CN102762340A

CN102762340A - Polishing pad and method of making the same

Info

Publication number: CN102762340A
Application number: CN2010800639123A
Authority: CN
Inventors: 李乃朝; 威廉·D·约瑟夫
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2009-12-22
Filing date: 2010-12-20
Publication date: 2012-10-31
Anticipated expiration: 2030-12-20
Also published as: US20130012108A1; TWI517975B; KR101855073B1; KR20120120247A; WO2011087737A3; SG181890A1; WO2011087737A2; JP2013515379A; TW201130656A; JP5728026B2

Abstract

The disclosure is directed to polishing pads with porous polishing layers, methods of making such polishing pads, and methods of using such pads in a polishing process. The polishing pad includes a compliant layer having first and second opposing sides and a porous polishing layer disposed on the first side of the compliant layer. The porous polishing layer includes 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 the crosslinked network. The porous polishing layer also includes polymer particles dispersed within the crosslinked network, wherein the polymer particles comprise at least one of thermoplastic polymers or thermoset polymers. The porous polishing layer typically also includes closed cell pores dispersed within the crosslinked network.

Description

Polishing pad and manufacturing approach thereof

The cross reference of related application

The rights and interests of the U.S. Provisional Patent Application of the U.S. Provisional Patent Application number submission on December 13rd, 61/288,982 and 2010 that the application requires to submit on December 22nd, 2009 number 61/422,442, the full content of these patent applications is incorporated the application into to quote mode as proof.

Background technology

In the manufacture process of semiconductor device and integrated circuit, come to handle times without number material layer and the apparatus structure of silicon chip to cover on forming through a series of deposition and etching step.Can use the polishing technology that is called as chemical mechanical planarization (CMP) to remove the surface imperfection thing (for example swelling, have zone, groove and the ditch of not equal altitude) that stays after deposition and the etching step; Target promptly has the height homogeneity for obtaining not have the level and smooth wafer surface of cut and depression (being called as the butterfly hole) on the entire wafer surface.

In typical C MP glossing; To press down to be affixed on the polishing pad and with respect to polishing pad in the situation that has hydraulic fluid like the substrate of wafer and so on and relatively move, said hydraulic fluid be generally the slurries of abrasive particle in water and/or etch chemistries.The various CMP polishing pads that use with abrasive water are published in for example U.S. Patent number 5,257,478 (people such as Hyde); 5,921,855 (people such as Osterheld); 6,126,532 (people such as Sevilla); Among 6,899,598 (Prasad) and 7,267,610 (people such as Elmufdi).The fixed-abrasive polishing pad is known, like U.S. Patent number 6,908, is given an example among 366 (Gagliardi), and wherein the form of the abrasive composites of the precise forming of abrasive grain Chang Yicong pad surface extension is fixed to the surface of pad usually.Recently, the polishing pad that has a plurality of polishing elements that extend from compressible bottom is described in the international application published WO/2006057714 (Bajaj).Although multiple polishing pad is known and is able to use; But the novel and improved polishing pad that is used for CMP is still being continued to seek in this area; In particular for wherein using bigger chip diameter, or need in the CMP technology of the higher wafer surface flatness and the polishing uniformity.

Summary of the invention

The invention provides porous polishing pad and the method for making this polishing pad, said polishing pad has polishing layer, and said polishing layer has heat cure component and radiation curable component.The hole joins in the said polishing layer through using polymer particle.Hole in the disclosed said porous polishing pad of the application is a closed pore, and its hole with the heat cure polishing pad of routine is compared has lower aperture unevenness and littler aperture usually.The control aperture is favourable with distribution, and is for example, favourable for the polishing performance of polishing pad.

In one aspect, the invention provides a kind of polishing pad, it comprises:

Compliant layers, it has the first and second relative sides; And

The porous polishing layer, it is arranged on first side of said compliant layers, and said porous polishing layer comprises:

Cross-linked network, it comprises heat cure component and radiation curable component, wherein said radiation curable component and said heat cure component covalent bonding in said cross-linked network;

Polymer particle, it is scattered in the cross-linked network; And

Closed pore, it is scattered in the said cross-linked network.In certain embodiments, the supporting course that comprises between said compliant layers and said porous polishing layer is paid somebody's debt and expected repayment later in said polishing.

On the other hand, the present invention provides a kind of method of making polishing pad, and said method comprises:

The composition that comprises heat-curable resin composition, radiation-curable resin composition and polymer particle is provided;

In said composition, form the hole;

Said composition is positioned on the supporting course; And

Through composition being exposed to radiation with partly solidified at least said radiation-curable resin composition, and with said composition heating with partly solidified at least said heat-curable resin composition, thereby on said supporting course, form the porous polishing layer.In certain embodiments, said method also comprises compliant layers is adhered on the surface of the said supporting course relative with said porous polishing layer.

On the other hand, the invention provides a kind of finishing method, it comprises:

The surface of substrate is contacted with porous polishing layer according to polishing pad of the present invention; And

Relatively move said polishing pad to denude the surface of said substrate about said substrate.

Have according to the exemplary embodiment of polishing pad of the present invention and to make it can be used in various characteristics and the characteristic of multiple polishing in using.In certain embodiments, the chemical mechanical planarization (CMP) of the polishing pad of the present invention wafer that can be particularly useful in making integrated circuit and semiconductor device, using.In certain embodiments, polishing pad described in the invention can provide in the following advantage some or all.

For example, in certain embodiments, polishing pad according to the present invention can be used for the hydraulic fluid that uses in the CMP technology is remained between polished surface and the polished substrate surface of pad at the interface, thereby improves the validity of hydraulic fluid in strengthening polishing.In other exemplary embodiments, can reduce or eliminate depression and/or the edge corrosion of wafer surface in polishing process according to polishing pad of the present invention.In certain exemplary embodiment, in CMP technology, use and polish the uniformity, more smooth polished wafer surface in the wafer that can be improved, derive from the condition of work and the uniformity of CMP technology of increase and improvement of the edge crystal grain productive rate of wafer according to polishing pad of the present invention.In a further embodiment, use according to polishing pad of the present invention and can allow in the surface evenness that keeps required degree, to handle larger-diameter wafer to obtain high chip productive rate, before the surperficial needs of pad are nursed one's health with the polishing uniformity that keeps wafer surface, handle more the polycrystalline sheet or to reduce the wearing and tearing on processing time and the pad conditioner device.

Among the present invention:

The standard deviation of " aperture unevenness " finger-hole footpath mean value multiply by 100 divided by average pore size.

Term " polyurethane " refer to have a more than amino-formate bond (NH-C (O)-O-), urea key (NH-C (O)-NH-or-NH-C (O)-N (R)-, wherein R can be hydrogen, aliphatic family, alicyclic or aromatic group), the polymer of the combination in any of biuret, allophanates, urea diketone or isocyanurate-bond.

Term " (methyl) acrylic acid ester " refers to acrylic acid ester and methacrylate, and it can comprise the combination of urethane acrylate, methacrylate and acrylic acid ester and methacrylate.

Term " polymerization " is meant the molecule with such structure, and this structure comprises a plurality of repetitions of spreading out from the unit of the molecule of low relative molecular weight.Term " polymerization () " comprise " oligomerization () ".

Term as " one ", " a kind of " and " said " is not to be intended to refer to that odd number is individual, but comprises general category, and object lesson wherein can be used to do explanation and uses.Term " one ", " a kind of " and " said " can exchange with term " at least a (at least a) " and use.

The phrase that followed is enumerated " at least a (individual) " and " comprising at least a (individual) " refer to comprise two or more multinomial combination in any in each and the listed items in the listed items.

Except as otherwise noted, all number ranges include their end points and the non integer value between the end points.

Various aspects and advantage to exemplary embodiment of the present invention gather.Above summary of the invention is not that intention is described each illustrated embodiment of the present invention or every kind of embodiment.The following accompanying drawing and the specific embodiment more specifically illustrate some embodiments of the present invention.

Description of drawings

Further describe exemplary embodiment of the present invention with reference to accompanying drawing, in the accompanying drawings:

Figure 1A and Figure 1B are respectively the cross sectional view of porous polishing pad in the prior art and the micrograph of vertical view;

Fig. 2 is the schematic side elevation according to an embodiment of polishing pad of the present invention;

Fig. 3 is the side view of the polishing pad with protrusion polishing element according to another embodiment of the invention;

Fig. 4 is the side view of the polishing pad with protrusion polishing element according to still another embodiment of the invention;

Fig. 5 A and Fig. 5 B can be used for forming according to the cross sectional view of the hardening composition of the instance 2 of polishing layer of the present invention and the micrograph of vertical view;

Fig. 6 A and Fig. 6 B are respectively cross sectional view and the micrographs of vertical view of the hardening composition of comparative example 3;

Fig. 7 A and Fig. 7 B can be used for forming according to the cross sectional view of the hardening composition of the instance 15 of polishing layer of the present invention and the micrograph of vertical view; And

Fig. 8 is the micrograph that can be used for forming according to the cross sectional view of the hardening composition of the instance 11 of polishing layer of the present invention.

Like reference numerals in the accompanying drawing is indicated similar member.Accompanying drawing not drawn on scale among the application, and in the accompanying drawings, the parts of polishing pad are shown with the size of stressing selected characteristic.

The specific embodiment

Typical C MP pad is made up of the thermosetting with hole (for example, polyurethane) material.Capable of usingly generate said hole like micro-balloon, Soluble Fiber, gas trapping (for example, on the spot or non-produce on the spot) and the several different methods of physics air capture.When these methods of use; Because the thermograde that in polymerisation, produces, epidermis/core effect that die casting produces, the distribution of fiber, the dissolution rate and the polishing chemical reaction of Soluble Fiber, hole dimension, pore volume and pore size distribution in the control pad can be challenging.

Some commercially available CMP spacers have the perforate pad structure that in the curing process of isocyanate resin, produces.Fig. 1 shows can be from PPG Industries (Pittsburgh, the cross sectional view and the vertical view of the perforate CMP pad made from commercial system that PA) obtains with trade name " S7 ".As shown in Figure 1, in this pad, the size in hole, shape and distribution are not controlled.

The present invention relates to improved porous polishing pad, wherein form closed pore usually with controlled dimensions and uniformity.A plurality of exemplary embodiment of the present invention below will be described.Exemplary embodiment of the present invention can be carried out multiple modification and change under the situation that does not break away from the spirit and scope of the present invention.Therefore, should be appreciated that embodiments of the invention should not be limited to the exemplary embodiment of the following stated, but the control of the restriction that should receive to provide in claims and any equivalent thereof.

Referring now to Fig. 2, porous polishing pad 2a comprises compliant layers 10a and is arranged on the porous polishing layer 12a on said compliant layers one side (that is an one of which first type surface).Optional supporting course 8a is between porous polishing layer 12a and compliant layers 10a, and it can be used among some embodiment and method of porous polishing pad of the present invention.The porous polishing layer comprises cross-linked network, is scattered in the polymer particle in the cross-linked network and is scattered in the closed pore in the cross-linked network.Forming the polishing pad and the method for cavity (for example, through corroding or dissolving), polishing pad according to the present invention was exactly porous before the polishing beginning than the component of in polishing process, removing polishing pad.

Exemplary polymer particle in polishing layer can comprise thermoplastic polymer particle, thermosetting polymer particle and their mixture.Term " thermoplastic polymer " refers to not crosslinked basically and does not form the polymeric material of three-dimensional network basically.Term " thermosetting " refers to crosslinked at least in fact polymer, and wherein said polymer has three-dimensional network basically.In certain embodiments; Polymer particle can be selected as and minimize the particles sintering that causes of heating (promptly; On the border of polymer particle, have minimum creeping (plastic flow), and between the particle of the polymer particle in polishing pad of the present invention seldom coalescence or do not have coalescence).In certain embodiments, when the polymer particle of pad comprises the granular thermoplastic polymer, can or prepare polishing pad below the weld point at granular thermoplastic polymer's fusion point.In other embodiments, polymer particle comprises thermosetting polymer.

