides a polishing method, the method comprising:
Contacting the surface of the substrate with the porous polishing layer of the polishing pad according to any one of the first to twenty-second embodiments;
Moving the polishing pad relative to the substrate to reduce the surface of the substrate.

  In the forty-sixth embodiment, the present disclosure provides the method of the forty-fifth embodiment, further comprising providing a working fluid to an interface between the porous polishing layer and the substrate surface.

  Next, exemplary polishing pads according to the present disclosure are illustrated with reference to the following non-limiting examples.

Test method 1: FESEM
Scanning electron micrographs (top and cross-sectional views) of the article were obtained using a Hitachi S-4500 FESEM, available from Hitachi High-Technologies Corporation (Tokyo, Japan) according to conventional procedures. The cross section of the article was obtained by cutting with a sharp razor blade. Subsequently, prior to the SEM test, the sample was sputter coated with Au / Pd using conventional techniques. Images of the cross section and top surface of the article were obtained.

Test Method: 2: Durometer Rex Gauge Company, Inc. Durometer readings were obtained using a Model 1500 Shore D durometer available from (Buffalo Grove, Illinois). The values reported in Table 1 are the average of five measurements, and each measurement was performed on a different polishing structure in the examples.

Test method 3: Pore diameter measurement with optical microscope Pore diameter average, pore diameter standard deviation (Std. Dev.), Pore diameter range (observed maximum pore diameter-observed minimum pore diameter), pore diameter non-uniformity (pore diameter standard deviation) Is divided by the average pore size and multiplied by 100) and porosity (the measured range of the image consisting of pores divided by the total range of the image and multiplied by 100) is available from Media Cybernetics (Bethesda, MD) Measurements were made using image analysis of optical images obtained using an MM-40 Nikon measuring microscope available from Nikon Instruments, Inc (Elgin, IL) in combination with Image-pro plus analysis software.

  Prior to optical imaging, samples were prepared as follows. Cut three abrasive structures from the article using a resin for embedding by Buehler using 3M Company (St. Paul, Minnesota) under the trade name "3M SCOTCH-WELD Epoxy Compounding / Adhesive DP270 CLEAR". (41, Lake Bluff, Illinois), sealed in a phenolic ring form with an outer diameter of 2.5 cm and an inner diameter of 2.2 cm. The structure embedded in the epoxy is described by Buehler Ltd. 6 steps at a down force of 4.25 psi (29.3 kPa) using a head and platen speed of 120 rpm in all 6 steps using the Ecomet 3 polisher available from Polished by process. In all cases, the indicated sandpaper or polishing pad was attached to the Ecomet 3 platen by using a pressure sensitive adhesive (psa).

  Step 1: 8 inch (20.3 cm) diameter, 240 grit disc obtained from 3M Company under the trade name “3M WETORDRY PSA Disc 21366”, polishing time was 3 minutes using water as the grinding fluid.

  Step 2: Buehler Ltd. From the brand name "CARBIMET 8" PSA Disc 30-5118-600-100, 8 inch diameter (20.3 cm), 600 grit disc, polishing time was 6 minutes using water as the grinding fluid.

  Step 3: Bühler Ltd. From the brand name “TEXMET 1500 Polishing Pad”, 40-8618, 8 inch (20.3 cm) diameter pad, polishing time as Allied High Tech Products, Inc. 6 minutes using 15 μm grade polycrystalline diamond suspension 90-30035 available from (Rancho Dominguez, California).

  Step 4: Buehler Ltd. From the brand name “TEXMET 1500 Polishing Pad”, 40-8618, 8 inch (20.3 cm) diameter pad, polishing time as Allied High Tech Products, Inc. 6 minutes using a 6 μm grade polycrystalline diamond suspension 90-30025 available from

  Step 5: Buehler Ltd. From the brand name “TEXMET 1500 Polishing Pad”, 40-8618, 8 inch (20.3 cm) diameter pad, polishing time as Allied High Tech Products, Inc. 6 minutes using a 3 μm grade polycrystalline diamond suspension 90-30020 available from

  Step 6: Buehler Ltd. From the brand name “TEXMET 1500 Polishing Pad”, 40-8618, 8 inch (20.3 cm) diameter pad, polishing time as Allied High Tech Products, Inc. 6 minutes using a 1 μm grade polycrystalline diamond suspension 90-30015 available from

  After polishing, the surface of the polished structure was then coated with carbon using conventional techniques using a sputtering coater available from Denton Vacuum, LLC (Moortown, NJ). Subsequently, optical imaging was performed.

