KR101855073B1 - Polishing pad and method of making the same - Google Patents

Abstract

The present invention relates to a polishing pad having a porous polishing layer, a method of manufacturing such a polishing pad, and a method of using such a pad in a polishing method. The polishing pad includes a compliant layer having first and second opposing faces and a porous polishing layer disposed on a first side of the compliant layer. The porous abrasive layer comprises a crosslinked network comprising a thermosetting component and a radiation cured component wherein the radiation cured component and the thermosetting component are covalently bonded in a crosslinked network. The porous abrasive layer also comprises polymer particles dispersed within the crosslinked network, wherein the polymer particles comprise at least one of a thermoplastic polymer or a thermosetting polymer. The porous abrasive layer typically also includes closed cell pores dispersed within the crosslinked network.

Description

BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates to a polishing pad,

Cross reference to related application

This application claims the benefit of U.S. Provisional Patent Application No. 61 / 288,982, filed December 22, 2009, and U.S. Provisional Patent Application No. 61 / 422,442, filed December 13, 2010, Which is incorporated herein by reference in its entirety.

During the fabrication of semiconductor devices and integrated circuits, the silicon wafers are repeatedly processed through a series of deposition and etching steps to form overlapping material layers and device structures. (Polishing) technique known as chemical mechanical planarization (CMP) for the purpose of obtaining a flat wafer surface with high uniformity across the wafer surface and no scratches or recesses (known as dishing) (For example, bumps, uneven rising regions, valleys, and trenches) can be removed.

In a typical CMP polishing process, a substrate, such as a wafer, is pressed against the polishing pad and moved relative to the polishing pad, typically in the presence of an etching chemical and / or a working liquid which is a slurry of abrasive particles in water. Various CMP polishing pads for use with polishing slurries are described, for example, in U.S. Patent No. 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 abrasive polishing pads are also known and are exemplified by, for example, U.S. Patent No. 6,908,366 (Gagliardi), wherein abrasive particles are typically formed from precisely shaped And is fixed to the pad surface in the form of a polishing compound. In recent years, polishing pads having a plurality of polishing elements extending from the compressible lower layer have been described in International Patent Publication No. WO / 2006057714 (Bajaj). Although a wide variety of polishing pads are known and used, the technology continues to seek new and improved polishing pads for CMP, particularly in CMP processes where large die diameters are used or where high levels of wafer surface planarity and polishing uniformity are required .

The present invention provides a porous polishing pad having a thermally cured component and a radiation cured component of an abrasive layer and a method of making such a polishing pad. Pores are included in the polishing layer through the use of polymer particles. The pores in the porous polishing pad disclosed herein are generally closed cell pores having a lower pore size non-uniformity and a smaller pore size than the pores of a conventional thermosetting polishing pad. Control over pore size and distribution can be beneficial, for example, in polishing performance of a polishing pad.

In one aspect,

A compliant layer having first and second opposing surfaces; And

A polishing pad comprising a porous polishing layer disposed on a first side of a compliant layer, the porous polishing layer comprising

A crosslinked network comprising a thermally cured component and a radiation cured component wherein the radiation cured component and the thermally cured component are covalently bonded in a crosslinked network;

Polymer particles dispersed within a crosslinked network; And

And closed cell pores dispersed within the crosslinked network. In some embodiments, the polishing pad further comprises a support layer interposed between the compliant layer and the porous polishing layer.

In another aspect, the present invention provides a method of making a polishing pad,

Providing a composition comprising a thermosetting resin composition, a radiation curable resin composition, and polymer particles;

Forming pores in the composition;

Placing the composition on a support layer; And

Exposing the composition to radiation and at least partially curing the thermosetting resin composition to at least partially cure the radiation curable resin composition, and heating the composition to form a porous abrasive layer on the support layer. In some embodiments, the method further comprises adhesively bonding the compliant layer to the surface of the support layer opposite the porous abrasive layer.

In a further aspect, the present invention provides a polishing method,

Contacting the substrate surface with the porous polishing layer of the polishing pad according to the present invention; And

And polishing the substrate surface by relatively moving the polishing pad relative to the substrate.

Exemplary embodiments of a polishing pad in accordance with the present invention have various features and characteristics that enable their use in a variety of polishing applications. In some embodiments, the polishing pad of the present invention may be particularly well suited for chemical mechanical planarization (CMP) of wafers used in the manufacture of integrated circuits and semiconductor devices. In some embodiments, the polishing pad described herein may provide some or all of the following advantages.

For example, in some embodiments, the polishing pad in accordance with the present invention serves to better retain the working liquid used in the CMP process at the interface between the polishing surface of the pad and the substrate surface being polished, The effectiveness of the working liquid can be improved. In another exemplary embodiment, a polishing pad according to the present invention can reduce or eliminate dishing and / or edge erosion of the wafer surface during polishing. In some exemplary embodiments, the polishing pad according to the present invention may be used in a CMP process to improve polishing in-wafer uniformity, a more planar polished wafer surface, increased edge die yield from the wafer, and improved CMP process operating conditions and / Consistency can be achieved. In a further embodiment, the use of a polishing pad in accordance with the present invention may be used to maintain the surface uniformity required to achieve high chip yields, or to allow polishing of more wafers before conditioning of the pad surface is required to maintain polishing uniformity of the wafer surface Or to allow machining of larger diameter wafers while reducing process time and wear of the pad conditioner.

In the present invention:

"Pore size non-uniformity" refers to the standard deviation of the pore size average divided by the average pore size and multiplied by 100.

The term "polyurethane" refers to any combination of more than one urethane bond (-NH-C (O) -O-), a urea bond (-NH-C (O) -NH- or -NH- N (R) -, where R may be a hydrogen, aliphatic, alicyclic or aromatic group), biuret, allophanate, uretdione, or isocyanurate linkages.

The term "(meth) acrylate" refers to acrylate and methacrylate, which may include urethane acrylate, methacrylate, and combinations of acrylate and methacrylate.

The term "polymeric" refers to a molecule having a structure in which units derived from molecules of low relative molecular mass are repeated many times. The term "polymeric" includes "oligomeric ".

Terms such as " a ", "an ", and" the "are intended to be non-exhaustive and include a generic class of specific examples that may be used for illustration. The terms indefinite article and definite article are used interchangeably with the term "at least one ".

The phrase " includes at least one of " and "includes at least one of" refers to any combination of items within the list and from two or more items in the list.

All numerical ranges include non-integer values between their endpoints and endpoints unless otherwise indicated.

Various aspects and advantages of exemplary embodiments of the present disclosure have been summarized. It is not intended to disclose each of the illustrated embodiments or all implementations of the invention. The following drawings and detailed description more particularly illustrate some embodiments of the invention.

Exemplary embodiments of the present invention are further described with reference to the accompanying drawings.
1A and 1B,
Figures 1a and 1b are cross-sectional and plan view micrographs of a porous polishing pad of the prior art, respectively.
2,
2 is a schematic side view of one embodiment of a polishing pad according to the present invention.
3,
3 is a side view of a polishing pad with a protruding abrasive element according to another embodiment of the present invention.
<Fig. 4>
4 is a side view of a polishing pad with a protruding abrasive element according to another embodiment of the present invention.
5A and 5B,
Figures 5A and 5B are cross-sectional and plan view micrographs of the cured composition of Example 2 useful for forming the abrasive layer according to the present invention.
6A and 6B,
6A and 6B are cross-sectional and plan-view micrographs of the cured composition of Comparative Example 3, respectively.
7A and 7B,
Figures 7a and 7b are cross-sectional and plan view micrographs of the cured composition of Example 15 useful for forming the abrasive layer according to the present invention.
8,
8 is a cross-sectional micrograph of the cured composition of Example 11 useful for forming an abrasive layer in accordance with the present invention.
Like numbers refer to like elements in the drawings. The drawings herein are not drawn to scale, and the components of the polishing pad in the figures are sized to emphasize the selected features.

Typical CMP pads are made from thermosetting (e.g., polyurethane) materials with pores. The pores may be created using a variety of methods, such as microballoon, soluble fibers, gas capture (e.g., generated in situ or off-site), and physical air capture. Control of the pore size, pore volume, and pore distribution across the pad can be controlled by the temperature gradient created during the polymerization, the skin / core effect resulting from the molding operation, the distribution of the fibers, the rate of dissolution of the soluble fibers, It can be difficult due to chemicals.

Some commercially available CMP pads have an open cell pad configuration created during thermal curing of the isocyanate resin. Figure 1 shows a cross-sectional view and a top view of a commercially prepared open-cell CMP pad available from PPG Industries of Pittsburgh, Pa. Under the trade designation "S7 ". As shown in Fig. 1, the size, shape, and distribution of the pores in this pad are not controlled.

The present invention is directed to an improved porous polishing pad typically formed with closed cell pores having a controlled size and uniformity. Various illustrative embodiments of the present invention will now be described. The exemplary embodiments of the present invention may have various modifications and changes without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the embodiments of the present invention should not be limited to the exemplary embodiments described below, but should be limited by the limitations set forth in the claims and any equivalents thereof.

Referring now to Fig. 2, porous polishing pad 2a includes a compliant layer 10a and a porous polishing layer 12a disposed on one side (i.e., one major surface) of the compliant layer. Between the porous polishing layer 12a and the compliant layer 10a an optional supporting layer 8a is provided which is useful in some embodiments of the porous polishing pad and method of the present invention. The porous abrasive layer comprises a crosslinked network, polymer particles dispersed within the crosslinked network, and closed cell pores dispersed within the crosslinked network. In contrast to polishing pads and methods in which the components of the polishing pad are removed during polishing (e.g., by corrosion or dissolution) to form pores, the polishing pad according to the present invention is porous prior to the start of the polishing process.

Exemplary polymer particles within the abrasive layer may comprise thermoplastic polymer particles, thermoset polymer particles, and mixtures thereof. The term "thermoplastic polymer " refers to a polymeric material that is not inherently cross-linked and does not essentially form a three-dimensional network. The term "thermosetting" refers to a polymer that is at least substantially crosslinked, wherein the polymer has essentially a three-dimensional network. In some embodiments, the polymer particles can be selected to minimize sintering of the particles upon heating (i.e., plastic flow is minimal at the interface of the polymer particles, and aggregation between particles of the polymer particles in the polishing pad of the present invention Almost nothing at all). In some embodiments, when the polymer particles of the pad comprise a particulate thermoplastic polymer, the polishing pad may be produced below the melting or sintering point of the particulate thermoplastic polymer. In another embodiment, the polymeric particles comprise a thermosetting polymer.

Polymer particles useful in the practice of the present invention may be prepared by a variety of methods (e. G., Condensation, free radical initiation, or a combination thereof). In yet another embodiment, the polymer may comprise interpenetrating polymer networks formed by stepwise or simultaneous condensation and free radical polymerization reactions. In the present invention, the term " interpenetrating polymer network (IPN) "refers to a combination of two polymers, both of which are in network form, wherein at least one polymer is instantly synthesized or cross-linked with the other being present. 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 crushed by cryogenic temperatures and classified into the desired particle size range. The shape of the polymer particles may be regular or irregular and may include shapes such as spheres, fibers, discs, flakes, and combinations or blends thereof. In some embodiments, the polymer particles are substantially spherical. The term "substantially spherical" refers to particles having a sphericity of 0.75 or greater (in some embodiments, 0.8, 0.85, 0.9, 0.95, 0.96, 0.97, or 0.98 or greater). In some embodiments, the polymer particles are fibers. Fibers useful in practicing the present invention typically have an aspect ratio (i.e., the longest dimension to the shortest dimension) of at least 1.5: 1, such as 2: 1, 3: 1, 4: 1, 5: , 25: 1, 50: 1, 75: 1, 100: 1 or more, or more. The fibers useful in the practice of the present invention may have an aspect ratio ranging from 2: 1 to 100: 1, from 5: 1 to 75: 1, or from 10: 1 to 50: 1.