Realize that the polymer particle that the present invention can use can pass through prepared in various methods (reaction that for example, condensation reaction, free radical cause or their combination).In another embodiment, polymer can comprise through progressively or the network polymers of the IPN that forms of the condensation reaction of carrying out simultaneously and Raolical polymerizable.In the present invention, term " polymer network of IPN " (IPN) is meant the combination that is two kinds of netted polymer, and is at least a just synthetic or crosslinked immediately after another kind occurs in the said polymer.Usually in IPN, between two kinds of polymer, do not exist and induce covalent bond.Therefore, except that mechanical mixture and copolymerization, the IPN representative can be with the various polymerization thing in another mechanism that physically combines.

Polymer particle can pass through prepared in various methods.In certain embodiments, bulky polymer can be ground and be categorized as the particle size range of expectation by low temperature.The shape of polymer particle can be rule or irregular, and can comprise following shape: ball, fiber, dish, thin slice and their combination or mixing.In certain embodiments, polymer particle is a substantially spherical.Term " substantially spherical " refers to that surface of sphere is at least the particle of 0.75 (in certain embodiments, at least 0.8,0.85,0.9,0.95,0.96,0.97 or 0.98).In certain embodiments, polymer particle is a fiber.The aspect ratio (that is, longest dimension is than the shortest size) that can be used for realizing fiber of the present invention is generally 1.5:1 at least, for example, and 2:1,3:1,4:1,5:1,10:1,25:1,50:1,75:1,100:1 or bigger at least.The aspect ratio that can be used for realizing fiber of the present invention is in the scope of 2:1 to 100:1,5:1 to 75:1 or 10:1 to 50:1.

In certain embodiments, the particle mean size of polymer particle is at least 5 (in certain embodiments, at least 7,10,15,20,25,30,40 or 50) micron.In certain embodiments, the particle mean size of polymer particle is (in certain embodiments, at the most 400,300,200 or 100) micron at the most 500.Said granularity is often referred to the diameter of particle; Yet, be that said granularity can refer to the full-size of particle among some embodiment of non-sphere (for example, fiber) at particle.Can confirm the particle mean size of polymer particle through conventional method.For example, the particle mean size of polymer particle light scattering technique capable of using is confirmed as utilizing by Beckman Coulter Incorporated manufacturing and from its Coulter LS Particle Size Analyzer that is purchased acquisition.In this specification and claims, " granularity " refers to based on through utilizing Coulter Counter LS Particle Size Analyzer to carry out the diameter or the full-size of the particle of the percent by volume that light scattering confirms.In this light scattering technique,, all confirm its granularity by revolution hydraulic radius (hydrodynamic radius of gyration) regardless of the true form of particle." on average " granularity is based on the average diameter of the particle of percent by volume.In certain embodiments, be among the embodiment of fiber especially at particle, according to confirming of conventional triage techniques, fiber has up to about 600,500 or 450 microns the maximum particle diameter of (30,35 or 40U.S.Mesh).For example, in certain embodiments, the screen cloth of the opening of at least 97%, 98% or 99% fiber through having 600,500 or 400 microns (30,35 or 40U.S.Mesh).

In certain embodiments, polymer particle has high evenness.In certain embodiments, the non-uniformity of the size of polymer particle is up to 75% (in certain embodiments, up to 70%, 65%, 60%, 65% or 50%).The granularity non-uniformity refers to that the granulometry deviation multiply by 100 divided by particle mean size.

In certain embodiments, polymer particle is solid basically.Among the application, term " solid basically " means that granular polymer is non-hollow, and for example, polymer particle is not the form of hollow microcapsules.Yet in certain embodiments, solid basically polymer particle can contain the bubble of capturing.

The suitable polymers particle comprises polyvinylchloride rope, polyethylene fluoride, polyethylene, polypropylene, nylon, Merlon, polyester, gathers (methyl) acrylic acid ester, polyethers, polyamide, polyurethane, polyepoxides, polystyrene, polyimides (for example, PEI), polysulfones and their mixture.In certain embodiments, the optional autohemagglutination of polymer particle (methyl) acrylic acid ester, polyurethane, polyepoxides and their mixture.

In certain embodiments, polymer particle comprises water soluble particle.Exemplary available water soluble particle by carbohydrate (for example comprises; Polysaccharide like dextrin, cyclodextrin, starch, mannitol and lactose), the particle processed of the combination in any of cellulose (for example, hydroxypropyl cellulose and methylcellulose), protein, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, PEO, water soluble light-sensitive resin, sulfonation polyisoprene, sulfonation polyisoprene copolymers and these materials.In certain embodiments, polymer particle comprises cellulose.In some of these embodiment, polymer particle comprises methylcellulose.Though in these embodiment, polymer particle comprises water soluble particle, polymer particle can form the hole in polishing layer when forming polishing layer.Do not need when forming the hole can be in polishing process the hydraulic fluid of dissolved particles.

In certain embodiments, polymer particle comprises polyurethane, its can by, for example, following material preparation: comprise the resin of at least two isocyanate groups, and/or have the blocked isocyanate reactant of the isocyanate groups of at least two end-blockings; With second resin, it has at least two groups that react with isocyanate groups.

In certain embodiments, first and second resins can mix, and polymerization or solidify to form bulk polyurethane, and it can be ground (for example, low temperature grinds) and classification alternatively subsequently.In certain embodiments, can form polymer particle through following steps: first resin and second mixed with resin are in the same place; While stirring said mixture slowly is poured in the deionized water of heating (alternatively, under the situation that has organic cosolvent and/or surfactant); Separate the bulk material (for example, through filtering) that forms; The bulk material that separates is dry and alternatively the granular polyurethane of drying is classified.In another embodiment, under the situation that has organic solvent (for example, alcohol, water-insoluble ether, side chain and straight-chain hydrocarbons, ketone, toluene, xylenes and their mixture), isocyanates and hydrogenous material can mix.

In certain embodiments, first resin that comprises at least two isocyanate groups can be selected from isocyanate functional monomer, isocyanate-functional prepolymers and their combination.Exemplary suitable isocyanate-monomer comprises aliphatic polymeric isocyanate; Ethylenic unsaturated polyester isocyanates; The alicyclic PIC; Aromatic poly-isocyanate, wherein isocyanate groups is not bonded directly to aromatic ring, for example, α, α ' XDI; Aromatic poly-isocyanate, wherein isocyanate groups is bonded directly to aromatic ring, for example, phenylene diisocyanate; Carbodiimide modified, urea modification and the biuret modified derivative of halogenation, alkylation, alkoxylate, nitrated and these PICs; And two polymerizations of these PICs and trimerization product.

The exemplary aliphatic PIC comprises ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates, nine methylene diisocyanates, 2,2'-dimethyl pentane vulcabond, 2,2; 4-trimethyl cyclohexane vulcabond, decamethylene vulcabond, 2; 4,4-trimethyl-cyclohexane vulcabond, 1,6; 1-hendecane triisocyanate, 1; 3,6-hexa-methylene triisocyanate, 1,8-vulcabond-4-(isocyanato-methyl) octane, 2; 5; 7-trimethylene-1,8-vulcabond-5-(isocyanato-methyl) octane, two (isocyanatoethyl)-carbonate, two (isocyanatoethyl) ether, 2-isocyanato-propyl group-2,6-two isocyanato-caproates, methyllysine vulcabond, methyllysine triisocyanate and their mixture.

Exemplary suitable ethylenic unsaturated polyester isocyanates can comprise butene diisocyanate and 1,3-butadiene-1,4-vulcabond.Exemplary suitable alicyclic PIC comprises IPDI, cyclohexane diisocyanate, methylcyclohexane diisocyanate, two (isocyanato-methyl) cyclohexane, two (isocyanato-cyclohexyl) methane, two (isocyanato-cyclohexyl)-2; 2-propane, two (isocyanato-cyclohexyl)-1,2-ethane, 2-isocyanato-methyl-3-(3-isocyanato-propyl group)-5-isocyanato-methyl-two ring [2.2.1]-heptane, 2-isocyanato-methyl-3-(3-isocyanato-propyl group)-6-isocyanato-methyl-two ring [2.2.1]-heptane, 2-isocyanato-methyl-2-(3-isocyanato-propyl group)-5-isocyanato-methyl-two ring [2.2.1]-heptane, 2-isocyanato-methyl-2-(3-isocyanato-propyl group)-6-isocyanato-methyl-two ring [2.2.1]-heptane, 2-isocyanato-methyl-3-(3-isocyanato-propyl group)-6-(2-isocyanatoethyl)-two ring [2.2.1]-heptane, 2-isocyanato-methyl-2-(3-isocyanato-propyl group)-5-(2-isocyanatoethyl)-two ring [2.2.1]-heptane, 2-isocyanato-methyl-2-(3-isocyanato-propyl group)-6-(2-isocyanatoethyl)-two ring [2.2.1]-heptane and their mixture.

Wherein the isocyanate groups exemplary aromatic poly-isocyanate that is not bonded directly to aromatic ring comprises two (isocyanatoethyl) benzene, α; α; α '; α '-tetramethylene diisocyanate, 1; Two (1-isocyanato--1-Methylethyl) benzene of 3-, two (isocyanato-butyl) benzene, two (isocyanato-methyl) naphthalene, two (isocyanato-methyl) diphenyl ether, two (isocyanatoethyl) phthalate ester, mesitylene triisocyanate, 2,5-two (isocyanato-methyl) furans and their mixture.

Wherein the isocyanate groups exemplary aromatic poly-isocyanate that is bonded directly to aromatic ring comprises phenylene vulcabond, ethyl phenylene vulcabond, isopropyl phenylene vulcabond, dimethyl phenylene vulcabond, diethyl phenylene vulcabond, diisopropyl phenylene vulcabond, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene vulcabond, diphenyl diisocyanate, adjacent tolidine vulcabond, 4; 4'-methyl diphenylene diisocyanate, two (3-methyl-4-isocyanato-propyl group) methane, two (isocyanato-phenyl) ethene, 3; 3'-dimethoxy-diphenyl-4; 4'-vulcabond, triphenylmethane triisocyanate, polymerization 4; 4'-methyl diphenylene diisocyanate, naphthalene triisocyanate, diphenyl methane-2; 4; 4'-triisocyanate, 4-MDPM-3; 5,2', 4'; 6'-five isocyanates, diphenyl ether vulcabond, two (isocyanato-phenyl ether) ethylene glycol, two (isocyanato-phenyl ether)-1, ammediol, Benzophenone vulcabond, carbazole vulcabond, ethyl carbazole vulcabond, dichloro carbazole vulcabond and their mixture.

In certain embodiments; First resin that comprises at least two kinds of isocyanate groups is selected from α; α '-XDI, α; α, α ' α '-tetramethylxylene diisocyanate, IPDI, two (isocyanato-cyclohexyl) methane, toluene di-isocyanate(TDI), 4,4'-methyl diphenylene diisocyanate and their mixture.

In certain embodiments, first resin that has at least two isocyanate groups can comprise the isocyanate-functional polyurethane prepolymer.The isocyanate-functional polyurethane prepolymer can be through multiple routine techniques preparation.In certain embodiments, can one react like at least a polyalcohol of glycol with like at least a isocyanate functional monomer of diisocyanate monomer and have the polyurethane prepolymer of at least two isocyanate groups with formation.Exemplary suitable isocyanate functional monomer comprises aforesaid isocyanate functional monomer.

Can be used for realizing that suitable isocyanate-functional polyurethane prepolymer of the present invention can have the molecular weight that on a large scale, changes.In certain embodiments, the number-average molecular weight of isocyanate-functional polyurethane prepolymer (Mn) can be from 500 to 15000, or from 500 to 5000, it is confirmed according to the gel permeation chromatography (GPC) that for example utilizes polystyrene standard.