Example 1
Example 1 is by placing 0.28 g 5350D, 2.15 g M1, 1.83 g PHP-75D, 1.27 g D100 and 0.06 g TPO-L in a 50 mL plastic beaker. Prepared. The components were mixed together by placing the beaker in an Awatori-Rentaro AR-500 Thinky Mixer (Thinky Corporation, manufactured by Tokyo, Japan) and operating the AR-500 in a two-step process. The second step was performed immediately after the first step, and the second step was performed for 15 seconds at the rotation of 30 rpm and the rotation of 2000 rpm to form a resin mixture. The mold was poured into a Teflon-coated, Ni-plated aluminum mold formed from an aluminum plate 19.5 cm long and 9.2 cm wide, which consisted of a square array of tapered cylindrical cavities. Is 7.8mm in diameter at the top of the cavity The cavity bottom had a diameter of 6.5 mm and a depth of 1.8 mm, the distance from the center of the cavity to the center was about 11.7 mm, a piece of polyurethane film, ST-1880 was used as the backing. The backing was cut to a size of about 12 cm × 10 cm and placed on a mold area containing the resin mixture, a quartz plate 28 cm long × 17 cm wide × 3.5 mm thick placed on a polyurethane backing, The resin was forced into the cavities, and a thin land area of about 0.5 mm thick consisting of the resin mixture was formed between the cavities.

  Mold, resin mixture, backing and quartz plate from two UV lamps (“V” bulb, Fusion Systems Inc. (Gaithersburg, Maryland)) operated at 157.5 watts / cm (about 400 watts / inch) (Available) The resin mixture was UV cured by passing under. The mold passed under light at a speed of about 2.4 meters / minute (about 8 feet / minute), and the radiation passed through the quartz plate and polyurethane backing to the resin mixture. The mold, partially cured resin mixture and polyurethane backing were then transferred to an air stream through a furnace having a set temperature of 100 ° C. for 2 hours to thermally cure the resin mixture. The cured article was removed from the mold by gently pulling the polyurethane backing to form an article, Example 1, having a structured abrasive structure.

(Example 2)
Example 2 is that the composition of the resin mixture was 0.58 g 5350D, 2.15 g M1, 1.83 g PHP-75D, 1.27 g D100 and 0.06 g TPO-L, Prepared in the same manner as in Example 1.

(Example 3)
Example 3 was prepared in the same manner as Example 1 except that curing was reversed, first heat curing followed by UV curing.

Example 4
Example 4 was prepared in the same manner as Example 2 except that curing was reversed, first heat curing followed by UV curing.

Comparative Example C1
Comparative Example C1 was prepared in the same manner as Example 1 except that 5350D was omitted from the resin mixture composition.

Comparative Example C2
Comparative Example C2 is a resin mixture with a composition of 0.31 g of 5350D, 2.15 g of M1, and 3.65 g of PHP-75D, using only 2 hours of thermal curing at 100 ° C., and UV curing step. Prepared in the same manner as Comparative Example C1 except that it was omitted.

Comparative Example C3
Comparative Example C3 was prepared in the same manner as Comparative Example C2, except that the composition of the resin mixture was 0.65 g of 5350D, 2.15 g of M1, and 3.65 g of PHP-75D.

(Example 5)
Example 5 was prepared by placing 9.49 g 5350D, 35.00 g M1, 29.69 g PHP-75D, 20.63 g D100 and 1.03 g TPO-L in a 500 mL plastic beaker. did. The components were mixed together by placing the beaker in an Awatori-Rentaro AR-500 Thinky Mixer and operating the AR-500 in a two step process. The first step was performed for 5 minutes at 1000 rpm rotation and 1000 pm rotation. A second step was performed immediately after the first step, and the second step was performed at 30 rpm for rotation and 2000 rpm for 15 seconds to form a resin mixture.