In some embodiments, the polymer particles may have an average particle size of at least 5 micrometers (in some embodiments, 7, 10, 15, 20, 25, 30, 40, or 50 or more). In some embodiments, the polymer particles may have a mean particle size of up to 500 micrometers (in some embodiments, up to 400, 300, 200, or 100). Particle size generally refers to the particle diameter, but in an embodiment where the particle is not spherical (e.g., fibers), the particle size can refer to the longest dimension of the particle. The average particle size 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 a light scattering technique, such as the Coulter LS particle size analyzer, available from Beckman Coulter Incorporated and available from. As used herein and in the claims, "particle size" refers to the diameter or the longest dimension of a particle based on volume%, as measured by light scattering using a Coulter counter LS particle size analyzer. In this light scattering technique, the size is measured from the hydrodynamic radius of rotation regardless of the actual shape of the particles. The "average" particle size is the average diameter of the particles based on volume%. In some embodiments, particularly those in which the particles are fibers, the fibers have a maximum particle size of at most about 600, 500, or 450 micrometers (30, 35, or 40 US mesh) when measured by conventional screening techniques, to be. For example, in some embodiments, at least 97, 98, or 99% of the fibers pass through a screen having openings of 600, 500, or 400 micrometers (30, 35, or 40 U.S. mesh).

In some embodiments, the polymer particles have high uniformity. In some embodiments, the non-uniformity of the polymer particle size is at most 75 (in some embodiments, at most 70, 65, 60, 65, or 50%). Particle size non-uniformity refers to dividing the particle size standard deviation by the average particle size and multiplying by 100.

In some embodiments, the polymer particles are substantially solid. As used herein, the term "substantially solid" means that the particulate polymer is not hollow, e.g., the polymer particles are not in the form of a hollow microcapsule. However, in some embodiments, the substantially hollow polymer particles may contain entrapped bubbles.

Suitable polymer particles include but are not limited to polyvinyl chloride, polyvinyl fluoride, polyethylene, polypropylene, nylon, polycarbonate, polyester, poly (meth) acrylate, polyether, polyamide, polyurethane, polyepoxide, polystyrene , Polyimides (e.g., polyetherimides), polysulfone, and mixtures thereof. In some embodiments, the polymer particles can be selected from poly (meth) acrylates, polyurethanes, polyepoxides, and mixtures thereof.

In some embodiments, the polymer particles comprise water-soluble particles. Exemplary useful water-soluble particles include sugars (e.g., polysaccharides such as dextrin, cyclodextrin, starch, mannitol, and lactose), cellulose (e.g., hydroxypropylcellulose and methylcellulose), proteins, polyvinylalcohol, poly Vinyl pyrrolidone, polyacrylic acid, polyethylene oxide, water-soluble photosensitive resin, sulfonated polyisoprene, sulfonated polyisoprene copolymer, and particles made of any combination thereof. In some embodiments, the polymer particles comprise cellulose. In some of these embodiments, the polymeric particles comprise methylcellulose. In these embodiments, even though the polymer particles include water-soluble particles, the polymer particles can form pores in the abrasive layer when the abrasive layer is formed. Working liquids capable of dissolving particles during polishing are not required for pore formation.

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

In some embodiments, the first and second resins may be mixed together and polymerized or cured to form a bulk polyurethane, which is then pulverized (e.g., pulverized at a cryogenic temperature) and optionally classified . In some embodiments, the polymer particles are prepared by polymerizing the first and second resins together, slowly pouring the mixture into heated deionized water (optionally in the presence of an organic co-solvent and / or a surfactant) with stirring, (E. G., By filtration), drying the isolated particulate material, and optionally separating the dried particulate polyurethane. In another embodiment, the isocyanate and hydrogen material may be mixed together in the presence of an organic solvent (e.g., an alcohol, a water-insoluble ether, a branched and straight chain hydrocarbon, a ketone, toluene, xylene, and mixtures thereof).

In some embodiments, the first resin comprising at least two isocyanate groups may be selected from an isocyanate functional monomer, an isocyanate functional prepolymer, and combinations thereof. Exemplary suitable isocyanate monomers include aliphatic polyisocyanates; Ethylenically unsaturated polyisocyanate; Alicyclic polyisocyanate; Aromatic polyisocyanates in which the isocyanate group is not directly bonded to the aromatic ring, such as alpha, alpha '-xylene diisocyanate; Aromatic polyisocyanates in which an isocyanate group is directly bonded to an aromatic ring, such as benzene diisocyanate; Halogenation, alkylation, alkoxylation, nitrification, carbodiimide-modified, urea-modified, and burette-modified derivatives of these polyisocyanates; And dimerization and trimerization products of these polyisocyanates.

Exemplary aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2'- Tetramethylhexane diisocyanate, decamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,1-undecane diisocyanate, 1,3,6-hexamethylene triisocyanate, Diisocyanatomethyl) octane, bis (isocyanoatomethyl) octane, 2,5,7-trimethyl-1,8-diisocyanato-5- Ethyl) -carbonate, bis (isocyanatoethyl) ether, 2-isocyanatopropyl-2,6-di Isocyanato hexanoate, lysine diisocyanate include methyl ester, lysine tri-isocyanate methyl ester, and mixtures thereof.

Exemplary suitable ethylenically unsaturated polyisocyanates include butene diisocyanate and 1,3-butadien-1,4-diisocyanate. Exemplary suitable alicyclic polyisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (Isocyanatocyclohexyl) -1,2-ethane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bis Isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) Isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- Isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyante Isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] Isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] Ethyl) -bicyclo [2.2.1] -heptane and mixtures thereof.

Exemplary aromatic polyisocyanates in which the isocyanate group is not directly bonded to the aromatic ring include bis (isocyanatoethyl) benzene, alpha, alpha, alpha ', alpha' -tetramethyl xylene diisocyanate, (Isocyanatoethyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) Tylene triisocyanate, 2,5-di (isocyanatomethyl) furan, and mixtures thereof.

Exemplary suitable aromatic polyisocyanates having an isocyanate group directly bonded to the aromatic ring include, but are not limited to, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisophenylene diisocyanate, Propylene diisocyanate, trimethyl benzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, ortho-tolidine diisocyanate, 4,4'-diphenyl methane diisocyanate, Bis (isocyanatophenyl) ethylene, 3,3'-dimethoxy-biphenyl-4,4'-diisocyanate, tri Nyl methane triisocyanate, polymeric 4,4'-diphenylmethane diisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 4-methyldiphenylmethane- 2 ', 4', 6'-pentaisocyanate, diphenyl ether diisocyanate, bis (isocyanatophenyl ether) ethylene glycol, bis (isocyanatophenyl ether) -1,3-propylene glycol, benzophenone diisocyanate , Carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate, and mixtures thereof.

In some embodiments, the first resin comprising at least two isocyanate groups is selected from the group consisting of alpha, alpha '-xylene diisocyanate, alpha, alpha, alpha', alpha '-tetramethyl xylene diisocyanate, isophorone diisocyanate, bis (Isocyanatocyclohexyl) 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. The isocyanate functional polyurethane prepolymer can be prepared by various 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 together to form a polyurethane prepolymer having at least two isocyanate groups. Exemplary suitable isocyanate functional monomers include the abovementioned isocyanate functional monomers.

Suitable isocyanate functional polyurethane prepolymers useful in the practice of the present invention may vary within wide ranges of molecular weight. In some embodiments, the isocyanate functional polyurethane prepolymer has a number average molecular weight (Mn) of from 500 to 15,000, or from 500 to 15,000, as measured by gel permeation chromatography (GPC) using, for example, polystyrene standards. 5000.

Exemplary polyols useful in preparing isocyanate functional polyurethane prepolymers include straight chain or branched chain alkane polyols such as 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, But are not limited to, 1,4-butanediol, 1,3-butanediol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, di-trimethylolpropane, erythritol, pentaerythritol, Lithol; Polyalkylene glycols such as di-, tri-, and tetraethylene glycols, and di-, tri- and tetrapropylene glycols; Cyclic alkane polyols such as cyclopentane diol, cyclohexane diol, cyclohexane triol, cyclohexane dimethanol, hydroxypropyl cyclohexanol and cyclohexane diethanol; Aromatic polyols such as dihydroxybenzene, benzene triol, hydroxybenzyl alcohol and dihydroxytoluene; Bisphenols such as 4,4'-isopropylidene diphenol (bisphenol A); 4,4'-dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein, bis (4-hydroxyphenyl) methane (bisphenol F) , 2-ethenediyl) bisphenol and 4,4'-sulfonylbisphenol; Halogenated bisphenols such as 4,4'-isopropylidenebis (2,6-dibromophenol), 4,4'-isopropylidenebis (2,6-dichlorophenol) and 4,4'-iso Propylidene bis (2,3,5,6-tetrachlorophenol); Alkoxylated bisphenols such as alkoxylated 4,4'-isopropylidene diphenols having at least one alkoxy group such as ethoxy, propoxy, alpha-butoxy and beta-butoxy groups; And the like, such as 4,4'-isopropylidene-biscyclohexanol, 4,4'-oxybiscyclohexanol, 4,4'-thiobiscyclohexanol and bis (4-hydroxycyclohexanol) And biscyclohexanol which can be prepared by hydrogenating the corresponding bisphenol.

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

In some embodiments, the 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 can be prepared in the presence of a catalyst. In some embodiments, the amount of catalyst used may be less than 5 wt%, or less than 3 wt%, or less than 1 wt%, based on the total weight of the polyol and the isocyanate functional monomer. In some embodiments, exemplary suitable catalysts include tin-containing adducts of organic acids such as divalent tin octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptoide, dibutyltin di Maleate, dimethyltin diacetate, dimethyltin dilaurate, 1,4-diazabicyclo [2.2.2] octane, and mixtures thereof. In another embodiment, the catalyst can be zinc octoate, bismuth, or ferric acetylacetate. Additional exemplary suitable catalysts include tertiary amines such as triethylamine, triisopropylamine and N, N-dimethylbenzylamine.

In some embodiments, for polyurethanes useful in the preparation of polymer particles, the first resin having at least two isocyanate groups comprises a capped isocyanate compound having at least two capped isocyanate groups. The term "capped isocyanate compound" refers to a monomer or prepolymer having terminal and / or pendant capped isocyanate groups that can be converted into an isocyanate group (i.e., free) that has been capped off and a separate or free capping group. Any of the foregoing examples of suitable isocyanate compounds may be capped. Exemplary non-transient capping groups of the capped isocyanate include 1H-azoles such as 1H-imidazole, 1H-pyrazole, 3,5-dimethyl-1H- pyrazole, 1H- 1H-1,2,3-benzotriazole, 1H-1,2,4-triazole, 1H-5-methyl-1,2,4-triazole and 1H- 4-triazole; Lactam such as e-caprolactam and 2-pyrrolidinone; Morpholine, for example 3-aminopropylmorpholine; And N-hydroxyphthalimide. Exemplary temporary capping groups of the capped isocyanate compound include alcohols such as propanol, isopropanol, butanol, isobutanol, tert-butanol and hexanol; Alkylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ethers (e.g., ethylene glycol monobutyl ether and ethylene glycol monohexyl ether), and propylene glycol monoalkyl ethers (e.g., propylene glycol monomethyl ether) ; And ketoximes such as methyl ethyl ketoxime.