The exemplary polyalcohol that can be used for preparing the isocyanate-functional polyurethane prepolymer comprises: the straight or branched alkyl polyols; As 1; 2-ethylene glycol, 1, ammediol, 1,2-propane diols, 1; 4-butanediol, 1,3-butanediol, glycerine, neopentyl glycol, trimethylolethane, trimethylolpropane, two-trimethylolpropane, erythrite, pentaerythrite and two-pentaerythrite; PAG, as two-, three-and tetrem enediol and two-, three-and tetrapropylene glycol; The cyclic alkyl polyalcohol is like pentamethylene glycol, cyclohexane diol, phloroglucitol, cyclohexanedimethanol, hydroxypropyl cyclohexanol and cyclohexane diethanol; Aromatic polyol is like dihydroxy benzenes, benzene triol, the pure and mild orcin of hydroxybenzyl; Bis-phenol, as 4,4'-isopropylidene xenol (bisphenol-A), 4; 4'-oxo biphenol, 4,4'-dihydroxy benzenes ketone, 4,4'-sulfo-biphenol, phenolphthalein, two (4-hydroxyphenyl) methane (Bisphenol F), 4; 4'-(1, the 2-ethenylidene) bis-phenol and 4,4'-sulphonyl bis-phenol; The halogenation bis-phenol, as 4,4'-isopropylidene two (2, the 6-dibromophenol), 4,4'-isopropylidene two (2, the 6-chlorophenesic acid) and 4,4'-isopropylidene two (2,3,5, the 6-tetrachlorophenol); The alkoxyl bis-phenol, like alkoxyl 4,4'-isopropylidene xenol, it has the one or more alkoxy bases like ethyoxyl, propoxyl group, α-butoxy and Beta-Butoxy group; With the dicyclo hexanol, it can prepare through making corresponding bis-phenol hydrogenation, as 4, and 4'-isopropylidene-dicyclo hexanol, 4,4'-oxo dicyclo hexanol, 4,4'-thiobis cyclohexanol and two (4-hydroxyl cyclohexanol) methane.

Other instance that can be used for preparing the suitable polyalcohol of isocyanate-functional polyurethane prepolymer comprises higher PAG, is the polyethylene glycol of from 200 to 2000 gram/moles like number-average molecular weight (Mn); The acrylic resin that has hydroxyl, those that form like the combined polymerization by (methyl) acrylic acid ester and hydroxy-functional (methyl) acrylic acid ester are like methyl methacrylate and hydroxyethyl methacrylate copolymer; And hydroxy-functionalized polyesters, those that form like reaction by glycol (like butanediol) and diacid or diester (adipic acid or diethylene adipate).In certain embodiments, can be used for realizing that polyalcohol of the present invention can have the number-average molecular weight of from 200 to 2000 gram/moles.

In certain embodiments, the isocyanate-functional polyurethane prepolymer can prepare through reacting like the vulcabond of toluene di-isocyanate(TDI) and like the PAG that gathers (oxolane).

In certain embodiments, the isocyanate-functional polyurethane prepolymer can prepare existing under the situation of catalyst.In certain embodiments, based on the gross weight of polyalcohol and isocyanate functional monomer, the amount of the catalyst of use can be less than 5 weight %, or is less than 3 weight %, or is less than 1 weight %.In certain embodiments; Exemplary appropriate catalyst comprises the inferior tin adduct of organic acid; Like stannous octoate, dibutyltin dilaurate, dibutyl tin diacetate, dibutyl tin mercaptides, dibutyl tin dimaleate, stannous methide diacetate, stannous methide dilaurate, 1,4-diazabicylo (2.2.2) octane and their mixture.In other embodiments, catalyst can be the acetylacetonate of zinc octoate, bismuth or iron.Other exemplary appropriate catalyst comprises tertiary amine, like triethylamine, tri-isopropyl amine and N, and the N-dimethyl benzylamine.

In certain embodiments, for the polyurethane that can be used for preparing polymer particle, first resin with at least two isocyanate groups comprises the blocked isocyanate compounds of the isocyanate groups with at least two end-blockings.Term " isocyanate compound of end-blocking " refers to have the monomer or the prepolymer of isocyanate groups end and/or side end-blocking, its isocyanate groups that can be converted into Kaifeng (that is, free) with separate or free end-capping group.The instance of any above-mentioned suitable isocyanate compound can be by end-blocking.The exemplary non-fugitive end-capping group of the isocyanates of end-blocking comprises: the 1H-azoles, and like 1H-imidazoles, 1H-pyrazoles, 3,5-dimethyl-1H-pyrazoles, 1H-1,2; 3-triazole, 1H-1,2,3-BTA, 1H-1; 2,4-triazole, 1H-5-methyl isophthalic acid, 2; 4-triazole and 1H-3-amino-1,2, the 4-triazole; Lactams is like e-caprolactam and 2-Pyrrolidone; Morpholine is like the 3-aminopropyl morpholine; With N-hydroxyl phthalimide.The exemplary fugitive end-capping group of blocked isocyanate compounds comprises: alcohol, like propyl alcohol, isopropyl alcohol, butanols, isobutanol, the tert-butyl alcohol and hexanol; The alkylidene ethylene glycol monoalkyl ether is like ethylene glycol monoalky lether (for example, ethylene glycol single-butyl ether and ethylene glycol list hexyl ether) and propyleneglycoles monoalky lether (for example, propyleneglycoles monomethyl ether); And ketoxime, like methyl ethyl ketoxime.

Though do not hope by any one theory; But it is believed that the isocyanate material that in having first resin of two isocyanate groups, comprises end-blocking at least can cause forming covalent bond with upper/lower positions: (a) between at least a portion of granular polyurethane particle; And/or (b) between at least a portion of at least a portion of granular polyurethane and cross-linked network.In certain embodiments; The isocyanate compound of end-blocking can be according to a certain amount of existence; Said amount makes based on total molar equivalent of the isocyanate groups of free isocyanate and end-blocking; The amount of the isocyanate groups of the first resin end-blocking is at least 5 moles of %, or at least 10 moles of %, or is less than 40 moles of % or is less than 50 moles of %.

Second resin with at least two groups that react with isocyanate groups can be selected from multiple material.In certain embodiments, second resin has the functional group that is selected from hydroxyl, sulfydryl, primary amine, secondary amine and their combination.The exemplary second suitable resin comprises aforesaid polyalcohol.

Second resin that in certain embodiments, can have at least two groups that can react with isocyanate groups comprises polyamine.Exemplary polyamine comprises polyethylene polyamine (ethyleneamine); As 1,2-ethylenediamine (EDA), diethylenetriamines (DETA), trien (TETA), TEPN (TEPA), five ethylidene hexylamines (PEHA), piperazine, diethylene diamine (DEDA) and 2-amino-1-ethyl piperazidine.Other exemplary suitable polyamine comprises one or more isomers of dialkyl group toluenediamine, as 3, and 5-dimethyl-2,4-toluenediamine, 3; 5-dimethyl-2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine, 3; 5-diethyl-2,6-toluenediamine, 3,5-diisopropyl-2; 4-toluenediamine, 3,5-diisopropyl-2,6-toluenediamine and their mixture.In certain embodiments, polyamine can be selected from methylene dianiline (MDA), trimethylene glycol two (para-aminobenzoate) and amine end-blocking oligomer and prepolymer.

In certain embodiments, suitable polyamine can be selected from based on 4,4'-methylene-two (dialkyl aniline) (for example 4; 4'-methylene-two (2, the 6-dimethylaniline), 4,4'-methylene-two (2; The 6-diethylaniline), 4,4'-methylene-two (2-ethyl-6-methylaniline), 4,4'-methylene-two (2; The 6-diisopropyl aniline), 4; 4'-methylene-two (2-isopropyl-6-methylaniline), 4, those of 4'-methylene-two (2,6-diethyl-3-chloro aminobenzen) and their mixture.

In certain embodiments, can carry out existing under the situation of catalyst with the second resins granular polyurethane of at least two groups of isocyanate-reactive with comprising by first resin that comprises at least two isocyanate groups.Appropriate catalyst comprises those that the above preparation that is directed against the isocyanate-functional polyurethane prepolymer is listed.

In certain embodiments; The molar equivalent ratio of isocyanate groups and isocyanate-reactive group of isocyanate groups and optional end-blocking that can be used for preparing granular polyurethane is for from 0.5:1.0 to 1.5:1.0; For example, from 0.7:1.0 to 1.3:1.0 or from 0.8:1.0 to 1.2:1.0.In certain embodiments, can prepare cross-linked polyurethane through second resin that utilization is less than the amount that requires with the Chemical Calculation mode, make amino-formate bond or urea key will with unnecessary isocyanate reaction.In other embodiments, difunctional compound is changed to the trifunctional compound and will causes more heat-staple chemical crosslinking.

Some available granular polyurethanes are commercially available; For example derive from Dainichiseika Color & Chemicals Mfg.Co. with trade name " DAIMIC-BEAZ "; Ltd.Advanced Polymers Group (Tokyo; Japan) granular polyurethane, it is divided into " UCN-5350D ", " UCN-5150D " and " UCN-5070D " grade; Derive from Negami Chemical Industrial Co. with trade name " ART PEARL ", Ltd. (Nomi-city, polyurethane particles Japan); And the thermoplastic polyurethane that for example derives from Bayer Corporation based on aliphatic polyether with trade name " TEXIN ".

In certain embodiments, can be used for realizing that suitable polymers particle of the present invention comprises granular polyepoxides.For example, granular polyepoxides can be by the product preparation of first resin with at least two epoxide groups and second resin with at least two groups that can react with the epoxide group of said epoxides.

In certain embodiments, comprise that first resin of at least two epoxide groups and second resin can mix, and polymerization or solidify to form the bulk polyepoxides, it can be ground (for example, low temperature grinds) and classification alternatively subsequently.In certain embodiments; Can form granular polyepoxides through following steps: with epoxy functional material and hydrogen official can material mixing together, the limit stirs in the deionized water that the companion limit slowly is poured into the gained mixture heating, separates the bulk material (for example, through filtering) that forms, with the bulk material drying of separating and alternatively the granular polyepoxides of drying is classified.

In certain embodiments, can be used for realizing that suitable epoxy functional material of the present invention comprises epoxide-functional monomer, epoxy-functional prepolymer and their combination.Exemplary suitable epoxide-functional monomer can comprise: the aliphatic poly epoxide, and as 1,2,3,4-bicyclic oxygen butane, 1,2,7,8-bicyclic oxygen octane; Alicyclic polyepoxides is as 1,2; 4,5-bicyclic oxygen cyclohexane, 1,2; 5; 6-bicyclic oxygen cyclooctane, 7-oxa--two ring [4.1.0] heptane-3-carboxylic acid 7-oxa--two ring [4.1.0] heptan-3-ylmethyl ester, 1,2-epoxy radicals-4-oxa-base-cyclohexane and 2,3-(glycidyl) cyclohexane; The aromatic series polyepoxides is like two (4-hydroxyphenyl) methane diglycidyl ether; Hydrogenated bisphenol A diepoxide and their mixture.The epoxide-functional monomer that can be used among the present invention is prepared by polyalcohol and epihalohydrin (for example, epoxychloropropane) reaction usually.The polyalcohol that can be used for preparing the epoxy functional monomer comprises those that the application had before given an example about the preparation of isocyanate-functional prepolymers.The available class of epoxide-functional monomer comprise by the prepared in reaction of bis-phenol and epoxychloropropane those (for example, 4, the reaction of 4'-isopropylidene xenol and epoxychloropropane, thus prepare 4,4'-isopropylidene xenol diglycidyl ether).

In certain embodiments, can be used for preparing the epoxy-functional prepolymer of specific ring oxide can be through preparing polymer polyatomic alcohol and epichlorohydrin reaction.Exemplary suitable polymers polyalcohol can comprise PAG, like polyethylene glycol and PolyTHF; PEPA; Polyurethane polyol; Gather ((methyl) acrylic acid ester) polyalcohol; With their mixture.