  Using a knife coater having a width of about 21 inches (53 cm) and a gap of 60 mil (1.52 mm), a resin mixture coating of approximately 28 cm × 28 cm was prepared on a 26 μm thick backing, the backing being a thermoplastic polyurethane (TPU), ESTANE 58887-NAT02 (available from Lubrizol Advanced Materials, Inc., Cleveland, OH) was extruded into a film form on a paper release liner at 182 ° C.

  The coated resin mixture and backing were placed on a 12 inch x 12 inch (30.5 cm x 30.5 cm) x 0.25 inch (6.35 mm) thick aluminum plate. 36 magnets having a diameter of 0.375 inch (9.6 mm) and a thickness of 0.125 inch (3.2 mm) were fitted into the recess at the rear of the aluminum plate. The 36 recesses were a square array, and the distance from the center of the recesses to the center was about 5 cm. The diameter and depth of the recess were 9.8 mm and 4.3 mm, respectively. A Teflon-coated metal sieve having a hexagonal array of circular holes each having a diameter of about 6.2 mm and a center-to-center distance of about 8 mm and a thickness of about 1.6 mm is placed over the resin mixture coating. did. The magnetic attraction between the screen and the magnet of the aluminum plate caused the resin mixture coating to pass through the screen, leaving a thin land area of coating between the metal screen and the backing. The coating was UV cured in the same manner as Example 1 except that no quartz plate was used. Thermal curing followed the same procedure as described in Example 1.

  After removal from the oven, the metal sieve was removed from the cured resin to form a textured pad surface adhered to the original, paper-lined polyurethane backing. The paper was removed and the opposite side of the polyurethane backing was exposed. Using a 127 μm thick transfer adhesive, 3M Adhesive Transfer Tape 9672 (manufactured by 3M Company), the polyurethane backing on the textured pad surface is approximately 30 cm × 30 cm × 0.0625 inch thick. (1.59 mm) polyurethane foam, Rogers “PORON” urethane foam, part number 4701-50-20062-04 (American Flexible Products, Inc., manufactured by Chaska, Minnesota) by hand. A 23 cm diameter pad having a central hole with a diameter of 18 mm was punched from the laminate to form a pad having the structured polishing structure of the present invention, Example 5.

Comparative Example C4
Comparative Example C4 is a resin mixture composition of 10.48 g of 5350D, 35.00 g of M1, 59.38 g of PHP-75D, using only 2 hours of thermal curing at 100 ° C., eliminating the UV curing step. Prepared in the same manner as in Example 5 except that.

  Using test methods 2 and 3, the durometer, average pore diameter, standard pore diameter deviation, standard pore diameter range, uniform pore diameter, and porosity of Examples 1 to 5 and Comparative Examples C1 to C4 were measured. The results are shown in Table 1 below.

^＊比較例Ｃ１は孔を有さなかったため、測定可能な孔径データは存在しなかった。

^{* Since} Comparative Example C1 did not have pores, there was no measurable pore size data.

(Example 6)
Example 6 was carried out except that the composition of the resin mixture was 0.28 g 5150D, 2.15 g M1, 1.83 g PHP-75D, 1.27 g D100 and 0.06 g TPO-L. Prepared as in Example 1.

Illustrative Example I-1
Illustrative Example I-1 had a resin mixture composition of 0.28 g 5070D, 2.15 g M1, 1.83 g PHP-75D, 1.27 g D100 and 0.06 g TPO-L. Except for the above, it was prepared in the same manner as in Example 1.

(Example 7)
Example 7 was prepared in the same manner as Example 1 except that the amount of 5350D was 0.05 g.

(Example 8)
Example 8 was prepared in the same manner as Example 1 except that the amount of 5350D was 0.14 g.

Example 9
Example 9 was prepared in the same manner as Example 1 except that the amount of 5350D was 0.93 g.

Illustrative Example I-2
Exemplary Example I-2 was prepared the same as Example 1 except that the amount of 5350D was 1.31 g.