Without wishing to be bound by any theory, the inclusion of an isocyanate material capped in a first resin having at least two isocyanate groups can be achieved by (a) between at least a portion of the particulate polyurethane particles; And / or (b) at least a portion of the crosslinked network with at least a portion of the particulate polyurethane. In some embodiments, the capped isocyanate compound is present in an amount of greater than or equal to 5 mole percent, or greater than or equal to 10 mole percent, or less than 40 mole percent, based on the total molar equivalent of the free isocyanate and capped isocyanate groups, Or less than 50 mole% of the capped isocyanate group.

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 polyols described above.

In some embodiments, the second resin that may have at least two groups that are reactive with the isocyanate group comprises a polyamine. Exemplary polyamines include but are not limited to ethylene amines such as ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine Diamine, diethylenediamine (DEDA), and 2-amino-1-ethylpiperazine. Further exemplary suitable polyamines include at least one isomer of dialkyl toluenediamine, such as 3,5-dimethyl-2,4-toluenediamine, 3,5-dimethyl-2,6-toluenediamine, 3 Diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, 3,5-diisopropyl-2,4-toluenediamine, Isopropyl-2,6-toluenediamine and mixtures thereof. In some embodiments, the polyamine can be selected from methylene dianiline, trimethylene glycol di (para-aminobenzoate), and amine-terminated oligomers and prepolymers.

In some embodiments, suitable polyamines include 4,4'-methylene-bis (dialkyl anilines) such as 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene Bis (2,6-diethylaniline), 4,4'-methylene-bis (2-ethyl-6-methylaniline), 4,4'- From those based on 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6- Can be selected.

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 an isocyanate may be carried out in the presence of a catalyst. Suitable catalysts include those listed above for the preparation of isocyanate functional polyurethane prepolymers.

In some embodiments, the molar equivalent ratio of isocyanate groups and optional capped isocyanate groups to isocyanate-reactive groups useful in preparing particulate polyurethanes is from 0.5: 1.0 to 1.5: 1.0, such as from 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 can be made using less than the stoichiometric amount of the second resin so that the urethane or urea bond will react with the remaining isocyanate. In another embodiment, bifunctional partial substitution by a trifunctional compound will result in a more thermally stable chemical cross-linking.

Some useful particulate polyurethanes are commercially available, for example, from Dainichiseika Color & Chemicals Mfg. Co., Ltd. Advanced Polymers Group, Advanced Polymers Group, Tokyo, Quot; UCN-5150D ", and "UCN-5070D" in DAIMIC-BEAZ; The polyurethane particles are available from Negami Chemical Industrial Co., Ltd., Nomi, Japan under the trade designation "ART PEARL "; The aliphatic polyether thermoplastic polyurethanes are available, for example, from Bayer Corporation under the trade designation "TEXIN ".

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

In some embodiments, the first resin and the second resin comprising at least two epoxide groups may be mixed together and polymerized or cured to form a bulk polyepoxide, which is then milled (e.g., at a cryogenic temperature Crushed), and can be selectively sorted. In some embodiments, the particulate polyepoxide is prepared by mixing the epoxide functional and the hydrogen functional material together, slowly pouring the mixture into the heated deionized water under agitation, and cooling the formed particulate material (e.g., by filtration) Isolated, and 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 invention include epoxide functional monomers, epoxide functional prepolymers, and combinations thereof. Exemplary suitable epoxide functional monomers include aliphatic polyepoxides such as 1,2,3,4-diepoxybutane, 1,2,7,8-diepoxyoctane; Alicyclic polyepoxide such as 1,2,4,5-diepoxy cyclohexane, 1,2,5,6-diepoxy cyclooctane, 7-oxa-bicyclo [4.1.0] -Carboxylic acid 7-oxa-bicyclo [4.1.0] hept-3-ylmethyl ester, 1,2-epoxy-4-oxiranyl-cyclohexane and 2,3- (epoxypropyl) cyclohexane; Aromatic polyepoxides such as bis (4-hydroxyphenyl) methane diglycidyl ether; Hydrogenated bisphenol A diepoxide and mixtures thereof. Epoxide functional monomers that may be useful in the present invention are typically prepared from the reaction of a polyol with an epihalohydrin, such as epichlorohydrin. Polyols that can be used to prepare epoxide functional monomers include those mentioned herein above in connection with the preparation of an isocyanate functional prepolymer. Useful classes of epoxide functional monomers include, but are not limited to, the reaction of bisphenol with epichlorohydrin (e.g., 4,4'-isopropylidene dies for making 4,4'-isopropylidene diphenol diglycidyl ether Reaction of phenol with epichlorohydrin).

In some embodiments, an epoxide functional prepolymer useful in the preparation of particulate epoxides can be prepared by reacting a polymeric polyol with epichlorohydrin. Exemplary suitable polymeric polyols include polyalkylene glycols such as polyethylene glycol and polytetrahydrofuran; Polyester polyols; Polyurethane polyols; Poly ((meth) acrylate) polyols; And mixtures thereof.

In some embodiments of the present invention, the epoxide functional prepolymer is an epoxy (meth) acrylate monomer that can be prepared from a (meth) acrylate monomer and an epoxide functional radical polymerizable monomer (e.g., glycidyl Functional poly ((meth) acrylate) polymers. Suitable epoxide functional prepolymers can have a wide range of molecular weights. In some embodiments, the molecular weight of the epoxide functional prepolymer may be from 500 to 15,000 grams / mole, or from 500 to 5000 grams / mole, as measured by gel permeation chromatography (GPC) using polystyrene standards.

The second resin having at least two groups reactive with the epoxide may comprise at least one of hydroxyl, mercapto, carboxylic acid, primary amine or secondary amine. In some embodiments, the second resin may comprise the polyols mentioned herein before. In another embodiment, the second resin may comprise the polyamines mentioned hereinabove. In some embodiments, suitable polyamines may comprise a polyamide prepolymer having at least two amine groups selected from a primary amine, a secondary amine, and combinations thereof. Suitable exemplary polyamide prepolymers include, for example, those available under the trade designation "VERSAMID" from Cognis Corporation, Coating &amp; Inks Division of Monheim, Germany have.

In some embodiments, the preparation of the particulate epoxide from a second resin comprising a first resin comprising at least two epoxide groups and at least two groups reactive with the epoxide may be carried out in the presence of a catalyst. Exemplary 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 can be less than 5 wt%, or less than 3 wt%, or less than 1 wt%, based on the total weight of the combined first and second resins.

The mole ratio of epoxide to epoxide-reactive groups in the reactants used to make the particulate cross-linked polyepoxide is typically from 0.5: 1.0 to 2.0: 1.0, such as from 0.7: 1.0 to 1.3: 1.0 or 0.8: 1.0 to 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 comprise known conventional additives. Examples of such additives include heat stabilizers, antioxidants, mold release agents, static dyes, pigments, softening additives such as alkoxylated phenol benzoates and poly (alkylene glycol) dibenzoates, and surfactants such as ethylene oxide / Propylene oxide block copolymer surfactant. In some embodiments, such additives may be present in a total amount of up to 10 wt%, or up to 5 wt%, or up to 3 wt%, based on the total weight of the blended first and second resins.

Other polymer particles useful in the practice of the present invention include, for example, those available from ROHM America, Incorporated of Lawrenceville, Ga., Under the trade designation " ROHADON " Include thermoplastic poly (meth) acrylates commercially available under the trade designation "Art Pearl " from The Company, Limited. Other polymer particles useful in the practice of the present invention include, for example, cellulose particles commercially available from the Dow Chemical Company, Midland, Mich., Under the trade designation "METHOCEL ".

The amount of polymer particles present in the polishing pad according to the present invention may vary. Interestingly, it has been found that, in some embodiments, the amount of polymer particles mixed using a given technique affects the porosity of the resulting abrasive layer in an unexpected manner. For example, when using a mixer with a combination of revolution and rotation, it has been found that particle levels of up to 20 wt% provide less pores than particle levels of up to 15 wt%. However, other mixing techniques can provide different results. In some embodiments, the polymer particles are present in an amount of 1 wt% or more, or 2.5 wt% or more, or 5 wt% or more, based on the total weight of the crosslinked network with the particulate polymer. In some embodiments, the polymer particles may be present in an amount of up to 25 wt%, or up to 20 wt%, or less than 20 wt%, based on the total weight of the crosslinked network with the polymer particles.

In some embodiments, including embodiments wherein the polymer particles are fibers, the polymer particles are present in an amount of up to 10 weight percent, or up to 5 weight percent, or less than 5 weight percent, based on the total weight of the crosslinked network with the polymer particles . Advantageously, the polymer particles in the form of fibers can provide a useful level of porosity at a level of up to 2% by weight, based on the total weight of the crosslinked network with the polymer particles. In some of these embodiments, the polymer particles are water soluble fibers (e. G., Methylcellulose fibers). As shown in Tables 1 and 2 of the Examples, higher levels of porosity are obtained in methylcellulose fibers than in equivalents based on the weight of spherical polyurethane particles. 8, which is a cross-sectional micrograph of the cured composition of Example 12, and Figs. 7a and 7b, which are cross-sectional and planar micrographs, respectively, of the cured composition of Example 15 show that 2 wt% To the same level of porosity as in 10 wt% particles (Figs. 7A and 7B) can be obtained.

Including low levels of particles to achieve the same porosity can be advantageous, for example, to improve uniformity in particle distribution across the crosslinked network and to maintain hardness at the pad surface during polishing.

A polishing pad according to the present invention comprises a polishing layer comprising polymer particles and a crosslinked network comprising a thermosetting component and a radiation cured component. A wide variety of suitable polymers may be useful for the formation of crosslinked networks. In some embodiments, the thermally cured component comprises at least one of a polyurethane, a polyepoxide, or a urethane-modified polyepoxide.

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

In some embodiments, the abrasive layer disclosed herein may comprise at least 75 wt%, or at least 80 wt%, or at least 85 wt% cross-linked network, based on the total weight of the crosslinked network with the polymeric particles . In some embodiments, the crosslinked network may be present in the polishing layer in an amount of up to 99 wt%, or up to 95 wt%, or up to 90 wt%, based on the total weight of the crosslinked network with the polymer particles.

The crosslinked network can be prepared by conventional polymerization technique methods. 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 thermally cured component may comprise a polyurethane formed by condensing a thermosetting resin composition comprising a polyurethane prepolymer with a polyamine. In some embodiments, the radiation cured component may comprise urethane-polyacrylate or urethane-polymethacrylate formed by polymerizing 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 thermal curing and radiation curing polymerization. In some embodiments, the radiation cured component (polyacrylate or polymethacrylate in some embodiments) is covalently bonded to the thermally cured component, e.g., via a urethane or urea linker.

Suitable thermosetting resin compositions useful in the practice of the present invention may include 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, or at least two epoxide groups, which may be a capped isocyanate group; And a second resin having at least two groups (e.g., hydroxyl, amino, carboxy, or mercaptan groups) reactive with the epoxide and / or the isocyanate.

Exemplary suitable first and second resins that can be used to prepare the thermoset components are, respectively, based on the particulate polyurethane, the isocyanates (including prepolymers) previously described herein, the capped isocyanates, the polyols and the polyamines Lt; / RTI &gt; The use of a capped isocyanate can delay the onset of gelation, for example, when the first and second resins are blended, which allows more time for mixing of the first and second resin and polymer particles .

Some isocyanate prepolymers useful as the first resin are commercially available, for example, the isocyanate prepolymer is available from Air Products and Chemicals, Inc., Allentown, Pa. AIRTHANE PHP-75D ". Some diamines useful as the second resin are commercially available, for example, oligomer diamines available from Air Products and Chemicals, Inc. under the trade designations "VERSALINK P250" and "VersaceLink P650".