In some embodiments of the invention; The epoxy-functional prepolymer can comprise that epoxy-functional gathers ((methyl) acrylic acid ester) polymer; It can be by (methyl) acrylate monomer and epoxy-functional free radical polymerizable monomer (for example, glycidyl (methyl) acrylic acid ester) preparation.Suitable epoxy-functional prepolymer can have the molecular weight of broad range.In certain embodiments, confirm that according to the gel permeation chromatography that for example utilizes polystyrene standard (GPC) molecular weight of epoxy-functional prepolymer can be from 500 to 15000 gram/moles, or from 500 to 5000 gram/moles.

Second resin with at least two groups that can react with epoxides can comprise at least a of hydroxyl, sulfydryl, carboxylic acid, primary amine or secondary amine.In certain embodiments, second resin can comprise the polyalcohol that the application had before given an example.In other embodiments, second resin can comprise the polyamine that the application had before given an example.In certain embodiments, suitable polyamine can comprise the polyamide prepolymer polymers with at least two amine groups that are selected from primary amine, secondary amine and their combination.Suitable exemplary polyamide prepolymer polymers for example can comprise and derives from Cognis Corporation with trade name " VERSAMID ", Coating & Inks Division (Monheim, Germany) those.

In certain embodiments, can carry out existing under the situation of catalyst by first resin that comprises at least two epoxide groups and the granular epoxides of second resins that comprises at least two groups that can react with epoxides.Exemplary appropriate catalyst comprises tertiary amine, like triethylamine, tri-isopropyl amine, three tert-butyl amines, tetrafluoro boric acid and N, N-dimethyl benzylamine.In certain embodiments, catalyst can add in second resin before mixing with epoxy functional materials.In certain embodiments, based on first resin that mixes and the gross weight of second resin, the amount of the catalyst of use can be less than 5 weight %, or is less than 3 weight %, or is less than 1 weight %.

The epoxide group and the molar equivalent ratio of epoxide reaction property group that are used to prepare the reactant of particulate crosslinked polyepoxides are generally from 0.5:1.0 to 2.0:1.0, for example, and from 0.7:1.0 to 1.3:1.0 or from 0.8:1.0 to 1.2:1.0.

In certain embodiments, first resin and/or second resin that have at least two isocyanate groups or at least two epoxide groups can comprise known conventional additives alternatively.The instance of these additives comprises heat stabilizer, anti-oxidant, releasing agent, static dyestuff, pigment, like alkoxyl phenol benzoate with gather the softening agent of (alkylene glycols) dibenzoate and like the surfactant of ethylene oxide/propylene oxide block copolymerization surfactant.In certain embodiments, based on first resin that mixes and the gross weight of second resin, the amount of these additives can amount to up to 10 weight %, or up to 5 weight %, or up to 3 weight %.

Can be used for realizing that other polymer particle of the present invention comprises thermoplastic poly (methyl) acrylic acid ester; It for example can trade name " ROHADON " derive from ROHM America; Incorporated (Lawrenceville; Georgia), and with trade name " ART PEARL " derive from Negami Chemical Industrial Co., Ltd..Can be used for realizing that other polymer particle of the present invention for example comprises derives from Dow Chemical Company (Midland, cellulose granules Michigan) with trade name " METHOCEL ".

The amount of the polymer particle that in polishing pad according to the present invention, exists can change.What is interesting is, according to finding, utilize the amount of the polymer particle that particular technology mixes to influence the porosity of gained polishing layer with unexpected mode in certain embodiments.For example, certificate is found, when using the blender that combines revolution and rotation, compares with the particle levels that reaches 15 weight %, and nearly the particle levels of 20 weight % provides less hole.Yet other hybrid technology can provide different results.In certain embodiments, based on the gross weight of granular polymer and cross-linked network, the amount that said polymer particle exists is at least 1 weight %, or at least 2.5 weight %, or at least 5 weight %.In certain embodiments, based on the gross weight of polymer particle and cross-linked network, the amount that said polymer particle exists is up to 25 weight %, or up to 20 weight %, or be less than 20 weight %.

In certain embodiments, comprise that polymer particle is the embodiment of fiber, based on the gross weight of polymer particle and cross-linked network, the amount that said polymer particle exists is up to 10 weight %, or up to 5 weight %, or be less than 5 weight %.Advantageously, though based on the amount of the polymer particle of the gross weight of polymer particle and cross-linked network under situation up to 2 weight %, the polymer particle of fibers form also can provide available porosity level.In some of these embodiment, polymer particle is water-soluble fibre (a for example methylcellulose fiber).Shown in table 1 and table 2 in the instance, the spherical polyurethane particles of comparing with equivalent weight with the methylcellulose fiber obtains higher levels of porosity.Visual comparison between Fig. 8 (micrograph of the cross sectional view of the hardening composition of instance 12) and Fig. 7 A and Fig. 7 B (being respectively cross sectional view and the micrograph of vertical view of the hardening composition of instance 15) demonstrates the porosity that can obtain par with 2 weight % fibers (Fig. 8) with 10 weight % particles (Fig. 7 A and Fig. 7 B).

For example, in polishing process, for the uniformity that improves the distribution of particles on the whole cross-linked network and in order to keep filling up the hardness on surface, the particle that mixes reduced levels possibly be favourable to obtain identical porosity.

Polishing pad according to the present invention comprises polishing layer, and this polishing layer comprises polymer particle and cross-linked network, and cross-linked network comprises and contains heat cure component and radiation curable component.Multiple suitable polymers can be used for forming cross-linked network.In certain embodiments, heat cure component comprises at least a of polyurethane, polyepoxides or urethane-modified polyepoxides.

Usually,, polymer particle forms cross-linked network of the present invention when existing.In certain embodiments, heat-curable resin composition and radiation-curable resin composition can react to form cross-linked network, and this moment, said curable compositions was under the situation that has polymer particle.

In certain embodiments, based on the gross weight of polymer particle and cross-linked network, the disclosed polishing layer of the application can comprise at least 75 weight %, or at least 80 weight %, or the cross-linked network of at least 85 weight %.In certain embodiments, based on the gross weight of polymer particle and cross-linked network, said cross-linked network can be in said polishing layer with up to 99 weight %, or up to 95 weight %, or exist up to the amount of 90 weight %.

Can prepare cross-linked network through conventional polymerization process.In certain embodiments, cross-linked network can being combined to form through condensation reaction, radical initiation reaction or they.In certain embodiments, heat cure component can comprise the polyurethane through the condensation reaction formation of heat-curable resin composition that comprises polyurethane prepolymer and polyamine.In certain embodiments, radiation curable component can comprise carbamate-polyacrylate or the carbamate-polymethacrylates that forms through in the polymerisation that has carbamate-diacrylate or carbamate-dimethylacrylate under the situation of light trigger.In certain embodiments, cross-linked network is the IPN network polymers that forms through the heat cure progressively carrying out or carry out simultaneously and radiation curing polymerisation.In certain embodiments, radiation curable component (polyacrylate or polymethacrylates in certain embodiments) is covalently bound to the heat cure component through carbamate or urea binding groups.

Can be used for realizing that suitable heat-curable resin composition of the present invention can comprise monomer, prepolymer and their mixture.In certain embodiments, heat-curable resin composition can contain catalyst, crosslinking agent, curing agent, solvent and other conventional additives known in the art.

In certain embodiments, heat-curable resin composition comprises: first resin, and it has at least two isocyanate groups (it also can be the isocyanate groups of end-blocking) or at least two epoxide groups; And second resin, it has at least two groups (for example, oh group, amino group, carboxyl group or thiol group) that can react with isocyanates and/or epoxides.

Can be used for preparing the optional isocyanates of before having described with reference to granular polyurethane in this application respectively certainly (comprising prepolymer) of the first and second exemplary suitable resins of heat cure component, isocyanates, polyalcohol and the polyamine of end-blocking.For example, when first and second resin combination, but the beginning of the isocyanates delay gelatinizing effect of use end-blocking, it can allow more time to be used for first and second resins are mixed with polymer particle.

Some isocyanate prepolymers that can be used as first resin are commercially available, for example derive from Air Products and Chemicals with trade name " AIRTHANE PHP-75D ", Inc. (Allentown, isocyanate prepolymer PA).Some diamines that can be used as second resin are commercially available, for example derive from Air Products and Chemicals, the oligomerization diamines of Inc. with trade name " VERSALINK P250 " and " VERSALINK P650 ".

In certain embodiments, comprise radiation curable resins and comprise that first resin with at least two isocyanate groups composition with the thermal curable resin of second resin with at least two groups that can react with isocyanate groups can further comprise catalyst.Exemplary appropriate catalyst can comprise in this application those of before having given an example with reference to being prepared in of granular polyurethane (for example, like the tertiary amine of triethylamine with like the organo-metallic compound of dibutyl tin dilaurate).In certain embodiments, catalyst can mix in second resin before first and second mixed with resin.In certain embodiments, based on first resin that mixes and the gross weight of second resin, catalyst can be according to being less than 5 weight %, or be less than 3 weight %, or the amount that is less than 1 weight % exists.The isocyanate groups of isocyanate groups in first resin and second resin and optional end-blocking and the molar equivalent ratio of isocyanate-reactive group can be from 0.5:1.0 to 2.0:1.0 respectively; For example, from 0.7:1.0 to 1.3:1.0 or from 0.8:1.0 to 1.2:1.0.

In certain embodiments; The heat cure component can be through will having at least two epoxide groups first resin prepare with second resin reaction with at least two groups (for example, oh group, amino group, carboxyl group or thiol group) that can react with epoxides.Exemplary suitable first resin with at least two epoxide groups and second resin comprise that any those are used to prepare epoxides, polyamine and the polyalcohol of granular polyepoxides, and be before said like the application.

In certain embodiments, comprise radiation curable resins and comprise that the composition of the thermal curable resin that is used to prepare first and second resins that gather epoxy radicals heat cure component also can comprise the epoxides ring opening catalyst.The exemplary appropriate catalyst that is used for the open loop of epoxides comprises any above those tertiary amine and the tetrafluoro boric acid of three tert-butylamines (for example, as) of describing.In certain embodiments, catalyst can add in second resin with first and second mixed with resin before.In certain embodiments, based on the gross weight of first resin and second resin, the epoxides ring opening catalyst can be according to being less than 5 weight %, or be less than 3 weight %, or the amount that is less than 1 weight % exists.The molar equivalent ratio of epoxide group in first resin and second resin and epoxide reaction property group can be from 0.5:1.0 to 2.0:1.0 respectively, or from 0.7:1.0 to 1.3:1.0, or from 0.8:1.0 to 1.2:1.0.

In certain embodiments, the thermal curable resin can comprise conventional additives.Exemplary suitable conventional additives comprises among the application with reference to any additives in those additives that are prepared in previous description of preparation granular polyurethane and granular polyepoxides, like releasing agent, dyestuff and softening agent.In certain embodiments, based on the gross weight of cross-linked network, the total amount of additive can be according to being less than 10 weight %, or be less than 5 weight %, or the amount that is less than 3 weight % exists.Conventional additives for example can add in first resin or in second resin.

Porous polishing pad according to the present invention comprises the polishing layer with radiation curable component.Radiation curable component comprises polyacrylate, polymethacrylates, polyvinylether, ethene polymers or polyepoxide.In certain embodiments, radiation curable component comprises at least a of polyacrylate or polymethacrylates.Radiation curable component can be by the radiation curable resins preparation that comprises at least two acrylic acid ester, methacrylate, vinyl (for example, vinyl group, allyl group or styrene group) or epoxide group.In certain embodiments, radiation curable resins comprises at least two acrylic acid ester or methacrylate based group.