  The results of the FESEM (Test Method 1) of Examples 6-9 showed that they had an acceptable level of porosity. The results of FESEM (Test Method 1) of Exemplary Examples I-1 and I-2 showed that they have a low level of porosity.

(Example 10)
Example 10 was prepared in the same manner as Example 5 except for the following changes. The composition of the resin mixture was 0.62 g A15LV, 23 g P-250, 15.83 g PHP-75D, 22 g D100, 1.1 g TPO-L, and 0.68 g DC5604. The ingredients were placed in a 500 mL plastic container and mixed.

  Sieve with resin mixture and TPU backing passes under two UV lamps (“V” bulb, available from Fusion Systems Inc.) operated at about 157.5 watts / cm (about 400 watts / inch) The resin mixture was UV cured. The resin mixture passed under light at a speed of about 2.4 meters / minute (8 feet / minute) and radiation passed through the resin mixture. The fluoropolymer-coated polyester film release liner obtained from 3M Company under the trade name “3M SCOTCHPAK 1022 Release Liner” was then placed on the screen to partially cure the resin mixture. The assembly was then turned over so that the polyurethane backing was on the top and the fluoropolymer coated polyester film / screen / partially cured resin mixture was on the bottom. The entire assembly was passed the same UV curing process a second time with a quartz plate on the backing. After completion of the second UV cure, the quartz plate and fluoropolymer coated polyester film are removed and the sieve / partially cured resin mixture / lining assembly is moved to an air stream through a furnace with a set temperature of 100 ° C. for 2 hours Then, the resin mixture was thermally cured. After cooling to room temperature, a 23 cm diameter pad with a 18 mm diameter central hole was fabricated as described in Example 5 to obtain Example 10.

(Example 11)
Example 11 was prepared in the same manner as Example 10 except that the weight of A15LV was 1.25 g.

(Example 12)
Example 12 was prepared in the same manner as Example 10 except that the weight of A15LV was 3.20 g.

(Example 13)
Example 13 was prepared in the same manner as Example 10 except that the weight of A15LV was 6.76 g.

(Example 14)
Example 14 was prepared by placing 6.88 g A15LV, 127.78 g P-250, 6.11 g TPO-L, and 3.51 g DC5604 in a 650 mL plastic container. The components were mixed together by placing the container in an Awatori-Rentaro AR-500 Thinky Mixer and operating the AR-500 at 1000 rpm rotation and 1000 rpm rotation for 4 minutes. The vessel was removed from the mixer and 87.29 g PHP-75D and 122.22 g D100 were added to the vessel. The mixture went through a two-step mixing process. The first step was performed for 4 minutes at 1000 rpm rotation and 1000 rpm rotation. A second step was performed immediately after the first step, and the second step was performed at 30 rpm for rotation and 2000 rpm for 15 seconds to form a resin mixture.

  Using a knife coater having a width of about 21 inches (53 cm) and a gap of 60 mils (1.52 mm), approximately 21 in × 23 in (53.3 cm × 58.4 cm) of the resin mixture coating is backed by 4 mil (102 μm) thickness. Prepared on a stretch, the backing was formed by extruding the TPU, “ESTANE 58309-022”, at 210 ° C. onto a conventional 4 mil (102 μm) polyester release liner in film form.

  The coated resin mixture and backing were placed on a 24 inch x 24 inch (61.0 cm x 61.0 cm) x 0.25 inch (6.35 mm) thick aluminum plate. 113 magnets having a diameter of 0.375 inch (9.6 mm) and a thickness of 0.125 inch (3.2 mm) were fitted into the recess at the rear of the aluminum plate. The recess was a linear array of 15 rows. Eight rows had 8 recesses per row, while 7 rows had 7 recesses per row. The spacing between the rows was 4 mm, while the spacing between the recesses in the rows was 7.5 mm. The first row of recesses (near the plate edge) had 8 recesses, and the second row had 7 recesses. This alternating pattern continued to the fifteenth row with 8 recesses. The even rows of recesses were positioned to be centered between the corresponding adjacent rows of recesses. The diameter and depth of the recess were 9.8 mm and 4.3 mm, respectively. Using a tape capable of handling high temperatures, the magnet was fixed in the recess. Teflon-coated metal sieve of about 24 in × 24 in (61.0 cm × 61.0 cm) and about 1.6 mm thick with a hexagonal array of circular holes each having a diameter of about 6.2 mm and a center-to-center distance of about 8 mm Was placed over the resin mixture coating. The magnetic attraction between the screen and the magnet of the aluminum plate caused the resin mixture coating to pass through the screen, leaving a thin land area of coating between the metal screen and the backing.