In some embodiments, a composition comprising a radiation curable resin and a thermosetting resin comprising a first resin having at least two isocyanate groups and a second resin having at least two groups reactive with an isocyanate group further comprises a catalyst . Exemplary suitable catalysts include those cited hereinbefore for the preparation of particulate polyurethanes (e. G. Tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate). In some embodiments, the catalyst may be incorporated into the second resin prior to compounding the first and second resins. In some embodiments, the catalyst may be present in an amount of less than 5 wt%, or less than 3 wt%, or less than 1 wt%, based on the total weight of the blended first and second resins. The molar equivalence ratio of the isocyanate groups in the first and second resins and the optional capped isocyanate groups to the isocyanate-reactive groups is from 0.5: 1.0 to 2.0: 1.0, or 0.7: 1.0 to 1.3: 1.0, or 0.8: 1.0 To 1.2: 1.0.

In some embodiments, the thermoset component comprises a first resin having at least two epoxide groups, and a second resin having at least two groups reactive with the epoxide group (e.g., hydroxyl, amino, carboxy, or mercapto groups) Can be prepared by reacting a second resin. An exemplary suitable first resin having at least two epoxide groups and a second resin may be any of their epoxides, polyamines, and polyols used to make the particulate polyepoxide as discussed hereinabove .

In some embodiments, a composition comprising a radiation curable resin and a thermosetting resin comprising first and second resins used to produce a polyepoxide side cured component may further comprise an epoxide ring opening catalyst have. Exemplary suitable catalysts for ring opening of epoxides include any of those mentioned above (e.g., tertiary amines such as tri-tert-butylamine and tetrafluoroboric acid). In some embodiments, the catalyst may be added into the second resin before mixing the first and second resins. In some embodiments, the epoxide ring opening catalyst may be present in an amount of less than 5 wt%, or less than 3 wt%, or less than 1 wt%, based on the total weight of the first and second resins. The molar equivalence ratio of the epoxide-reactive groups in the first and second resins may be from 0.5: 1.0 to 2.0: 1.0, 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 resin may comprise conventional additives. Exemplary suitable conventional additives include particulate polyurethanes and any of their additives previously described herein for the preparation of particulate polyepoxides, such as mold release agents, dyes, and plasticizers. In some embodiments, the additive may be present in a total amount of less than 10 wt%, or less than 5 wt%, or less than 3 wt%, based on the total weight of the crosslinked network. Conventional additives may be added, for example, to either the first or second resin.

A porous polishing pad according to the present invention comprises an abrasive layer having a radiation cured component. The radiation cured component comprises at least one of polyacrylate, polymethacrylate, poly (vinyl ether), polyvinyl, or polyepoxide. In some embodiments, the radiation cured component comprises at least one of polyacrylate or polymethacrylate. The radiation cured component may be prepared from a radiation curable resin comprising at least two acrylates, methacrylates, vinyl (e.g., 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 multifunctional isocyanate material having at least two (meth) acrylate-modified isocyanate groups, which may be a terminal and / (For example, a hydroxyl, amino group, or mercapto group) with an isocyanate group-containing polyurethane prepolymer (e.g., the polyurethane prepolymer described above in connection with the preparation of the particulate polyurethane) (Meth) acrylate. &Lt; / RTI &gt;

Exemplary suitable hydroxy or amino functional (meth) acrylates include hydroxyalkyl acrylates and methacrylates (e.g., 2-hydroxyethyl acrylate (HEA), 2-hydroxyethylmethyl acrylate (HEMA ), 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 1,3-dihydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl acrylate and methacrylate, 2-hydroxybutyl (Meth) acrylate, 2-hydroxyalkyl (meth) acryloylphosphate, 4-hydroxycyclohexyl (meth) acrylate, (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (Meth) acrylate, N-alkyl-N-hydroxyethyl acrylamide and methacrylamide, hydroxyethyl-beta-carboxyethyl acrylate , Hydroxyhexyl acrylate, hydroxyoctyl methacrylate, polypropylene glycol monomethacrylate, propylene glycol monomethacrylate, caprolactone acrylate, t-butylaminoethyl methacrylate, and mixtures thereof) . Many of these are available from commercial sources, for example, useful hydroxyethyl acrylate and hydroxypropyl acrylate are available from Dow Chemical (Midland, Mich., USA) and Osaka Organic Chemical Industry Ltd. &lt; RTI ID = 0.0 &gt; (Osaka, Japan). Useful hydroxybutyl acrylate is available from Osaka Organic Chemicals Industries Limited. Useful hydroxypolyester acrylates are available from Dow Chemical Company under the trade designation "TONE MONOMER M-100" and from Osaka Organic Chemical Industries Limited under the trademark "VISCOAT 2308 ". Useful hydroxy polyether acrylates are available from Bayer Chemicals (Pittsburgh, Pa.) Under the trade designation "ARCOL R-2731 &quot;.

The (meth) acrylate group may be located on the prepolymer as a pendant, at the end, or a combination thereof. In some embodiments, the prepolymer can be end-capped with a (meth) acrylate group. Radiation-curable resins can be prepared, for example, by reacting (meth) acrylates having isocyanate-reactive functional groups with polyisocyanate prepolymers, typically in the presence of an excess of an isocyanate. In some embodiments, the (meth) acrylate having an isocyanate reactive functional group is present in an amount of from about 10% to about 80%, from about 20% to about 70%, or from about 30% to about 80%, of the isocyanate groups on the isocyanate- Reacted with an isocyanate functional prepolymer in an amount such that about 60% is reacted with a (meth) acrylate having an isocyanate reactive functional group.

Partial (meth) acrylate-modified multifunctional isocyanate materials having at least two (meth) acrylate-modified isocyanate groups are commercially available, such as isocyanate urethane acrylate, available from Bayer, Inc. of Pittsburgh, Pa. Available from Bayer Materials Science under the trade designations "DESMOLUX D100", "Desmorux VPLS 2396" and "Desmorux XP2510".

Compositions comprising a radiation curable composition and a thermosetting composition typically also comprise a photoinitiator or combination of photoinitiators. Useful photoinitiators include, for example, benzoin, benzoin acetals (e.g., benzyl dimethyl ketal), benzoin ethers (e.g., benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether Hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-isopropylphenyl) - 2-methylpropan-1-one), benzoyl cyclohexanol, dialkoxyacetophenone derivatives (for example, 2,2-diethoxyacetophenone), acylphosphine oxides (for example, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, Methylthiophenylmorpholinocarbonate (e.g., 2-methyl-1-4 (methylthio) and phenyl-2- Le poly-1-propanone), and morpholino phenyl amino ketones, including, "alpha cleavage type" photoinitiators; A hydrogen extraction photoinitiator comprising a photoinitiator and a public reagent based on benzophenone, thioxanthone, benzyl, camphorquinone, and ketocoumarin; And combinations thereof. In some embodiments, the photoinitiator is acylphosphine oxide (e.g., bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) - , 4-trimethylpentyl) phosphine oxide, and 2,4,4-trimethylbenzoyldiphenylphosphine oxide).

Exemplary useful commercially available photoinitiators include those sold under the trade designations IRGACURE 369, IRGACURE 819, IRGACURE &lt; RTI ID = 0.0 &gt; 819 & , "Irgacure CGI 403", "Irgacure 651", "Irgacure 1841", "Irgacure 29594", "DAROCUR 1173", "Darocur 4265", and "CGI 1700" Available. The photoinitiator is preferably present in an amount sufficient to provide the desired photopolymerization rate. The amount will depend in part on the light source, the thickness of the layer to be exposed to radiation energy, and the extinction coefficient of the photoinitiator depending on the wavelength. Typically, the photoinitiator component will be present in an amount of at least about 0.01% by weight, at least about 0.1% by weight, at least about 0.2% by weight, at most about 10% by weight, or up to about 5% by weight.

The radiation curable and thermosetting compositions can be thoroughly mixed in a composition for making the porous polishing pad disclosed herein. In some embodiments, the composition comprises at least about 10 (in some embodiments, at least about 15, 20, 25, 30, or 40 or more) weight percent radiation curable compositions and at most about 85 (in some embodiments, , Up to about 80, 75, 70, 65, 60, 55, or 50 weight percent of radiation curable compositions. In some embodiments, the composition comprises about 15 (in some embodiments, about 20, 25, 30, 35, 40, 45, 50, 55, or 60) weight percent or more thermosetting composition and a maximum About 90 (in some embodiments, up to about 85, 80, or 75) percent by weight thermosetting composition.

In some embodiments, the composition comprising the thermosetting resin composition, the radiation curable resin composition, and the polymer particles further comprises a surfactant. Similarly, in some embodiments, a crosslinked network comprising a thermally cured component and a radiation cured component, polymer particles dispersed within the crosslinked network, and a porous structure comprising closed cell pores dispersed within the crosslinked network The abrasive layer further comprises a surfactant dispersed within the crosslinked network. Examples of surfactants that may be useful in the practice of the present invention include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants (e.g., zwitterionic surfactants), and combinations thereof do. Each of these types of surfactants may include fluorine-based, silicone, and hydrocarbon-based surfactants.

Exemplary useful cationic surfactants include aliphatic ammonium salts. Exemplary useful anionic surfactants include carboxylic acid salts (e.g., fatty acid salts and alkyl ether carboxylic acid salts), sulfonates (e.g., alkylbenzenesulfonates, alkylnaphthalenesulfonates, and alpha-olefin sulfonates) , Sulfates (e.g., higher alcohol sulfate ester and alkyl ether sulfate), and phosphates (e.g., alkyl phosphates). Exemplary useful nonionic surfactants include polyoxyethylene alkyl ethers, ether esters (e.g., polyoxyethylene ethers of glycerin esters), esters (e.g., polyethylene glycol fatty acid esters, glycerin esters, sorbitan esters) Silicone glycol copolymers such as those available under the trade designation "DABCO" from Air Products of Allentown, Pa., USA. The surfactant may be present in the composition or in the polishing layer in an amount of, for example, up to 10% by weight (in some embodiments up to 4, 3, or 2% by weight) based on the total weight of the composition or porous abrasive layer. In some embodiments, the surfactant is present in an amount of at least 1% based on the total weight of the composition or porous abrasive layer. The present invention provides a method of manufacturing a polishing pad as described herein. The method includes forming pores in a composition comprising a thermosetting resin composition, a radiation curable resin composition, and polymer particles. In some embodiments, the step of forming pores in the composition is carried out by mixing the composition. Mixing can be accomplished in a variety of techniques, for example using mechanical mixers or manual mixing. In some embodiments, the mixing process (and mechanical mixer) may include both orbital and rotational. The particle size and loading of the polymer particles can affect the porosity of the resulting abrasive layer, as described above.

In some embodiments, the thermosetting resin composition, the radiation curable resin composition, and the composition comprising the polymer particles may be mixed together and placed on the support layer. An open mold (e.g., top or uncoated mold) on top of the support layer may be useful for forming the desired shape of the abrasive layer. The mixture may be dispensed into the mold by mechanical means to uniformly fill the mold. Suitable mechanical means may include the use of low pressure squeeze or compression rollers.