In certain embodiments; Radiation curable resins can comprise (methyl) the acrylate modified polyfunctional isocyanate's material with at least two (methyl) acrylate modified isocyanate groups; It can be (for example for example has end and/or the polyurethane prepolymer of side isocyanate groups; Those polyurethane prepolymers that more than combine the preparation of granular polyurethane to describe) with have the product of (methyl) acrylic acid ester of isocyanate-reactive functional group (for example, hydroxyl, amine groups or sulfydryl group).

Exemplary suitable hydroxyl or amino-functional (methyl) acrylic acid ester comprise hydroxyalkyl acrylates and methacrylate; For example 2-hydroxyethylmethacry,ate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylic acid ester, 3-hydroxypropyl acrylic acid ester (HPA), 2-hydroxy propyl methacrylate, 3-hydroxy propyl methacrylate, 1; 3-dihydroxypropyl acrylic acid ester, 2; 3-dihydroxypropyl acrylic acid ester and methacrylate, 2-hydroxyethyl acrylamide and Methacrylamide, 2-hydroxybutyl (methyl) acrylic acid ester, 4-hydroxybutyl (methyl) acrylic acid ester, 2-hydroxyl-3-phenoxy propyl (methyl) acrylic acid ester, 1; 4-butanediol one (methyl) acrylic acid ester, 2-hydroxy alkyl (methyl) acryloyl phosphate, 4-hydroxy-cyclohexyl (methyl) acrylic acid ester, 1,6-hexylene glycol one (methyl) acrylic acid ester, neopentyl glycol one (methyl) acrylic acid ester, trimethylolpropane two (methyl) acrylic acid ester, trimethylolethane two (methyl) acrylic acid ester, pentaerythrite three (methyl) acrylic acid ester, dipentaerythritol five (methyl) acrylic acid ester; N-alkyl-N-hydroxyethyl acrylamide and Methacrylamide, hydroxyethyl-β carboxy ethyl acrylic acid ester, hydroxyl ethylhexyl acrylate, hydroxyl octyl group methacrylate, polypropylene glycol monomethyl acrylic acid ester, propane diols monomethyl acrylic acid ester, caprolactone acrylic acid ester, t-butyl amino-ethyl methacrylate and their mixture.Many commercial sources of passing through in these obtain; For example available hydroxyethylmethacry,ate and hydroxypropyl acrylic acid ester can be from Dow Chemical (Midland; Mich.) and Osaka Organic Chemical Industry Ltd. (Osaka Japan) is purchased acquisition.Available hydroxybutyl acrylic acid ester can be purchased acquisition from Osaka Organic Chemical Industry Ltd..Available hydroxyl polyester acrylic acid ester can trade name " TONE MONOMER M-100 " derive from Dow Chemical Company and derive from Osaka Organic Chemical Industry Ltd. with trade name " VISCOAT 2308 ".Available hydroxy polyethers acrylic acid ester can trade name " ARCOL R-2731 " derive from Bayer Chemicals (Pittsburgh, Pa.).

Sidepiece, end or sidepiece end that (methyl) acrylate group can be positioned on the prepolymer have.In certain embodiments, prepolymer is by (methyl) acrylate group end-blocking.For example, exist under the situation of excess isocyanate usually, can react the resin for preparing radiation-hardenable through (methyl) acrylic acid ester and the polyisocyanate prepolymer that will have isocyanate-reactive functional group.In certain embodiments; (methyl) acrylic acid ester and certain amount of isocyanate functional propolymer reaction with isocyanate-reactive functional group, make from about 10% to about 80%, from about 20% to about 70% on the isocyanate-functional prepolymers or from about 30% to about 60% isocyanate groups with have (methyl) acrylate reactions of isocyanate-reactive functional group.

Some (methyl) acrylate modified multiple functionalized isocyanate material with at least two (methyl) acrylate modified isocyanate groups is commercially available; For example derive from Bayer Materials Science (Pittsburgh, isocyanates urethane acrylate PA) with trade name " DESMOLUX D100 ", " DESMOLUX VPLS 2396 " and " DESMOLUX XP2510 ".

The composition that comprises radiation-hardenable composition and heat curable composition also comprises the combination of light trigger or multiple light trigger usually.Available light trigger comprises: for example; " α cracking type " light trigger; It for example comprises styrax, styrax acetal (for example dimethyl benzyl ketone), benzoin ether (for example benzoin ethyl ether, benzoin isobutyl propyl group ether and benzoin isobutyl butyl ether), hydroxy alkyl phenyl ketone (for example 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone and 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone), benzoyl cyclohexanol, dialkoxy acetophenone derivs (for example 2; The 2-diethoxy acetophenone), the acyl phosphine oxide (for example, two (2,4; The 6-trimethylbenzoyl)-phosphniline oxide, two (2; 6-dimethoxy benzoyl)-(2,4, the 4-tri-methyl-amyl) phosphine oxide and 2; 4,4-trimethylbenzoyl diphenyl phosphine oxide), methyl sulfenyl phenylmorpholine ketone (for example 2-methyl isophthalic acid-4 (methyl mercapto) and phenyl-2-morpholine-1-acetone) and morpholinyl phenyl amino ketones; Based on benzophenone, thioxanthones, benzyl, camphorquinone and ketone group cumarin take the hydrogen light trigger by force, it comprises light trigger and coinitiator; With their mixture.In certain embodiments, light trigger is an acyl phosphine oxide (for example, two (2,4; The 6-trimethylbenzoyl)-phosphniline oxide, two (2,6-dimethoxy benzoyl)-(2,4; The 4-tri-methyl-amyl) phosphine oxide and 2,4,4-trimethylbenzoyl diphenyl phosphine oxide).

Exemplary available commercially available light trigger can obtain by following trade name " IRGACURE369 ", " IRGACURE 819 ", " IRGACURE CGI 403 ", " IRGACURE651 ", " IRGACURE 1841 ", " IRGACURE 29594 ", " DAROCUR1173 ", " DAROCUR 4265 " and " CGI1700 "; All these can derive from Ciba Specialty Chemicals (Ardsley, N.Y.).Light trigger is preferably according to being enough to provide the photopolymerisable amount of ideal rate to exist.This amount will partly depend on light source, wait to be exposed to the thickness and the extinction coefficient of light trigger under said wavelength of the layer of emittance.Usually, the light trigger component will be with at least about 0.01 weight %, and at least about 0.1 weight %, at least about 0.2 weight %, the amount of about at the most 10 weight % or about at the most 5 weight % exists.

Radiation-hardenable composition and heat curable composition can be in the composition intimate admixture that is used for preparing the disclosed porous polishing pad of the application.In certain embodiments; Gross weight based on said composition; Said composition comprises at least about 10 (in certain embodiments; At least about 15,20,25,30 or 40) radiation-hardenable composition of weight % and the radiation-hardenable composition of about at the most 85 (in certain embodiments, about at the most 80,75,70,65,60,55 or 50) weight %.In certain embodiments; Gross weight based on said composition; Said composition comprises at least about 15 (in certain embodiments; At least about 20,25,30,35,40,45,50,55 or 60) heat curable composition of weight % and the heat curable composition of about at the most 90 (in certain embodiments, about at the most 85,80 or 75) weight %.

In certain embodiments, the said composition that comprises heat-curable resin composition, radiation-curable resin composition and polymer particle also comprises surfactant.Similarly; In certain embodiments, comprise that cross-linked network (comprising heat cure component and radiation curable component), the porous polishing layer that is distributed in the polymer particle in the said cross-linked network and is distributed in the closed pore in the said cross-linked network also comprise the surfactant that is distributed in the said cross-linked network.Can be used for realizing that the instance of surfactant of the present invention comprises anion surfactant, cationic surfactant, non-ionic surface active agent, amphoteric surfactant (for example, zwitterionic surfactant) and their composition.Each comprised fluorochemical in the surfactant of these types, organosilicon and based on the surfactant of hydrocarbon.

Exemplary available cationic surfactant comprises the aliphatic ammonium salt.Exemplary available anion surfactant comprises that carboxylate (for example; Soap and alkyl ether carboxy acid salt), sulfonate (for example; Alkylbenzenesulfonate, alkylnaphthalene sulfonate and alpha-alkene sulfonate), sulfate (for example; Higher alcohol sulfate salt and alkyl ether sulfate) and phosphate (for example, alkylphosphonic).Exemplary available ionic surfactant pack (is for example drawn together polyoxyethylene alkyl ether, ether-ether class; The APEO of glyceride), the ester class (for example; Cithrol, glyceride, sorbitan ester) and the organosilicon glycol copolymer; As deriving from Air Products (Allentown, Pennsylvania) those with trade name " DABCO ".Surfactant can be present in the composition or in the polishing layer, and for example based on the gross weight of composition or porous polishing layer, surfactant exists according to the amount of (in certain embodiments, at the most 4,3 or 2) weight % at the most 10.In certain embodiments, based on the gross weight of composition or porous polishing layer, surfactant exists according to the amount of at least 1 weight %.The invention provides the method for the described polishing pad of a kind of the application of manufacturing.Said method comprises: in the composition that comprises said heat-curable resin composition, said radiation-curable resin composition and polymer particle, form the hole.In certain embodiments, the step that in said composition, forms the hole realizes through said composition is mixed.Multiple technologies capable of using are mixed, and for example, utilize machine mixer or manually stirring.In certain embodiments, hybrid technique (and machine mixer) can comprise rotation and revolve round the sun the two.The filling of granularity and polymer particle can influence the porosity of gained polishing layer, as stated.

In certain embodiments, the said composition that comprises heat-curable resin composition, radiation-curable resin composition and polymer particle can mix and place on the supporting course.Open mold on the supporting course top (for example, do not push up or do not have capping) can be used for forming the polishing layer of required form.Mixture can be distributed in the said mould with the said mould of even filling through mechanical means.Suitable mechanical means can comprise the low pressure mold pressing or use hold-down roller.

The method of making polishing pad disclosed by the invention also comprises through composition being exposed to radiation with partly solidified at least radiation-hardenable composition, and with said composition heating with partly solidified at least said thermal curable resin, thereby form polishing layer.Radiation is ultraviolet radiation (that is radiation in from about 200nm to the scope of about 400nm) normally.At least the required amount of radiation of partly solidified said composition will depend on a plurality of factors, comprise the angle that for example is exposed to radiation, the thickness of composition, the amount of the polymerizable groups in the said composition and the type and the amount of light trigger.Usually, at the composition that is just transmitting at conveyor system, said conveyor system provides the radiation that is suitable for composition to absorb the speed through the UV source that distributes to wavelength from the UV light source direct projection of about 200nm to 400nm.Available UV light source for example comprises ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low intensity fluorescence lamp, metal halide lamp, microwave illuminating lamp, xenon lamp, comprises for example excimer laser and the laser beam sources of argon ion laser and their combination.Said subsequently composition can place baking oven; For example up to about 180 ℃, up to about 150 ℃, up to about 135 ℃ or continue a period of time (for example, from 30 minutes to 24 hours) under the high temperature of (for example from 80 ℃ to 120 ℃, 80 ℃ to 110 ℃ or 90 ℃ to 100 ℃) up to about 120 ℃.Being exposed to radiation and Re Ke carries out or carries out simultaneously by arbitrary order.In certain embodiments, the execution that is exposed to radiation is prior to being exposed to heat.

Polishing pad of the present invention can have one or more working faces, wherein among the application, and the face of the polishing pad that " working face " refers to contact with surface with polished article.In certain embodiments, polished article can be silicon chip.In certain embodiments, the working face of polishing pad can have the surface characteristics like groove, groove, eyelet and their combination.These surface characteristics can improve the one or more of following characteristic: the motion of (1) polishing slurries between the surface of the working face of said pad and polished article; (2) grinding-material is from the said surface removal and the transmission of polished article; Or the polishing or the planarization efficiency of (3) polishing pad.