  The resin mixture was cured according to the same curing procedure as in Example 10. After removal from the oven, the metal sieve was removed from the cured resin to form a textured pad surface adhered to the original polyester-lined polyurethane backing. Using a 127 μm thick transfer adhesive, “3M ADHESIVE TRANSFER TAPE 9672” (manufactured by 3M Company), the polyester release liner on the textured pad surface is approximately 21 in × 23 in (53.3 cm × 58.4). X Laminated by hand on a piece of polyurethane foam of thickness 0.0787 inch (2 mm). A pad having a structured polishing structure of the present invention, Example 14, was formed by punching a pad having a diameter of 20.0 in (50.8 cm) from the laminate.

Comparative Example C5
Comparative Example C5 was prepared in the same manner as Example 10 except that A15LV was omitted from the resin mixture composition.

Comparative Example C6
Comparative Example C6 has a resin mixture composition of 1.44 g A15LV, 23 g P-250, 47.50 g PHP-75D, and 0.68 g DC5604, using only a 2 hour heat cure at 100 ° C. This was prepared in the same manner as in Example 10 except that the UV curing step was omitted.

Comparative Example C7
Comparative Example C7 was prepared in the same manner as Comparative Example C6, except that A15LV was omitted from the resin mixture composition.

(Example 15)
Example 15 has a resin mixture composition of 7.58 g 5350D, 28.00 g M1, 23.75 g PHP-75D, 16.50 g D100, 0.83 g TPO-L and 0.77 g DC5604. Prepared in the same manner as in Example 5 except that

Comparative Example C8
Comparative Example C8 has a resin mixture composition of 8.39 g of 5350D, 28.00 g of M1, 47.50 g of PHP-75D and 3.5 g of DC5604, using only 2 hours of thermal curing at 100 ° C. This was prepared in the same manner as in Example 15 except that the UV curing step was omitted.

  Using Test Methods 2 and 3, the durometer, average pore diameter, standard pore diameter deviation, standard pore diameter range, uniform pore diameter, and porosity of Examples 10 to 15 and Comparative Examples C5 to C8 were measured. The results are shown in Table 2 below.

  Throughout this specification, references to “one embodiment”, “some embodiments”, “one or more embodiments”, or “embodiments” refer to the term “embodiment”. Certain exemplary features, structures, materials, or characteristics of the embodiments are not limited to some exemplary embodiments of the present disclosure, regardless of whether the term “exemplary” was previously included. In at least one embodiment. Thus, appearances of phrases such as “in one or more embodiments”, “in some embodiments”, “in one embodiment”, or “in an embodiment” are various places throughout the specification. Does not necessarily refer to the same embodiment of the several representative embodiments of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined into one or more embodiments in any suitable manner.

  While several representative embodiments have been described in detail herein, it should be understood that those skilled in the art will understand alternatives, modifications, and equivalents of these embodiments upon understanding the above description. Can be easily recalled. Accordingly, it is to be understood that this disclosure should not be unduly limited to the exemplary embodiments described hereinabove. In particular, as used herein, when numerical ranges by endpoints are described, it is intended to include all numbers subsumed within that range (eg 1 to 5 is 1, 1.5, 2 2.75, 3, 3.80, 4, and 5). In addition, throughout this document, all numbers used are considered modified by the term “about”. Further, all publications and patents referred to herein are in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. To the same extent, incorporated herein by reference.

  Various representative embodiments have been described. These and other embodiments are within the scope of the following claims.