The method of making a polishing pad disclosed herein also includes forming the polishing layer by at least partially curing the radiation curable composition by exposing the composition to radiation and heating the composition to at least partially cure the thermosetting resin. The radiation is typically ultraviolet radiation (i.e., radiation in the range of about 200 nm to about 400 nm). The amount of radiation required to at least partially cure the composition will depend on a variety of factors including, for example, the exposure angle to radiation, the thickness of the composition, the amount of polymerizable group in the composition, and the type and amount of photoinitiator. Typically, a UV light source having a wavelength of from about 200 nm to about 400 nm is directed to a composition that is transported on a conveyor system that provides a through rate through a UV source that is compatible with the radiation absorption profile of the composition. 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 driven lamps, xenon lamps such as excimer lasers and argon- A beam source, and combinations thereof. The composition may then be heated to a temperature of, for example, up to about 180 캜, up to about 150 캜, up to about 135 캜, or up to about 120 캜 (e.g., from 80 캜 to 120 캜, 80 캜 to 110 캜, (For example, 30 minutes to 24 hours) in an oven at an elevated temperature of about &lt; RTI ID = 0.0 &gt; 100 C &lt; / RTI &gt; Exposure to radiation and heating may be performed sequentially or simultaneously. In some embodiments, exposure to radiation is performed prior to heating.

The polishing pad of the present invention may have one or more work surfaces, as used herein, refers to a surface of a polishing pad that is capable of contacting a surface of an article to be polished. In some embodiments, the article to be polished may be a silicon wafer. In some embodiments, the work surface of the polishing pad may have surface features such as channels, grooves, holes, and combinations thereof. These surface features can improve one or more of the following features: (1) movement of the polishing slurry between the working surface of the pad and the surface of the article being polished; (2) removing and transporting the polished material from the surface of the article being polished; Or (3) the polishing or planarization efficiency of the polishing pad.

The surface features can be incorporated into the working surface of the polishing pad by a variety of methods. In some embodiments, the working surface of the pad can be mechanically altered, for example by polishing or cutting. In another embodiment, the surface feature may provide at least one internal surface of the mold with a raised feature that can be imprinted into the working surface of the pad during formation of the pad, for example, Lt; / RTI &gt; The surface features can be distributed in the form of a random or uniform pattern across the working surface of the polishing pad. Exemplary surface feature patterns may include helical, circular, square, network lines, and waffle-like patterns.

In some embodiments, a polishing pad according to or according to the present invention comprises a separate polishing element that protrudes from the support layer. Referring now to FIG. 3, there is shown an embodiment of a polishing pad 2 comprising a plurality of polishing elements 4, each polishing element 4 being secured to an optional supporting layer 8. The polishing pad 2 further comprises a compliant layer 10. Typically, the abrasive layer comprising the separate abrasive elements is a continuous layer, but this is not shown in Fig. Between the separate abrasive elements, the film may have a thickness, for example up to 0.01, 0.02, or 0.03 mm. In another embodiment, an abrasive layer comprising a separate abrasive element may have discontinuities within the film, for example, between separate abrasive elements. The abrasive elements 4 are fixed to the support layer in the illustrated embodiment with a thin film layer (not shown) between the abrasive elements 4, so that at least one of the other abrasive elements 4 of the abrasive element 4 The abrasive element 4 typically remains movable independently of the axis perpendicular to the abrasive surface 14 of each of the abrasive elements 4, As shown, each of the polishing elements 4 generally has a plurality of pores 15 distributed substantially throughout the entire polishing element 4.

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

Referring to Figure 4, there is shown another exemplary embodiment of a polishing pad 2 ', wherein the polishing pad 2' comprises a compliant layer 2 having a first major surface and a second major surface opposite the first major surface, (30); A plurality of abrasive elements (24) each having a land area (25) for securing each abrasive element (24) to a first major surface of the compliant layer (30); And an optional guide plate (31) having a first major surface and a second major surface opposite the first major surface, the guide plate (31) having a plurality of abrasive elements (32) on the first major surface of the compliant layer (24) and the first major surface of the guide plate (31) is on the circle from the compliant layer (30).

As illustrated by FIG. 4, each abrasive element 24 extends from a first major surface of the guide plate 31 along a first direction substantially perpendicular to the first major surface. In the particular embodiment illustrated by Fig. 4, each of the porous abrasive elements 24 is also shown having a plurality of pores 15 distributed substantially throughout the entire abrasive element 24. In addition, in the particular embodiment illustrated by Fig. 4, three abrasive elements 24 are shown, all abrasive elements 24 being distributed across the porous abrasive surface 23 and virtually the entire abrasive element 24 Lt; RTI ID = 0.0 &gt; 15 &lt; / RTI &gt; It will be appreciated, however, that a large number of abrasive elements 24 may be used, and that the number of porous abrasive elements may be selected as many as one abrasive element, as many as all abrasive elements, or any number therebetween .

The optional abrasive composition dispensing layer 28 is further illustrated by FIG. During the polishing process, the optional polishing composition dispensing layer 28 aids in dispensing the working liquid and / or polishing slurry to the individual polishing elements 24. As illustrated by FIG. 4, a plurality of apertures 26 extending through at least the guide plate 31 and the optional polishing composition distribution layer 28 may also be provided. In some embodiments, the guide plate 31 may also serve as a polishing composition distribution layer.

4, each of the abrasive elements 24 has a land area 25, and each abrasive element 24 has a corresponding land area 25 in contact with the guide plate 31 To the first major surface of the compliant layer 30, as shown in FIG. At least a portion of each abrasive element 24 extends into a corresponding aperture 26 and each abrasive element 24 also passes through a corresponding aperture 26 and extends from the first major surface of the guide plate 31 Extend outwardly. The plurality of openings 26 of the guide plate 31 serve to guide the lateral arrangement of the abrasive elements 24 on the support layer 30 while engaging the respective land areas 25, And fixes the corresponding abrasive element 24 to the support layer 30.

As a result, during the polishing process, the abrasive element 24 is free to be independently displaced in a direction substantially perpendicular to the first major surface of the support layer 30, while still being guided by the guide plate 31 to the compliant layer 30). In some embodiments, this may permit the use of non-compliant polishing elements, for example, porous polishing elements having pores substantially distributed at or near the polishing surface only.

4, the abrasive element 24 additionally comprises an optional adhesive layer 34 positioned at the interface between the compliant layer 30 and the guide plate 31 to form a compliant layer 30, (30). However, other joining methods may be used, including direct bonding of the abrasive element 24 to the compliant layer 30 using, for example, heat and pressure.

4, the plurality of openings may be arranged as an array of openings, wherein at least a portion of the openings 26 define an undercut area of the main bore and guide plate 31, And the undercut area forms a shoulder that engages the corresponding abrasive element land area 25 so that the abrasive element 24 is not required between the abrasive element 24 and the compliant layer 30, Lt; / RTI &gt;

A second optional adhesive layer 36 may also be used to secure the optional polishing composition dispensing layer 28 to the first major surface of the guide plate 31, as illustrated by FIG. In addition, in the specific embodiment illustrated by FIG. 4, a polishing pad 2 ', which can be used to secure the polishing pad 2' to a polishing platen (not shown in FIG. 4) of a CMP polishing apparatus (not shown in FIG. 4) Sensitive adhesive layer 32 is shown adjacent to the support layer 30, which is opposite to the guide plate 31. As shown in Fig.

The guide plate and / or distribution layer may also be used in connection with the embodiment shown in Fig. 3 in which the porous abrasive element 4 does not have a land area. The support layer 8 may be removed in the presence of a guide plate and the porous abrasive element may be secured to the compliant layer 10, for example, using an adhesive.

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

In the case of a cylindrical abrasive element 4, 24 having a circular cross section, the cross-sectional diameter of the abrasive elements 4, 24 in a direction substantially parallel to the abrasive surfaces 14, 23 may be about 50 microns to about 20 millimeters Sectional diameter in some embodiments is from about 1 mm to about 15 mm, and in other embodiments, the cross-sectional diameter is from about 5 mm to about 15 mm (or even from about 5 mm to about 10 mm). In the case of a non-cylindrical polishing element having a non-circular cross-section, the characteristic dimensions can be used to characterize the size of the polishing element by a specific height, width, and length. In some exemplary embodiments, the characteristic dimension may be selected to be from about 0.1 mm to about 30 mm.

In another exemplary embodiment, the cross-sectional area of each of the polishing elements 4, 24 in a direction generally parallel to the polishing surfaces 14, 23 may be between about 1 mm &lt; 2 &gt; and about 1,000 mm & To about 500 mm &lt; 2 &gt;, in another embodiment, from about 20 mm &lt; 2 &gt; to about 250 mm &lt; 2 &gt;.

The polishing element (4 in Fig. 3, 24 in Fig. 4) may be distributed on the major surface of the compliant layer (10 in Fig. 3, 30 in Fig. 3) in a very diverse pattern, depending on the intended application, It may be regular or irregular. The abrasive element may be present substantially on the entire surface of the compliant layer, or there may be a support layer region that does not include abrasive elements. In some embodiments, the abrasive element has an average surface coverage of the compliant layer, as determined by the number of abrasive elements, the cross-sectional area of each abrasive element, and the cross-sectional area of the polishing pad, of the total area of the major surface of the compliant layer About 30% to about 95%.

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

Prior to the first use of the polishing pad (2 in FIG. 3, 2 'in FIG. 4) in a polishing operation, in some exemplary embodiments, each of the polishing elements (4 in FIG. 3 and 24 in FIG. 3) 3 to 10, and in FIG. 4, 30). In another exemplary embodiment, each abrasive element extends along a first direction at least about 0.25 mm above a plane that includes a guide plate (31 in Fig. 4). In a further exemplary embodiment, each abrasive element extends along a first direction at least about 0.25 mm above the plane comprising the support layer (10 in Figure 3). In a further exemplary embodiment, the height of the base or abrasive surface of the abrasive element (2 in Fig. 3, 2 ' in Fig. 4) May be 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 material selected for use.

Referring again to FIG. 4, the depth and spacing of the apertures 26 across the polishing composition distribution layer 28 and the guide plate 31 may vary as required for a particular CMP process. Each of the abrasive elements 24 is maintained in a planar orientation relative to each other and to the abrasive composition distribution layer 28 and guide plate 31 and protrudes above the surface of the abrasive composition distribution layer 28 and guide plate 31 .

In some exemplary embodiments, the abrasive elements (4 in FIG. 3, 24 in FIG. 3) on the guide plate 31 and any polishing composition distribution layer (28 in FIG. 4) or on the support layer The volume produced by the extension may provide space for dispensing the polishing composition on the surface of the polishing composition distribution layer (28 in FIG. 4) or the support layer (FIG. 3 in FIG. 3). The polishing element (4 in Fig. 3, Fig. 4 in Fig. 4) has the same characteristics as the material characteristic of the abrasive element and the abrasive composition (the working liquid and / or the polishing liquid) on the surface of the polishing composition distribution layer (28 in Fig. 4) (FIG. 4) 28 or the support layer (8 in FIG. 3) by an amount that is at least partially dependent on the desired flow of the polishing composition (e.g., polishing slurry).

Guide plates useful in some embodiments may be made from a wide variety of materials, such as polymers, copolymers, polymer blends, polymer composites, or combinations thereof. Nonconductive and liquid impermeable polymeric materials are generally preferred, and polycarbonates have been found to be particularly useful.

Optional abrasive composition dispensing layers useful in some embodiments can also be made from a wide variety of polymeric materials. The polishing composition dispensing layer, in some embodiments, comprises at least one hydrophilic polymer. Preferred hydrophilic polymers include polyurethanes, polyacrylates, polyvinyl alcohols, polyoxymethylene, and combinations thereof. The polymeric material is preferably porous and more preferably comprises a foam to provide a positive pressure towards the substrate during the polishing operation when the polishing composition distribution layer is compressed. Foamed or porous materials with open or closed cells may be desirable in some embodiments. In certain embodiments, the polishing composition dispensing layer has a porosity of from about 10% to about 90%. In an alternative embodiment, the layer of abrasive composition comprises a hydrogel material, such as, for example, a hydrophilic urethane, which is capable of absorbing water, preferably in the range of about 5 to about 60 weight percent, to provide a lubricating surface during the polishing operation .