Surface characteristics can add in the working face of polishing pad through several different methods.In certain embodiments, the working face of pad can be through grinding or the mechanically change of cutting quilt.In other embodiments, in molding process, can surface characteristics be added in the working face of pad, for example, through at least a inner surface of mould provides raised features, said raised features can be stamped in the forming process of pad in the working face that fills up.Surface characteristics can according at random or uniform pattern be distributed on the entire working surface of polishing pad.The example surface characteristic pattern can comprise spirality, circle, square, cross spider and waffle-like pattern.

In certain embodiments, according to the present invention or polishing pad constructed in accordance comprise from the outstanding separation polishing element of supporting course.Referring now to Fig. 3, show the embodiment of polishing pad 2, it comprises a plurality of polishing elements 4, each polishing element 4 is fixed to optional supporting course 8.Polishing pad 2 also comprises compliant layers 10.Usually, the polishing layer that comprises the polishing element of separation is a pantostrat, although this is not shown in Fig. 3.Between the polishing element that separates, film can have for example maximum 0.01,0.02 or the thickness of 0.03mm.In other embodiments, the polishing layer that comprises the polishing element of separation can have and is interrupted, and for example has in the film between the polishing element that separates and is interrupted.Because polishing element 4 is fixed on the supporting course in the illustrated embodiment; And the thin layer (not shown) is between polishing element 4; Therefore polish element 4 and be restricted, but but polish element 4 self-movements on the axis of the polished surface 14 that polishes element 4 perpendicular to each usually with respect to one or more transverse movement that other polishes element 4.As shown in the figure, each polishing element 4 has a plurality of holes 15 that spread all over whole polishing element 4 distributions basically usually.

In the embodiment shown in fig. 3, polishing element 4 is illustrated as for example through being directly bonded on first major opposing side that is fixed to supporting course 8 on the supporting course 8.Polishing element 4 can be directly molded and be cured on the supporting course 8.In other embodiments, polishing element 4 can be connected on the supporting course 8 or utilize adhesive to be directly connected on the compliant layers 10.In these embodiment, the porous polishing layer is discontinuity layer normally.In specific embodiment shown in Figure 3; It is adjacent with compliant layers 10 that optional pressure sensitive adhesive layer 12 is shown; Relative with supporting course 8, said pressure sensitive adhesive layer 12 can be used for polishing pad 2 is fixed to the polishing platen (not shown among Fig. 3) in the CMP polissoir (not shown among Fig. 3).

With reference to Fig. 4, show another exemplary embodiment of polishing pad 2', shown in polishing pad 2' comprise: compliant layers 30, it has first major opposing side and second major opposing side relative with first major opposing side; A plurality of polishing elements 24, each polishing element 24 has the base surface area 25 that is used for each polishing element 24 is fixed to first major opposing side of compliant layers 30; And optional guide plate 31; It has first first type surface and with the first first type surface opposite second major surface; Said guide plate 31 is arranged to said a plurality of polishing elements 24 is arranged on first major opposing side of compliant layers 30, and first first type surface of said guide plate 31 is away from compliant layers 30.

As shown in Figure 4, each polishing element 24 extends along the first direction that is substantially perpendicular to said first major opposing side from first first type surface of guide plate 31.In specific embodiment shown in Figure 4, each in the porous polishing element 24 also is shown to have and spreads all over a plurality of holes 15 that whole polishing element 24 distributes basically.In addition, in specific embodiment shown in Figure 4, show three polishing elements 24, and all polishing elements 24 all are shown the porous polishing element that comprises porous polished surface 23 and hole 15, said hole spreads all over whole polishing element 24 basically and distributes.Yet, should be appreciated that and can use any amount of polishing element 24, and the quantity of porous polishing element may be selected to be few to a polishing element, nearly all polishing elements, or any amount between the two.

Optional polishing composition distribution layer 28 illustrates through Fig. 4 in addition.In glossing, optional polishing composition distribution layer 28 helps hydraulic fluid and/or polishing slurries are distributed on the single polishing element 24.A plurality of holes 26 also can be set to extend through said at least guide plate 31 and said optional polishing composition distribution layer 28, as shown in Figure 4.In certain embodiments, guide plate 31 also can be used as the polishing composition distribution layer.

As shown in Figure 4, in certain embodiments, each polishing element 24 has base surface area 25, and the engaging on first major opposing side that is fixed to compliant layers 30 of second first type surface of each polishing element 24 through corresponding base surface area 25 and guide plate 31.At least a portion of each polishing element 24 stretches in the corresponding hole 26, and each polishing element 24 also passes corresponding hole 26 and stretches out from first first type surface of guide plate 31.Therefore, said a plurality of holes 26 of guide plate 31 are used to guide transversely arranged on supporting course 30 of polishing element 24, also engage so that each corresponding polishing element 24 is fixed on the supporting course 30 with each base surface area 25 simultaneously.

As a result, in polishing process, the freedom displacement independently on the direction of first major opposing side that is basically perpendicular to supporting course 30 of polishing element 24 still remains fixed on the compliant layers 30 through guide plate 31 simultaneously.In certain embodiments, this can allow to use immalleable polishing element, for example, has the porous polishing element in the hole that is distributed on the polished surface basically or only depends on nearly polished surface distribution.

In the specific embodiment shown in Fig. 4, polishing element 24 utilizes the optional adhesive phase 34 at the interface that is arranged between compliant layers 30 and the guide plate 31 to be fixed in addition on first major opposing side of compliant layers 30.Yet, can use other method of attachment, for example heat and pressure will polish element 24 and be directly connected on the compliant layers 30 to comprise utilization.

In Fig. 4 among the unshowned associated exemplary embodiment; The array of pore-forming can be arranged in a plurality of holes; At least a portion of its mesopore 26 comprises the undercut area of main aperture and guide plate 31; And undercut area forms shoulder, and said shoulder engages with corresponding polishing element base surface area 25, thereby maintenance is polished element 24 and need not to polish the adhesive between element 24 and the compliant layers 30.

In addition, can use the second optional adhesive phase 36 optional polishing composition distribution layer 28 to be fixed on first first type surface of guide plate 31, as shown in Figure 4.Also have; In specific embodiment shown in Figure 4; Optional pressure sensitive adhesive layer 32 and supporting course 30 adjacent settings are shown; Relative with guide plate 31, said pressure sensitive adhesive layer can be used for polishing pad 2 ' is fixed to the polishing platen (not shown among Fig. 4) in the CMP polissoir (not shown among Fig. 4).

Guide plate and/or distribution layer also can be used in combination with the embodiment shown in Fig. 3, and in the embodiment shown in fig. 3, porous polishing element 4 does not have base surface area.Can remove supporting course 8 existing under the situation of guide plate, and porous polishing element can for example utilize adhesive on compliant layers 10.

Passing the polishing element 4 and the polishing element 4 of 24 interceptings and 24 shape of cross section along the direction that is roughly parallel to

polished surface

14 and 23 can differ widely according to intended use.Have the cylindrical polishing element 4 and 24 that is generally circular cross section although Fig. 3 and Fig. 4 show, other shape of cross sections also can, and possibly be desirable in certain embodiments.For example, available circle, ellipse, triangle, square, rectangle, hexagon and trapezoidal cross sectional shape.

For cylindrical polishing element 4 and 24 with circular cross section; Polishing element 4 and 24 can be about 50 μ m to about 20mm along the cross-sectional diameter that is roughly parallel to the direction of

polished surface

14 and 23; In certain embodiments this cross-sectional diameter for about 1mm to about 15mm, and this cross-sectional diameter is about 5mm about 15mm (or even about 5mm extremely about 10mm) extremely in other embodiments.Non-cylindrical polishing element for having non-circular cross sections can use the characteristic sizes such as height, width and length of appointment to characterize the size of polishing element.In certain exemplary embodiment, characteristic size may be selected to be about 0.1mm to about 30mm.

In other exemplary embodiments, each polishing element 4 and 24 can be about 1mm along the cross-sectional area that is parallel to the direction of

polished surface

14 and 23 usually ²To about 1,000mm ², be about 10mm in other embodiments ²To about 500mm ², and in addition be about 20mm among other the embodiment ²To about 250mm ²

Polishing element (4 among Fig. 3,24 among Fig. 4) can multiple pattern distribution on the major opposing side of compliant layers (10 among Fig. 3,30 among Fig. 4), said pattern depends on intended use, and said pattern can be regular or irregular.The polishing element can be positioned on the whole basically surface of compliant layers, perhaps can exist not comprise the supporting course zone of polishing element.In certain embodiments, the average surface percentage of coverage of compliant layers of polishing element be the compliant layers first type surface the gross area about 30% to about 95%, the cross-sectional area of this quantity by the polishing element, each polishing element and the cross-sectional area of polishing pad are confirmed.

In certain exemplary embodiment, the scope of the cross-sectional area of polishing pad on the direction that is roughly parallel to the polishing pad first type surface is about 100cm ²To about 300000cm ², be about 1000cm in other embodiments ²To about 100000cm ², and in addition be about 2000cm among other the embodiment ²To about 50000cm ²

In polishing operation, use polishing pad (2 among Fig. 3 for the first time; 2' among Fig. 4) before, in certain exemplary embodiment, each polishing element (4 among Fig. 3; Among Fig. 4 24) extend along the direction of first major opposing side that is basically perpendicular to compliant layers (10 among Fig. 3,30 among Fig. 4).In other exemplary embodiment, each polishing element extends at least about 0.25mm in the top on the plane that comprises guide plate (31 among Fig. 4) along first direction.In other exemplary embodiment, each polishing element along top that first direction extends to the plane that comprises supporting course (10 among Fig. 3) at least about 0.25mm.In other exemplary embodiment; Polished surface (14 among Fig. 3; Among Fig. 4 23) at polishing element (2 among Fig. 3; The height of base portion 2 ' among Fig. 4) or top, bottom can be 0.25mm, 0.5mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, 5.0mm, 10mm or higher, depends on employed polishing composition and the selected material that is used to polish element.

Refer again to Fig. 4, the degree of depth and the spacing that spread all over the hole 26 of whole polishing composition distribution layer 28 and guide plate 31 can change according to the needs of concrete CMP technology.Polishing element 24 respectively relative to each other and polishing composition distribution layer 28 remain on planar orientation with guide plate 31, and be projected into the surface of polishing composition distribution layer 28 and guide plate 31.

In certain exemplary embodiment; Extending the volume that is produced in the top of guide plate 31 and any polishing composition distribution layer (28 among Fig. 4) or supporting course (8 among Fig. 3) through polishing element (4 among Fig. 3,24 among Fig. 4) can provide the space to be used for polishing composition is distributed to the surface of polishing composition distribution layer (Fig. 4 28) or supporting course (8 among Fig. 3).Polishing element (4 among Fig. 3; Among Fig. 4 24) give prominence in polishing composition distribution layer (28 among Fig. 4) or supporting course (8 among Fig. 3) top, overhang depends in part on material behavior and the polishing composition (hydraulic fluid and/or abrasive fluid) of the polishing element lip-deep required flow behavior at polishing composition distribution layer (28 among Fig. 4) or supporting course (8 among Fig. 3) at least.

Available in certain embodiments guide plate can be made of a variety of materials, for example polymer, copolymer, polymer blend, polymer composites or their combination.Usually preferred insulation and polymeric material liquid non-permeate, and found that Merlon is especially available.

The optional polishing composition distribution layer that can be used for some embodiment also can be processed by the multiple polymers material.In certain embodiments, the polishing composition distribution layer can comprise at least a hydrophilic polymer.Preferred hydrophilic comprises polyurethane, polyacrylate, polyvinyl alcohol, polyoxyethylene methylene and their combination.Polymeric material is preferably porous, more preferably comprises foam, with in the polishing operation process, when compression polishing composition distribution layer, the normal pressure towards substrate is provided.The porous or the foamed materials that can preferably have in certain embodiments, perforate or closed pore.In some specific embodiments, the polishing composition distribution layer has the porosity between about 10% to about 90%.In alternative embodiment; The polishing composition layer can comprise the for example hydrogel material of hydrophilic ammonia carbamate and so on; This hydrophilic material can absorb preferably the water to about 60 weight % scopes at about 5 weight %, thereby in the polishing operation process, lubricated surface is provided.