Claims (23)

A flexible layer having opposing first and second surfaces;
A porous polishing layer disposed on the first surface of the flexible layer, the porous polishing layer comprising:
A crosslinked network comprising a thermosetting component and a radiation curable component, wherein the radiation curable component and the thermosetting component are covalently bonded in the crosslinked network; and
Polymer particles dispersed in the crosslinked network;
A polishing pad comprising closed cell pores dispersed in the crosslinked network.   The polishing pad according to claim 1, further comprising a support layer interposed between the flexible layer and the porous polishing layer.   3. The thermosetting component comprises at least one of polyurethane or polyepoxide, and the radiation curable component comprises at least one of polyacrylate, polymethacrylate, poly (vinyl ether), polyvinyl, or polyepoxide. The polishing pad described in 1.   The polishing pad according to claim 1, wherein the thermosetting component and the polymer particles each independently include polyurethane, and the radiation curable component includes at least one of polyacrylate or polymethacrylate.   The polishing pad according to any one of claims 1 to 4, wherein the polymer particles are covalently bonded to at least one of the thermosetting component or the radiation curable component in the crosslinked network.   The polishing pad according to claim 4, wherein the polyacrylate or polymethacrylate is covalently bonded to the thermosetting component via a urethane or urea bonding group. A method for manufacturing a polishing pad, comprising:
Providing a thermosetting resin composition, a radiation curable resin composition, and a composition comprising polymer particles;
Forming pores in the composition;
Disposing the composition on a support layer;
Exposing the composition to radiation to at least partially cure the radiation curable resin composition, heating the composition to at least partially cure the thermosetting resin composition; Forming a porous polishing layer on the support layer.   The method of claim 7, further comprising adhesively bonding a flexible layer to a surface of the support layer opposite the porous polishing layer.   The thermosetting resin composition comprises a first resin having at least two isocyanate groups or at least two epoxide groups, and at least one second resin having at least two hydroxyl, amino, carboxy, or mercaptan groups. The method of claim 7 or 8, wherein the radiation curable composition comprises at least two acrylate, methacrylate, vinyl, or epoxide groups.   The first resin has at least two isocyanate groups, the second resin has at least two hydroxyl groups or at least two amino groups, and the radiation curable composition has at least two acrylate or methacrylate groups 10. The method of claim 9, wherein the radiation curable composition further comprises at least one of an isocyanate group or a hydroxyl group.   The method according to any one of claims 7 to 10, wherein the composition further comprises a surfactant.   The method according to any one of claims 7 to 11, wherein the holes are closed-cell holes.   The polishing pad or method according to any one of claims 1 to 12, wherein the porous polishing layer has a Shore D hardness of at least 40 as measured by Test Method 2.   The polishing pad or method according to any one of claims 1 to 13, wherein the polymer particles have an average particle size in the range of 5 micrometers to 500 micrometers.   The polishing pad or method according to claim 1, wherein the polymer particles are substantially spherical.   The polishing pad or method according to any one of claims 1 to 15, wherein the polymer particles are fibers.   17. A polishing pad or method according to any one of the preceding claims, wherein the polymer particles are present up to 20 weight percent, based on the total weight of the porous polishing layer.   The polishing pad or method according to claim 1, wherein the holes have a hole diameter non-uniformity of up to 75 percent.   The polishing pad or method according to any one of the preceding claims, wherein the holes have an average pore diameter in the range of 5 micrometers to 100 micrometers.   20. A polishing pad or method according to any one of the preceding claims, wherein the polishing layer comprises a separate polishing element protruding from the support layer or the flexible layer.   21. Polishing according to any one of the preceding claims, wherein at least one of the support layer or the soft layer comprises at least one of silicone, natural rubber, styrene-butadiene rubber, neoprene, polyolefin, or polyurethane. Pad or method.   The polishing pad or method according to claim 1, wherein at least a portion of the polishing pad is transparent. The surface of a substrate according to any one of claims 13 to 22 as claimed in any one of claims 1 to 6, or as a dependent claim of any one of claims 1 to 6. Contacting the porous polishing layer of the polishing pad;
Moving the polishing pad relative to the substrate to scrub the surface of the substrate.

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