In some exemplary embodiments, the polishing composition distribution layer can distribute the polishing composition substantially uniformly across the surface of the substrate to be polished to provide a more uniform polishing. The polishing composition distribution layer can optionally control the flow rate of the polishing composition during polishing, including flow resistance elements, such as baffles, grooves (not shown), pores, and the like. In a further exemplary embodiment, the polishing composition distribution layer may comprise various layers of different materials to achieve the desired polishing composition flow rate at varying depths from the polishing surface.

In some exemplary embodiments, the at least one abrasive element may include an open core region or cavity defined within the abrasive element, but such an arrangement is not required. In some embodiments, the core of the abrasive element may include a sensor for detecting pressure, conductivity, capacitance, eddy current, etc., as described in International Patent Publication No. WO 2006/055720 (Torgerson et al.).

In some embodiments of the polishing pad and / or polishing pad manufacturing method disclosed herein, the support layer comprises a flexible and compliant material. The support layer is typically a film that provides a surface upon which a composition comprising a thermosetting resin composition and a radiation curable resin composition can be cured thereon. In some exemplary embodiments in which the porous abrasive layer comprises abrasive elements, a support layer may be formed as a single sheet of abrasive elements secured to the support layer in an abrasive element, at least a portion of which comprises a porous abrasive element.

The support layer also serves to protect the compliant layer from water or other fluid in the polishing composition while the polishing pad is in use. The support layer is generally fluid impermeable, but a permeable material may be used in combination with an optional barrier to prevent or inhibit fluid penetration through the support layer. In some exemplary embodiments, the support layer comprises a polymeric material selected from silicon, 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 can be made, for example, by extruding a material (e.g., silicone, natural rubber, styrene-butadiene rubber, neoprene, polyurethane, polyolefin, and combinations thereof) into a film. In some embodiments, the material is available from, for example, Lubrizol Advanced Materials, Inc. of Cleveland, Ohio under the trade designation "ESTANE 58887-NAT02" Is a polyurethane available under the trade designation "PELLETHANE ", for example" Peltan 2102-65D " from Dow Chemical, Midland, Mich. ST-1882 ", "ST-1035 "," SS-3331 ", "SS- 1495L ", and" ST- , And "ST-1880 ".

In some embodiments of the polishing pad and / or polishing pad manufacturing methods disclosed herein, the compliant layer comprises a flexible and compliant material, such as a compliant rubber or polymer. The compliant layer is generally compressible to provide a positive pressure towards the polishing surface and may help to provide contact uniformity, for example, between the polishing pad and the surface of the substrate being polished. In some exemplary embodiments, the compliant layer is made of a compressible polymeric material (e.g., a foamed polymeric material made of natural rubber, synthetic rubber, or thermoplastic elastomer). Closed cell porous materials may be useful. In some embodiments, the compliant layer comprises polyurethane and may be, for example, a foamed polyurethane or polyurethane impregnated felt. The thickness of the compliant layer may range, for example, from 0.2 to 3 mm. In some exemplary embodiments where the abrasive layer comprises abrasive elements, the abrasive element, at least a portion of which comprises a porous abrasive element, includes a compliant layer formed as a single sheet of abrasive elements secured to a compliant layer, which may be a porous compliant layer .

In some exemplary embodiments, the compliant layer comprises a polymeric material selected from silicone, natural rubber, styrene-butadiene rubber, neoprene, polyolefin, polyurethane, and combinations thereof. The compliant 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 (although the permeable material may be used in combination with the support layer as described above).

A suitable purchasable compliant layer includes, for example, Rogers Corp, Inc. of Rogers, Connecticut, USA, having product descriptions 4701-60-20062-04, 4701-50-20062-04, 4701-40-20062-04. ) Available under the trade designation "PORON ". Other suitable compliant layers include, for example, polyurethane-impregnated polyester felt available under the trade designation "SUBA IV " from Rodel, Incorporated of Newark, Del. Included is a bonded rubber sheet available under the trade designation "BONDTEX " from Lube Light Cypress Sponge Rubber Products, Inc., Santa Ana, Calif.

In some embodiments of the methods of making an abrasive pad and / or a polishing pad as disclosed herein, the polishing pad may comprise a window extending through the pad in a direction perpendicular to the polishing surface, A transparent layer and / or a transparent abrasive element may be used to allow the optical end point of the polishing process, as described in US Pat.

The term "transparent layer " as used above includes a layer comprising a transparent region, which may be made of the same or different material as the rest of the layer. In some exemplary embodiments, at least one of the areas of the abrasive element, the support layer, the compliant layer, or the abrasive layer or the support layer may be transparent, or may be transparent by applying heat and / or pressure to the material. In some embodiments, the transparent material is cast in place (e.g., using a mold) in an opening appropriately positioned within the layer (e.g., within the abrasive layer, support layer, or compliant layer) Can be generated. In some embodiments, the polishing layer is cured in the presence of the preformed window to create a transparent region within the polishing layer. In some embodiments, the entire support layer and / or compliant layer may be made of a material that can be transparent or transparent to energy within the range of wavelength (s) of interest utilized by the endpoint detection device. Transparent materials suitable for transparent elements, layers or regions include, for example, transparent polyurethanes.

Moreover, as used above, the term "transparent" is intended to include elements, layers and / or regions that are substantially transparent to energy within the range of wavelength (s) of interest utilized by the endpoint detection apparatus. In some exemplary embodiments, the endpoint detection device utilizes one or more sources of electromagnetic energy 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 that at least about 25% (e.g., at least about 35%, at least about 50%, at least about 60% 70% or more, about 80% or more, about 90% or more, or about 95% or more) is transmitted therethrough.

In some exemplary embodiments, the support layer is transparent. In some embodiments, the polishing layer is transparent. In some exemplary embodiments, including the embodiment illustrated in FIG. 3, at least one polishing element is transparent. In some embodiments, the support layer is transparent, at least a portion of the abrasive layer (e.g., abrasive element) is transparent, and there is a hole in the compliant layer aligned with the transparent portion of the abrasive layer.

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

The present invention further relates to a method of using a polishing pad as described above in an abrasive process comprising contacting the surface of a substrate with a porous abrasive layer of a polishing pad according to the present invention, And polishing the surface of the substrate. In some embodiments, the porous polishing layer of the polishing pad comprises a plurality of polishing elements, at least some of which are porous. In some exemplary embodiments, a working liquid may be provided at the interface between the polishing pad surface and the substrate surface. Suitable working liquids are described, for example, in U.S. Patent No. 6,238,592 (Hardy et al.) And 6,491,843 (Srinivasan et al.) And International Patent Publication No. WO 2002/33736 Includes the described.

In some embodiments, the polishing pad of the present invention and / or the polishing pad of the polishing pad made according to the method of the present invention may have an average pore size of greater than or equal to 5 micrometers, greater than or equal to 10 micrometers, or greater than or equal to 15 micrometers. 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 from 5 to 100, from 5 to 75, from 5 to 50, from 5 to 40, or from 5 to 30 micrometers. In some embodiments (e.g., embodiments wherein at least one of the surfactants is included or the polymer particles are fibers), the polishing pad may have an average pore size of up to 30, 25, or 20 micrometers. The pore size generally refers to the pore diameter. However, in embodiments where the pores are non-spherical, the pore size can refer to the largest dimension of the pores. In some embodiments, the pore size non-uniformity ranges from 40 to 75% or from 40 to 60%. In some embodiments, the pore size non-uniformity is at most 75, 70, 65, 60, 55, or 50%. On the contrary, the comparative composition comprising the thermosetting composition may have a pore size non-uniformity of greater than 80, 90 or 100%. In some embodiments, the polishing layer in the polishing pad according to the present invention may have a porosity in the range of 5 to 60%, or in the range of 5 to 55%, in the range of 10 to 50%, or in the range of 10 to 40%.

The difference between the control of the pore size in the polishing layer according to the invention and in the comparative thermosetting composition is illustrated in Figures 5A, 5B, 6A and 6B. Figures 5A and 5B are cross-sectional and plan-view micrographs of the cured compositions described in Example 2 of the following examples, respectively. On the other hand, FIGS. 6A and 6B are cross-sectional and plan-view micrographs of the cured composition of Comparative Example 3, respectively. Both Example 2 and Comparative Example 3 were prepared using 10 wt% polymer particles and mixed in the same manner. However, Example 2 was cured by both radiation curing and thermal curing, and Comparative Example 3 was cured by thermal curing alone. Micrographs illustrate that the pores of Example 2 are better controlled than the pores of Comparative Example 3. The data in Table 1 of the following examples also support that the size range is lower, the pore size non-uniformity is lower, and the hardness is higher in Example 2 than in Comparative Example 3. [

Without wishing to be bound by theory, it is believed that control over pore size and pore size non-uniformity can be correlated to the hardness of the polishing layer. In some embodiments, the porous abrasive layer has a hardness of 40, 45, or greater than 50 Shore D. The hardness can be measured according to Test Method 2, for example, as described in the following examples. On the contrary, the comparative composition comprising the thermosetting composition may have a hardness of less than 40 Shore D.

Surfactants are useful, for example, in the compositions and porous polishing layers disclosed herein to reduce pore size and pore size range and improve pore distribution, as compared to double curing methods, typically without the presence of a surfactant. In other words, the addition of a surfactant can help to provide better control over pore size distribution and pore size, density and shape, which in turn can lead to uniform performance (e. G., Removal rate and uniformity within the wafer) It can have a positive impact on core metrics. The cross-sectional and cross-sectional micrographs of the cured compositions described in Example 15, below, of each of the following Examples, in FIGS. 7a and 7b, show that addition of a surfactant can have a positive effect on pore size range and pore distribution . For example, the pore size range in Example 15 is lower than in Example 2, which has the same number of polymer particles and is prepared in the same manner, but without a surfactant.

In selected embodiments of the present invention

In the first embodiment,

A compliant layer having first and second opposing faces; And

A polishing pad comprising a porous polishing layer disposed on a first side of a compliant layer, the porous polishing layer comprising

A crosslinked network comprising a thermally cured component and a radiation cured component wherein the radiation cured component and the thermally cured component are covalently bonded in a crosslinked network;

Polymer particles dispersed within a crosslinked network; And

And closed cell pores dispersed within the crosslinked network.

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

In a third embodiment, the present invention provides a polishing pad according to the first or second embodiment, wherein the thermosetting component comprises at least one of polyurethane or polyepoxide and the radiation cured component is a poly Acrylate, polymethacrylate, poly (vinyl ether), polyvinyl, or polyepoxide.

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

In a fifth embodiment, the present invention provides a polishing pad according to any one of the first to fourth embodiments, wherein the polymer particles are shared by at least one of a thermally cured component or a radiation cured component in a cross- .

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

In a seventh embodiment, the present invention 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 invention provides a polishing pad according to any preceding embodiment, wherein the porous polishing layer has a hardness of greater than 40 Shore D as measured by Test Method 2. [

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

In a tenth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the polymer particles are substantially spherical.

In an eleventh embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the polymer particles are fibers.

In a twelfth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the polymer particles are present at a maximum of 20% by weight based on the total weight of the porous polishing layer.

In a thirteenth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the pores have a pore size non-uniformity of at most 75%.

In a fourteenth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the pores have an average pore size in the range of 5 micrometers to 100 micrometers.