In certain exemplary embodiment, the polishing composition distribution layer can be evenly distributed in polishing composition on the whole substrate surface that polishes basically, and polishing more uniformly can be provided like this.The polishing composition distribution layer comprises like the choked flow element in spoiler, groove (not shown in the accompanying drawing), hole or the like and so on to regulate the flow velocity of polishing composition in polishing process alternatively.In other exemplary embodiment, the polishing composition distribution layer can comprise various different material layers, so that obtain required polishing composition flow velocity at the different depth place apart from polished surface.

In certain exemplary embodiment, be limited to interior hollow zone or the cavity of polishing element one or more the comprising in the polishing element, but this arrangement is optional.In certain embodiments, described in International Patent Application Publication No. WO 2006/055720, the core of polishing element can comprise the sensor of detected pressures, conductibility, electric capacity, eddy current or the like.

In some embodiment of polishing pad disclosed by the invention and/or its manufacturing approach, supporting course comprises flexible and submissive material.Supporting course is film normally, the surface that it provides the composition that comprises heat-curable resin composition and radiation-curable resin composition to be cured above that.The porous polishing layer comprises among the certain exemplary embodiment that polishes element therein, and the polishing element can form the integrated sheet material that the polishing element is fixed to supporting course with supporting course, and at least a portion of said polishing element comprises porous polishing element.

When polishing pad was used, supporting course also was used for protecting compliant layers to exempt from into water or other fluid of polishing composition.Supporting course is generally liquid non-permeate (but permeable material can use with optional barrier layer, to stop or suppression fluid is penetrated in the supporting course).In certain exemplary embodiment, supporting course comprises and is selected from following listed polymeric material: organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyurethane, polyolefin and their combination.Supporting course also can comprise multiple other materials, for example filler, particle, fiber, reinforcing agent or the like.In certain embodiments, supporting course is transparent.

Supporting course can for example be processed through material (for example, organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyurethane, polyolefin and their combination) is extruded into film.In certain embodiments; Said material is can derive from Lubrizol Advanced Materials with trade name " ESTANE 58887-NAT02 "; Inc. (Cleveland; OH) or with trade name " PELLETHANE " (for example, " PELLETHANE 2102-65D ") can derive from Dow Chemical (Midland, polyurethane MI).The commercially available film that can be used as supporting course for example comprises can derive from Stevens Urethane (Easthampton, polyurethane film Massachusetts) with trade name " ST-1882 ", " ST-1035 ", " SS-3331 ", " SS-1495L " and " ST-1880 ".

In some embodiment of polishing pad disclosed by the invention and/or its manufacturing approach, compliant layers comprises flexible and submissive material, like submissive rubber or polymer.Compliant layers can be compressed so that the normal pressure towards polished surface to be provided usually, and can for example help to provide the contact between polishing pad and the polished substrate surface even.In certain exemplary embodiment, compliant layers is processed by compressible polymeric material (for example, by the foamed polymer material of processing like natural rubber, synthetic rubber or thermoplastic elastomer (TPE)).The closed pore porous material is available.In certain embodiments, compliant layers comprises polyurethane, and can be the felt of polyurathamc for example or polyurethane insulating dipping.The thickness of compliant layers can be for example in 0.2 to 3mm scope.The porous polishing layer comprises among the certain exemplary embodiment that polishes element therein; The polishing element can form the integrated sheet material that the polishing element is fixed to compliant layers (can be the porous compliant layers) with compliant layers, and at least a portion of said polishing element comprises porous polishing element.

In certain exemplary embodiment, compliant layers comprises and is selected from following listed polymeric material: organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyolefin, polyurethane and their combination.Supporting course also can comprise multiple other materials, for example filler, particle, fiber, reinforcing agent or the like.In certain embodiments, compliant layers is fluid impermeable (but permeable material can be used in combination with above-described supporting course).

Suitable commercially available compliant layers for example comprises can derive from Rogers Corp. (Rogers, microvoid polyurethane CT) with trade name " PORON " (description of product that for example has 4701-60-20062-04,4701-50-20062-04,4701-40-20062-04).Other suitable compliant layers for example comprises can derive from Rodel with trade name " SUBA IV "; Incorporated (Newark; The polyester felt of DE) polyurethane insulating dipping and can derive from Rubberite Cypress Sponge Rubber Products with trade name " BONDTEX "; Inc. (Santa Ana, adhesive rubber sheet material CA).

In some embodiment of polishing pad disclosed by the invention and/or its manufacturing approach; Said polishing pad can comprise the window that extends through said pad along the direction perpendicular to polished surface; Maybe can use hyaline layer and/or transparent polishing element; Thereby allow the optical end point monitoring of polishing process, like the description among the International Patent Application Publication No. WO 2009/140622 people such as () Bajaj.

The term " hyaline layer " that uses above is intended to comprise the layer with transparent region, and said transparent region can be by processing with the identical or different material of the remainder of this layer.In certain exemplary embodiment, it is transparent that at least a in the zone of polishing element, supporting course, compliant layers or polishing layer or supporting course can be, and maybe can be formed into transparent through material being applied heat and/or pressure.In certain embodiments, transparent material can be poured into a mould in the opening (for example, utilizing mould) that is arranged in suitably in the layer, to create transparent region (for example, in polishing layer, supporting course or compliant layers).In certain embodiments, polishing layer solidifies under the situation that has the preformed window, in polishing layer, to create transparent region.In certain embodiments, whole supporting course and/or compliant layers can be processed by following material, this material for the energy in the wave-length coverage paid close attention to that uses by the end-point detection device be transparent maybe can be made as transparent.The suitable transparent materials that is used for transparent element, layer or zone comprises (for example) transparent polyurethane.

In addition, as top used, term " transparent " is intended to comprise element, layer and/or the zone for the energy substantial transparent of being used by the end-point detection device in the wave-length coverage of paying close attention to.In certain exemplary embodiment, the end-point detection device utilizes one or more electromagnetic energy source emission forms to be ultraviolet light, visible light, infrared light, microwave, radio wave, their radiation of combination or the like.In certain embodiments; Term " transparent " be meant the energy that shines the relevant wavelength on transparent element, layer or the zone at least about 25% (as, at least about 35%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%) see through from it.

In certain exemplary embodiment, supporting course is transparent.In certain embodiments, polishing layer is transparent.In the certain exemplary embodiment that comprises the embodiment shown in above Fig. 3, at least a polishing element is transparent.In certain embodiments, supporting course is transparent, and at least a portion of polishing layer (for example, the polishing element) is transparent, and in compliant layers, has the hole of aliging with the transparent part of polishing layer.

In the other exemplary embodiment that comprises embodiment shown in above Fig. 4, at least a polishing element is transparent, and shown in adhesive phase and compliant layers also be transparent.In other exemplary embodiment, being combined as of compliant layers, guide plate, polishing composition distribution layer, at least a polishing element or they is transparent.

The invention still further relates in glossing the method for using above-mentioned polishing pad, said method comprises that the surface that makes substrate contacts with porous polishing layer according to polishing pad of the present invention; With relatively move said polishing pad to denude the surface of said substrate about said substrate.In certain embodiments, the porous polishing layer of polishing pad comprises a plurality of polishing elements, and wherein at least some are porous.In certain exemplary embodiment, can hydraulic fluid be provided between pad interface and the substrate surface at the interface.Suitable hydraulic fluid for example comprises at U.S. Patent number 6,238,592 people such as () Hardy, 6,491,843 people such as () Srinivasan and in International Patent Application Publication No. WO2002/33736 people such as () Her, describe those.

In certain embodiments, the polishing layer in the of the present invention and/or prepared according to the methods of the invention polishing pad can have the average pore size of at least 5 microns, at least 10 microns or at least 15 microns.In certain embodiments, the average pore size of polishing pad is 100,75,50,45 or 40 microns at the most.For example, average pore size can be in from 5 to 100,5 to 75,5 to 50,5 to 40 or 5 to 30 microns scope.(for example comprising that at least a surfactant or polymer particle are among the embodiment of fiber) in certain embodiments, the average pore size of polishing pad can be 30,25 or 20 microns at the most.The diameter of the common finger-hole in said aperture.Yet, be among the aspheric embodiment in the hole, but the full-size of aperture finger-hole.In certain embodiments, the unevenness in aperture is in from 40% to 75% scope, or in from 40% to 60% scope.In certain embodiments, the unevenness in aperture is at the most 75%, 70%, 65%, 60%, 55% or 50%.By contrast, the comparative example composition that comprises heat curable composition can have the aperture unevenness greater than 80%, 90% or 100%.In certain embodiments, can be in from 5% to 60% scope according to the porosity of the polishing layer in the polishing pad of the present invention, or in from 5% to 55%, 10% to 50% or 10% to 40% scope.

Control shows through Fig. 5 A, Fig. 5 B, Fig. 6 A and Fig. 6 B according to the difference of the aperture in the polishing layer of the present invention with the aperture in the heat curable composition in comparative example.Fig. 5 A and Fig. 5 B are respectively the cross sectional view of the hardening composition of describing in the instance 2 in following instance part and the micrograph of vertical view.As a comparison, Fig. 6 A and Fig. 6 B are respectively cross sectional view and the micrographs of vertical view of the hardening composition of comparative example 3.The two all utilizes instance 2 and comparative example 3 preparation of 10 weight % polymer particles and mixes in the same manner.Yet the two is cured instance 2 through radiation curing and heat cure, and comparative example 3 only is cured through heat cure.Micrograph shows the hole of the boring ratio comparative example 3 in the instance 2 and is controlled better.Data in the following instance in the table 1 have also been supported to compare with comparative example 3 and have been had less size range, lower aperture unevenness and higher hardness in the instance 2.

Under not expecting by the prerequisite of theory, it is believed that maybe be relevant with the hardness of polishing layer to the control of aperture and aperture unevenness.In certain embodiments, the hardness of porous polishing layer is at least 40,45 or 50 Shore D hardness.For example, said hardness can be measured according to the method for testing of describing in the following instance 2.By contrast, the comparative example composition that comprises heat curable composition can have the Shore D hardness less than 40.

Surfactant can be used in composition disclosed by the invention and the porous polishing layer, and for example, reducing aperture and pore diameter range usually, and the dual cure method of comparing under the situation that does not have surfactant is improved pore size distribution better.In other words, add the better control that surfactant can help to provide the shape in pore-size distribution and size, density and hole, can play positive role to the key metrics standard of even performance (for example, clearance and in wafer the uniformity) then.Micrograph among Fig. 7 A and Fig. 7 B (being respectively the cross sectional view of the hardening composition of description in the instance 15 in the following instance part and the micrograph of vertical view) shows the interpolation surfactant and can play positive role to pore diameter range and pore size distribution.For example, with have equal number and polymer particle and according to the same way as preparation and there is not the instance 2 of surfactant to compare, in instance 15, have littler pore diameter range.

The selected embodiment of the present invention

In first embodiment, the invention provides a kind of polishing pad, it comprises:

Compliant layers, it has the first and second relative sides; And

The porous polishing layer, it is arranged on first side of compliant layers, and said porous polishing layer comprises:

Cross-linked network, it comprises heat cure component and radiation curable component, wherein said radiation curable component and said heat cure component covalent bonding are in said cross-linked network;

Polymer particle, it is dispersed in the said cross-linked network; And

Closed pore, it is dispersed in the said cross-linked network.

In a second embodiment, the invention provides a kind of polishing pad, also comprise the supporting course that is arranged between said compliant layers and the said porous polishing layer according to first embodiment.