In a fifteenth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the polishing layer comprises a separate polishing element projecting from the support layer or the compliant layer.

In a sixteenth embodiment, the present invention provides a polishing pad according to the fifteenth embodiment, wherein each of the polishing elements has an end on a circle from the support layer, and the distal end is moved in an axis perpendicular to the polishing surface of the polishing element It is possible.

In a seventeenth aspect, the present invention further provides a polishing pad according to the fifteenth or sixteenth embodiment, further comprising a guide plate having a plurality of openings, each of the separate polishing elements projecting through one of the plurality of openings do.

In an eighteenth embodiment, the present invention provides a polishing pad according to any one of the fifteenth to seventeenth embodiments, wherein the polishing element is fixed to the compliant layer using an adhesive.

In a nineteenth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the compliant layer comprises at least one of silicon, natural rubber, styrene-butadiene rubber, neoprene, polyolefin, or polyurethane .

In a twentieth embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein at least a portion of the polishing pad is transparent.

In a twenty-first embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the polymer particles are water soluble.

In a twenty-second embodiment, the present invention provides a polishing pad according to any preceding embodiment, wherein the porous polishing layer further comprises a surfactant in the crosslinked network.

In a twenty-third embodiment, the present invention provides a method of making a polishing pad,

Providing a composition comprising a thermosetting resin composition, a radiation curable resin composition, and polymer particles;

Forming pores in the composition;

Placing the composition on a support layer; And

Exposing the composition to radiation and at least partially curing the thermosetting resin composition to at least partially cure the radiation curable resin composition, and heating the composition to form a porous abrasive layer on the support layer.

In a twenty-fourth aspect, the present invention provides a method according to the twenty-third embodiment, further comprising the step of adhesively bonding the compliant layer to the surface of the support layer opposite to the porous abrasive layer.

In a twenty-fifth embodiment, the present invention provides a method according to the twenty-third or twenty-fourth embodiment, wherein the thermosetting resin composition comprises a first resin having at least two isocyanate groups or at least two epoxide groups and at least two At least a second resin having a hydroxyl, amino, carboxy, or mercaptan group, wherein the radiation curable composition comprises at least two acrylates, methacrylates, vinyls, or epoxide groups.

In a twenty-sixth embodiment, the present invention provides a method according to the twenty-fifth embodiment 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 , The radiation curable composition 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, the present invention 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 invention provides a method according to any one of the twenty-third to twenty seventh embodiments, further comprising the step of locating the open mold in the composition on the support layer prior to forming the porous abrasive layer.

In a twenty-ninth embodiment, the present invention provides a method according to any one of the twenty-third to twenty-eighth embodiments, wherein the pores are closed cell pores.

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

In a thirtieth embodiment, the present invention provides a method according to any one of the twenty-third to thirty-first aspects, wherein the polymer particles have an average particle size in the range of from 5 micrometers to 500 micrometers.

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

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

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

In a 36 th embodiment, the present invention provides a method according to any one of the 23 th to 35 th embodiments wherein the polymer particles are present at up to 20 wt% based on the total weight of the porous abrasive layer.

In a thirty-seventh embodiment, the present invention provides a method according to any one of the twenty-third to thirty-sixth aspects, wherein the pores have a pore size non-uniformity of at most 75%.

In a thirty-38th embodiment, the present invention provides a method according to any one of the twenty-third to thirty-seventh embodiments, wherein the pores have an average pore size ranging from 5 micrometers to 100 micrometers.

In a 39th embodiment, the present invention provides a method according to any one of the 23rd to 38th embodiments, wherein the polishing layer comprises a separate abrasive element secured to the support layer and projecting therefrom.

In a 40 th embodiment, the present invention provides a method according to the 39 th embodiment, wherein each of the separate abrasive elements has a fixed end and an end on the circle from the support layer, the distal end being perpendicular to the abrasive surface of the abrasive element Lt; / RTI &gt; axis.

In a forty-first embodiment, the present invention provides a method according to any one of the twenty-third to thirty-eighth embodiments, wherein the abrasive layer comprises a separate abrasive element projecting from the compliant layer, And the distal end is movable in an axis perpendicular to the polishing surface of the abrasive element.

In a 42nd embodiment, the present invention provides a method according to any one of &lt; RTI ID = 0.0 &gt; 39th &lt; / RTI &gt; to 41st embodiments, further comprising a guide plate each having a plurality of openings, to provide.

In a forty-third embodiment, the present invention provides a method according to any one of the twenty-third to forty-ninth embodiments, wherein the support layer comprises at least one of silicon, natural rubber, styrene-butadiene rubber, neoprene, polyolefin or polyurethane One.

In a 44th embodiment, the present invention provides a method according to any one of the 23rd to 43rd embodiments, wherein at least a portion of the polishing pad is transparent.

In a forty-fifth embodiment, the present invention provides a polishing method,

Contacting the substrate surface with a porous polishing layer of a polishing pad according to any one of the first to twenty-second embodiments; And

And polishing the substrate surface by relatively moving the polishing pad relative to the substrate.

In a forty-sixth embodiment, the present invention provides a process of the forty-fifth embodiment, further comprising the step of providing a working liquid at the interface between the porous polishing layer and the substrate surface.

An exemplary polishing pad according to the present invention will now be illustrated with reference to the following non-limiting embodiments.

Test method 1: FESEM

According to conventional procedures, scanning electron micrographs (plan and sectional views) of the article were obtained using a Hitachi S-4500 FESEM available from Hitachi High-Technologies Corporation, Tokyo, Japan. Cross sections of the articles were obtained by cutting with a sharp razor blade. Subsequently, the samples were sputter coated with Au / Pd using conventional techniques prior to SEM inspection. An image of the cross section and plane of the article was obtained.

Test method: 2: Hardness

Hardness measurements were made using a Model 1500 Shore D hardness meter available from Rex Gauge Company, Inc., Buffalo Grove, Illinois, USA. The values recorded in Table 1 are the average of 5 measurements, each measurement being made on the different polishing features of the example.

Test method 3: Measurement of pore size through optical microscope

Pore size average, pore size standard deviation (Std. Dev.), Pore size range (observed maximum pore-observed minimum pore size), pore size non-uniformity (pore size standard deviation / average pore size x 100) (Measured area of the image of the pore / total area of the image x 100) was measured with an image-proplus analysis software available from Media Cybernetics, Bethesda, Md., USA, Was determined using image analysis of optical images obtained using a MM-40 Nikon measurement microscope available from Nikon Instruments, Inc.

Prior to optical image formation, samples were prepared in the following order. Three abrasive features were cut from the article and the 3M SCOTCH-WELD Epoxy Potting Compound / Adhesive DP270 clear from the 3M Company, St. Paul, Minn. (CLEAR) " was sealed in the form of a phenol ring having an inside diameter of 2.5 cm and an inside diameter of 2.2 cm available from Buehler Ltd., Lake Bluff 41, Illinois, USA. The features embedded in the epoxy were micro-polished using a Ecomet 3 grinder-grinder available from Mueller Limited, using a 6-step process with a down force of 29.3 ㎪ (4.25 psi) During all six steps, the head and platen speed was 120 rpm. In all cases, the sandpaper or polishing pad indicated was mounted on the platen of ECOMET 3 using a pressure sensitive adhesive (psa).

Step 1: 20.3 cm (8 inch) diameter, 240 grit disks, obtained from 3M Company under the trade designation "3M WETORDRY PSA Disc 21366 ", grinding time was 3 minutes using water as a grinding fluid .

Step 2: A 20.3 cm (8 inch) diameter, 600 grit disk, obtained from Poller Limited under the trade designation "CARBIMET 8" PSA disk 30-5118-600-100, grinding time, Min.

Step 3: A 20.3 cm (8 ") diameter pad, available from Dow Corning Limited under the trade designation" TEXMET 1500 Polishing Pad ", 40-8618, For 6 minutes using a 15 탆 grade polycrystalline diamond suspension 90-30035 available from Allied High Tech Products,

Step 4: 20.3 cm (8 inch) diameter pad, obtained from Dow Corning Limited under the trade designation "Texmet 1500 Polishing Pad ", 40-8618, polishing time is 6 탆 grade available from Allied High Tech Products, And using a polycrystalline diamond suspension 90-30025 for 6 minutes.

Step 5: 20.3 cm (8 inch) diameter pad, obtained from Voller Limited, Texte 1500 Polishing Pad, 40-8618, polishing time, 3 占 퐉 grade available from Allied High Tech Products, And using a polycrystalline diamond suspension 90-30020 for 6 minutes.

Step 6: 20.3 cm (8 inch) diameter pad, obtained from Dow Corning Limited, Texex 1500 Polishing Pad, 40-8618, polishing time, 1 占 퐉 grade available from Allied High Tech Products, Using a polycrystalline diamond suspension 90-30015 for 6 minutes.

After polishing, the polished surface of the feature was coated with carbon using a conventional technique using a sputter coater available from Denton Vacuum, LLC, Moorestown, NJ, USA. Optical image formation was subsequently carried out.

Example 1

Example 1 was prepared by placing 0.28 g of 5350D, 2.15 g of M1, 1.83 g of PHP-75D, 1.27 g of D100 and 0.06 g of TPO-L in a 50 mL plastic beaker. The beaker is placed in an Awatori-Rentaro AR-500 Thinky Mixer (obtained from Thinky Corporation, Tokyo, Japan) and the AR-500 is operated in a two-step process to convert the ingredients And mixed together. The first step was carried out for 5 minutes with rotation of 1000 rpm and revolutions of 1000 rpm. The second step was immediately followed by the first step and was carried out for 15 seconds with rotation of 30 rpm and revolution of 2000 rpm to form a resin mixture. The resin mixture was poured into a Teflon coated, Ni plated aluminum mold formed from an aluminum plate having a length of 19.5 cm and a width of 9.2 cm. The mold consisted of a square array of tapered cylindrical cavities. The cavity was 7.8 mm in diameter at the top of the cavity and 6.5 mm in diameter at the bottom of the cavity and 1.8 mm in depth. The distance from the center to the center between the cavities was about 11.7 mm. One piece of polyurethane film ST-1880 was used as backing. The backing was cut to a size of about 12 cm x 10 cm and placed on the area of the mold containing the resin mixture. A quartz plate of 28 cm length x 17 cm wide x 3.5 mm thick was placed on top of the polyurethane backing and the resin was forced into the cavity to create a thin land area of about 0.5 mm thick of the resin mixture between the cavities.

The mold, resin mixture, backing and quartz plates were placed in two ultraviolet lamps (Fusion Systems Inc., Gaithersburg, Maryland, USA) operating at about 157.5 watts / "V" bulb) to UV cure the resin mixture. The mold was passed under light at a rate of about 2.4 meters per minute (8 feet per minute) and the radiation passed through the quartz plate and the polyurethane backing to reach the resin mixture. The mold, the partially cured resin mixture and the polyurethane backing were then thermally cured by moving the air flow through the oven with a set temperature of 100 DEG C for 2 hours. The cured article was removed from the mold by gently pulling the polyurethane backing to form Example 1, an article having structured abrasive features.

Example 2

Example 2 was prepared in the same manner as in Example 1, except that the composition of the resin mixture was 0.550 g of 5350D, 2.15 g of M1, 1.83 g of PHP-75D, 1.27 g of D100 and 0.06 g of TPO-L .

Example 3

Example 3 was prepared in the same manner as Example 1, except that the curing was carried out in the reverse order and the heat curing first followed by UV curing.

Example 4

Example 4 was prepared in the same manner as in Example 2, except that the curing was carried out in the reverse order, followed by thermosetting followed by UV curing.

Comparative Example C1

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

Comparative Example C2

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

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 of 5350D, 35.00 g of M1, 29.69 g of PHP-75D, 20.63 g of D100 and 1.03 g of TPO-L in a 500 mL plastic beaker. The ingredients were mixed together by placing the beaker in an AR-500 tincture mixer with Awatori-Lentar and operating the AR-500 in a two-step process. The first step was carried out for 5 minutes with rotation of 1000 rpm and revolutions of 1000 rpm. The second step was immediately followed by the first step and was carried out for 15 seconds with rotation of 30 rpm and revolution of 2000 rpm to form a resin mixture.

Approximately 28 cm x 28 cm coating of the resin mixture was coated with a thermoplastic polyurethane (TPU), ESTAN 58887-NAT02 (trade name) using a knife coater with a width of about 53 cm (21 inches) and a gap of 1.52 mm (Available from Lubrizol Advanced Materials, Inc., Cleveland, Ohio, USA) was prepared on a 26 um thick backing formed by extruding in film form at 182 DEG C on a paper release liner.

The coated resin mixture and backing were placed on a 30.5 cm x 30.5 cm (12 inch x 12 inch) aluminum plate with a thickness of 6.35 mm (0.25 inch). 36 magnets with a diameter of 9.6 mm (0.375 inches) and a thickness of 3.2 mm (0.125 inches) were fitted into the recess in the back of the aluminum plate. The 36 recesses were square arrays with a distance of about 5 cm from the center to the center between the recesses. The diameter and depth of the recesses were 9.8 ㎜ and 4.3 ㎜, respectively. Approximately 41 cm x 30 cm Teflon coated metal screen, having a hexagonal array of circular holes with a diameter of approximately 6.2 mm and a center-to-center distance of approximately 8 mm, having a thickness of approximately 1.6 mm, was placed on top of the resin mixture coating I have. The magnetic attraction between the screen and the magnet in the aluminum plate forced the screen to pass through the resin mixture coating leaving a thin land area of the coating between the metal screen and the backing. The UV curing of the coating was carried out in the same manner as in Example 1 except that no quartz plate was used. Thermal curing was followed using the same procedure as described in Example 1.

After removal from the oven, the metal screen was removed from the cured resin to form a textured pad surface bonded to the original paper backed polyurethane backing. The paper was removed to expose the opposing side of the polyurethane backing. Using a 3M Adhesive Transfer Tape 9672 (available from 3M Company), 127 탆 thick transcription adhesive, the polyurethane backing of the textured pad surface was transferred to a 30 cm x 1.59 mm (0.0625 inch) (PORON) urethane foam, part number 4701-50-20062-04 (American Flexible Products, Inc., Charska, MN, USA) A 23 cm diameter pad with a 18 mm diameter center hole was die cut from the laminate to form a pad with the structured polishing features of the present invention, Example 5.

Comparative Example C4

Comparative Example C4 shows that the composition of the resin mixture is 5350D of 10.48 g, M1 of 35.00 g, and 59.38 g of PHP-75D, except that only the thermal curing at 100 ° C for 2 hours is used and the UV curing step is omitted Was prepared in the same manner as in Example 5.

The hardness, pore size average, pore size standard deviation, pore size range, pore size non-uniformity and porosity of Examples 1 to 5 and Comparative Examples C1 to C4 were measured using Test Method 2 and Test Method 3 Respectively. The results are shown in Table 1 below.

[Table 1]

Example 6

Example 6 was prepared in the same manner as in Example 1 except that the composition of the resin mixture was 5150D of 0.28 g, M1 of 2.15 g, PHP-75D of 1.83 g, D100 of 1.27 g and TPO-L of 0.06 g .

Exemplary Embodiment I-1

Exemplary Embodiment I-1 is similar to Example I-1 except that the composition of the resin mixture is 5070 D, 2.15 g M1, 1.83 g PHP-75D, 1.27 g D100 and 0.06 g TPO-L, Were prepared in the same manner.

Example 7

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

Example 8

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

Example 9

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

Exemplary Embodiment I-2

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

The FESEM (Test Method 1) results of Examples 6 to 9 show that they have an acceptable level of porosity. The FESEM (Test Method 1) results of Example I-1 and Example I-2 showed that they had low levels of porosity.

Example 10

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

The screen with the TPU backing and resin mixture was placed under two ultraviolet light lamps operating at 157.5 watts / cm (400 watts / inch) ("V" bulb available from Fusion Systems Inc., Gaithersburg, Md.) And the resin mixture was UV-cured. The resin mixture was passed under light at a rate of about 2.4 meters per minute (8 feet per minute) and the radiation passed through the resin mixture. Thereafter, a fluoropolymer coated polyester film release liner, available from 3M Company as the trade name "SCOTCHPAK 1022 Release Liner" was placed on the screen and the resin mixture partially cured. The assembly was then turned upside down with the polyurethane backing up and the fluoropolymer coated polyester film / screen / partially cured resin mixture to go to the bottom. The quartz plate was placed on top of the backing and the entire assembly was passed through a second identical UV curing process. After the second UV curing was completed, the quartz plate and the fluoropolymer coated polyester film were removed and the screen / partially cured resin mixture / backing assembly was transferred to the air flow through the oven at a set temperature of 100 DEG C for 2 hours The resin mixture was thermally cured. After cooling to room temperature, a 23 cm diameter pad with a central hole of 18 mm diameter was made as described in Example 5 to produce Example 10.

Example 11

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

Example 12

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

Example  13

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

Example 14

Example 14 was prepared by placing 6.88 g of A15LV, 127.78 g of P-250, 6.11 g of TPO-L and 3.51 g of DC5604 in a 650 ml plastic vessel. The ingredients were mixed together by placing the container in an AR-500 tinky mixer with Awatori-Lentar and operating the AR-500 for 4 minutes at 1000 rpm revolutions and 1000 rpm revolutions. The vessel was removed from the mixer and 87.29 g of PHP-75D and 122.22 g of D100 were added to the vessel. The mixture was subjected to a two-step mixing process. The first step was carried out for 4 minutes with rotation of 1000 rpm and revolutions of 1000 rpm. The second step was immediately followed by the first step and was carried out for 15 seconds with rotation of 30 rpm and revolution of 2000 rpm to form a resin mixture.

Approximately 53.3 cm x 58.4 cm (21 in x 23 in) coating of the resin mixture was applied using a knife coater with a width of about 53 cm (21 inches) and a gap of 1.52 mm (60 mils) 58309-022 "was produced on a 102 mm (4 mil) thick backing formed by extruding in film form at 210 DEG C onto a conventional 102 mu m (4 mil) polyester release liner.

The coated resin mixture and backing were placed on an aluminum plate of 61.0 cm x 61.0 cm (24 inches x 24 inches) with a thickness of 6.35 mm (0.25 inches). 113 magnets with a diameter of 9.6 mm (0.375 inches) and a thickness of 3.2 mm (0.125 inches) were fitted into the recess in the back of the aluminum plate. The recess was a linear array of 15 rows. The eight columns had eight recesses per column while the seven columns had seven recesses per column. 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 the recess (near the edge of the plate) had eight recesses, and the second row had seven recesses. This alternating pattern continued to the 15th column with 8 recesses. The recesses of the even-numbered columns are positioned such that they are centered between the corresponding adjacent column recesses. The diameter and depth of the recesses were 9.8 ㎜ and 4.3 ㎜, respectively. The magnet was fixed in the recess using a tape that could be handled at high temperatures. Teflon coated metal screens of about 61.0 cm x 61.0 cm (24 in x 24 in) with a hexagonal array of circular holes of about 6.2 mm in diameter and about 8 mm in diameter from center to center, about 1.6 mm thick Was placed on top of the resin mixture coating. The magnetic attraction between the screen and the magnet in the aluminum plate forced the screen to pass through the resin mixture coating, leaving a thin land area of the coating between the metal screen and the backing.

The resin mixture was cured according to the same curing procedure of Example 10. After removal from the oven, the metal screen was removed from the cured resin to form a textured pad surface bonded to the original polyester backed polyurethane TPU backing. Using a "3M adhesive transfer tape 9672" (available from 3M Company), a 127 탆 thick transcription adhesive, the polyester release liner on the textured pad surface was applied to an approximately 53.3 cm x 58.4 Cm &lt; / RTI &gt; (21 in x 23 in) polyurethane foam pieces. A pad with a diameter of 20.0 in. (50.8 cm) in diameter was die cut from the laminate to form a pad having the structured abrasive features of the present invention, Example 14.

Comparative Example C5

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

Comparative Example C6

Comparative Example C6 was prepared by using only the thermosetting at 100 DEG C for 2 hours with A15LV having a composition of resin mixture of 1.44 g, 23 g of P-250, 47.50 g of PHP-75D and 0.68 g of DC5604, Was prepared in the same manner as in Example 10.

Comparative Example C7

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

Example 15

Example 15 was prepared in the same manner as in Example 5 except that the composition of the resin mixture was 7.550 g of 5350D, 28.00 g of M1, 23.75 g of PHP-75D, 16.50 g of D100, 0.83 g of TPO-L and 0.77 g of DC5604. .

Comparative Example C8

In Comparative Example C8, the composition of the resin mixture was 5350D of 8.39 g, 28.00 g of M1, 47.50 g of PHP-75D and 3.5 g of DC5604, using only thermal curing at 100 占 폚 for 2 hours and omitting the UV curing step Was prepared in the same manner as in Example 15.

The hardness, pore size average, pore size standard deviation, pore size range, pore size non-uniformity and porosity of Examples 10 to 15 and Comparative Examples C5 to C8 were measured using Test Method 2 and Test Method 3 Respectively. The results are shown in Table 2 below.

[Table 2]

Reference throughout this specification to "one embodiment," " some embodiments, "" one or more embodiments, " or" an embodiment, " Means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of some exemplary embodiments of the invention. Thus, the appearances of the phrase " in one or more embodiments, "in some embodiments," in an embodiment, "or" in an embodiment, " But are not to be construed as being limited to the same embodiments. In addition, certain features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

While the specification concludes with a description of some exemplary embodiments in detail, those skilled in the art will readily appreciate that many modifications, variations, and equivalents may be resorted to, Therefore, it should be understood that the present invention should not be unduly limited to the exemplary embodiments described above. In particular, as used herein, reference to a numerical range by an endpoint is intended to include all numerals contained within that range (e.g., 1 to 5 are 1, 1.5, 2, 2.75, 3 , 3.80, 4, and 5). In addition, all numbers used herein are assumed to be modified by the term "about ". In addition, all publications and patents cited in this specification are herein incorporated by reference in their entirety, as if each individual publication or patent was specifically and individually indicated to be incorporated by reference.

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

Claims (23)

A compliant layer having first and second opposing surfaces; And
A porous abrasive layer disposed on a first side of the compliant layer, the porous abrasive layer comprising
A crosslinked network comprising a thermally cured component and a radiation cured component, wherein the radiation cured component and the thermally cured component are covalently bonded in a crosslinked network;
Polymer particles dispersed within a crosslinked network; And
And a closed cell pore dispersed within the crosslinked network. The polishing pad of claim 1, further comprising a support layer interposed between the compliant layer and the porous abrasive layer. Providing a composition comprising a thermosetting resin composition, a radiation curable resin composition, and polymer particles;
Forming pores in the composition;
Placing the composition on a support layer; And
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 to form a porous polishing layer on the support layer, &Lt; / RTI &gt; Contacting the substrate surface with the porous polishing layer of the polishing pad of claim 1 or 2; And
And polishing the substrate surface by relatively moving the polishing pad relative to the substrate. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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