In the 3rd embodiment; The invention provides a kind of polishing pad according to first or second embodiment; Wherein said heat cure component comprises at least a of polyurethane or polyepoxide, and wherein said radiation curable component comprises at least a in polyacrylate, polymethacrylates, polyvinylether, ethene polymers or the polyepoxides.

In the 4th embodiment, the invention provides a kind of polishing pad according to first or second embodiment, wherein said heat cure component and said polymer particle comprise polyurethane independently of one another.

In the 5th embodiment, the invention provides a kind of polishing pad of any according among first to fourth embodiment, wherein said polymer particle is covalently bound at least a of said heat cure component or said radiation curable component in the said cross-linked network.

In the 6th embodiment, the invention provides a kind of polishing pad of any according among first to the 5th embodiment, wherein radiation curable component comprises at least a of polyacrylate or polymethacrylates.

In the 7th embodiment, the invention provides a kind of polishing pad according to the 6th embodiment, wherein said polyacrylate or polymethacrylates are covalently bound to said heat cure component through amino-formate bond or urea linking group.

In the 8th embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, the hardness that wherein said porous polishing layer is measured through method of testing 2 is at least 40 Shore D hardness.

In the 9th embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein the particle mean size of polymer particle is in 5 microns to 500 microns scope.

In the tenth embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein said polymer particle is spherical basically.

In the 11 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein said polymer particle is a fiber.

In the 12 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein said polymer particle exists with the maximum 20 weight % based on the gross weight of porous polishing layer.

In the 13 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, the aperture unevenness in wherein said hole is 75% to the maximum.

In the 14 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, the average pore size of its mesopore is in 5 microns to 100 microns scope.

In the 15 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein said polishing layer comprises from the polishing element of the outstanding separation of supporting course or compliant layers.

In the 16 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein polish element and have far-end separately, and wherein said far-end is removable on the axis perpendicular to the polished surface that polishes element away from supporting course.

In the 17 embodiment, the invention provides and a kind ofly also comprise the guide plate that wherein has a plurality of openings according to the 15 or the polishing pad of the 16 embodiment, it is outstanding that the polishing element of said separation passes one of said a plurality of openings separately.

In the 18 embodiment, the invention provides a kind of polishing pad of any according among the 15 to the 17 embodiment, wherein polish element through adhesive on compliant layers.

In the 19 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, wherein said compliant layers comprises at least a of organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyolefin or polyurethane.

In the 20 embodiment, the invention provides a kind of polishing pad according to arbitrary previous embodiment, at least a portion of wherein said polishing pad is transparent.

In the 21 embodiment, the invention provides a kind of polishing pad, wherein said polymer particle water soluble according to arbitrary previous embodiment.

In the 22 embodiment, the present invention provides a kind of polishing pad according to arbitrary previous embodiment, and wherein said porous polishing layer also is included in the surfactant in the cross-linked network.

In the 23 embodiment, the invention provides a kind of method of making polishing pad, said method comprises:

In said composition, form the hole;

Said composition is positioned on the supporting course; And

Through composition being exposed to radiation with partly solidified at least said radiation-curable resin composition, and with said composition heating with partly solidified at least said heat-curable resin composition, thereby on supporting course, form the porous polishing layer.

In the 24 embodiment, the invention provides a kind of method according to the 23 embodiment, also comprise compliant layers adhesively is attached on the surface of the said supporting course relative with said porous polishing layer.

In the 25 embodiment; The invention provides a kind of according to the 23 or the method for the 24 embodiment; Wherein said heat-curable resin composition comprises first resin with at least two isocyanate groups or at least two epoxide groups and has at least two second resin in hydroxyl, amino, carboxyl or the mercapto groups, and wherein said radiation-hardenable composition comprises at least two kinds in acrylic acid ester, methacrylate, vinyl or the epoxide group.

In the 26 embodiment; The invention provides a kind of method according to the 25 embodiment; Wherein said first resin has at least two isocyanate groups; Wherein said second resin has at least two oh groups or at least two amino groups, and wherein said radiation-hardenable composition comprises at least two acrylic acid ester or methacrylate based group, and wherein said radiation-hardenable composition also comprises at least a isocyanate groups or oh group.

In the 27 embodiment, the invention provides a kind of method according to the 26 embodiment, wherein said radiation-hardenable composition is aliphatic, isocyanate-functional urethane acrylate or methacrylate.

In the 28 embodiment, the invention provides a kind of method of any according among the 23 to the 27 embodiment, also be included in and form before the porous polishing layer, open mold is positioned in the above composition of supporting course.

In the 29 embodiment, the present invention has proposed a kind of confession according to any the method among the 23 to the 28 embodiment, and wherein said hole is a closed pore.

In the 30 embodiment, the invention provides a kind of method of any according among the 23 to the 29 embodiment, wherein said composition also comprises surfactant.

In the 31 embodiment, the invention provides a kind of method of any according among the 23 to the 30 embodiment, the hardness that wherein said porous polishing layer is measured through method of testing 2 is at least 40 Shore D hardness.

In the 32 embodiment, the invention provides a kind of method of any according among the 23 to the 31 embodiment, the particle mean size of wherein said polymer particle is in 5 microns to 500 microns scope.

In the 33 embodiment, the invention provides a kind of method of any according among the 23 to the 32 embodiment, wherein said polymer particle is spherical basically.

In the 34 embodiment, the invention provides a kind of method of any according among the 23 to the 33 embodiment, wherein said polymer particle is a fiber.

Implemented in a kind of example the 35, the present invention provides according to any the method among the 23 to the 34 embodiment, wherein said polymer particle water soluble.

In the 36 embodiment, the invention provides a kind of method of any according among the 23 to the 35 embodiment, wherein said polymer particle exists with the maximum 20 weight % based on the gross weight of porous polishing layer.

In the 37 embodiment, the present invention provides according to the method for any among a kind of the 23 to the 36 embodiment, and the aperture unevenness in wherein said hole is up to 75%.

In the 38 embodiment, the invention provides a kind of method of any according among the 23 to the 37 embodiment, the average pore size in wherein said hole is in 5 microns to 100 microns scope.

In the 39 embodiment, the invention provides a kind of method of any according among the 23 to the 38 embodiment, wherein said polishing layer comprises and is fixed to supporting course and from the polishing element of the outstanding separation of supporting course.

In the 40 embodiment; The invention provides a kind of method according to the 39 embodiment; The polishing element of wherein said separation has fixation ends and separately away from the far-end of supporting course, and wherein said far-end is removable on the axis perpendicular to the polished surface of polishing element.

In the 41 embodiment; The invention provides a kind of method of any according among the 23 to the 38 embodiment; Wherein said polishing layer comprises from the polishing element of the outstanding separation of compliant layers; Wherein said polishing element has the far-end away from supporting course separately, and wherein said far-end is removable on the axis perpendicular to the polished surface that polishes element.

In the 42 embodiment, the invention provides a kind of method of any according among the 29 to the 41 embodiment, also comprise the guide plate that wherein has a plurality of openings, it is outstanding that the polishing element of said separation passes one of said a plurality of openings separately.

In the 43 embodiment; The invention provides a kind of method of any according among the 29 to the 42 embodiment, wherein said supporting course comprises at least a of organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyolefin or polyurethane.

In the 44 embodiment, the invention provides a kind of method of any according among the 23 to the 43 embodiment, at least a portion of wherein said polishing pad is transparent.

In 45 embodiment, the invention provides a kind of finishing method, it comprises:

With the surface of substrate with contact according to any the porous polishing layer of polishing pad among the first to the 22 embodiment; And

Move said polishing pad to grind the surface of said substrate with respect to said substrate.

In the 46 embodiment, the invention provides a kind of method according to the 45 embodiment, comprise that also the interface between said porous polishing layer and said substrate surface provides working fluid.

To combine following limiting examples to set forth now according to exemplary polishing pad of the present invention.

Instance

Method of testing 1:FESEM

(Tokyo, Hitachi S-4500 FESEM Japan) obtains the scanning electron microscopy (vertical view and cross sectional view) to article can to derive from Hitachi High-Technologies Corporation according to the conventional program utilization.Through utilizing sharp razor blade cutting to obtain the cross section of article.Before the SEM inspection, utilize routine techniques with the coating of sample sputter successively Au/Pd.Obtain the two the image of cross section and top of article.

Method of testing: 2: durometer

Utilization can derive from Rex Gauge Company, Inc., and Buffalo Grove, the model of Illinois is that 1500 Shore D durometers carry out the durometer measurement.The value of report is the mean value of five measurement results in the table 1, and each measurement result is to carry out to the difference polishing characteristic of instance.

Method of testing 3: confirm the aperture through light microscope

Confirming of aperture mean value, aperture standard deviation (standard deviation), pore diameter range (observed maximum sized hole deducts the hole of observed minimum dimension), aperture unevenness (the aperture standard deviation multiply by 100 divided by average pore size) and porosity (measured area that comprises the hole in the image multiply by 100 divided by the gross area of image) through utilizing graphical analysis to realize to optical imagery; Said optical imagery utilization can derive from Nikon Instruments; Inc. (Elgin; IL) MM-40 Nikon measuring microscope combines to derive from Media Cybernetics, and (Bethesda, Image-pro plus analysis software MD) obtains.

Before optical imagery, prepare sample in such a way.Three polishing characteristics can be derived from (the St.Paul of 3M company from the article cutting and through utilizing with trade name " 3M SCOTCH-WELD Epoxy Potting Compound/Adhesive DP270 CLEAR "; Minnesota) perfusion compound is sealed in and can derives from Buehler Ltd. (41; Lake Bluff is among the Phenolic ring form of 2.5cm external diameter * 2.2cm internal diameter Illinois).Be built in Ecomet 3 grinder-polishers that characteristic use in the epoxy resin can derive from Buehler Ltd. and adopt six process finishing polishes, downward pressure: 4.25psi (29.3kPa), the head of all six steps and platen rotating speed: 120rpm.In all cases, sign sand paper or polishing pad are installed on the platen of Ecomet 3 through using contact adhesive (psa).

Step 1: obtain the 240Grit abrasive disk of 8 inch diameters with trade name " 3M WETORDRY PSA Disc 21366 " from 3M company, milling time is 3 minutes, and wherein water is polishing fluid.

Step 2: obtain the 600Grit abrasive disk of 8 inch diameters with trade name " CARBIMET 8 " PSA Disc 30-5118-600-100 from Buehler Ltd., milling time is 6 minutes, and wherein water is polishing fluid.

Step 3: with trade name " TEXMET 1500Polishing Pad "; 40-8618 can derive from the 8 inch diameter pads of Buehler Ltd.; Utilization can derive from Allied High Tech Products; Inc. (Rancho Dominguez, 15 μ m grade polycrystalline diamond suspension 90-30035 California) are as polishing fluids, and polishing time is 6 minutes.

Step 4: with trade name " TEXMET 1500Polishing Pad "; 40-8618 can derive from the 8 inch diameter pads of Buehler Ltd.; Utilization can derive from Allied High Tech Products; Inc. 6 μ m grade polycrystalline diamond suspension 90-30025 are as polishing fluids, and polishing time is 6 minutes.

Step 5: with trade name " TEXMET 1500Polishing Pad "; 40-8618 can derive from the 8 inch diameter pads of Buehler Ltd.; Utilization can derive from Allied High Tech Products; Inc. 3 μ m grade polycrystalline diamond suspension 90-30020 are as polishing fluids, and polishing time is 6 minutes.

Step 6: with trade name " TEXMET 1500Polishing Pad "; 40-8618 can derive from the 8 inch diameter pads of Buehler Ltd.; Utilization can derive from Allied High Tech Products; Inc. 1 μ m grade polycrystalline diamond suspension 90-30015 is as polishing fluids, and polishing time is 6 minutes.

After polishing, the polished surface of feature utilizes subsequently and can derive from Denton Vacuum, and (Moorestown, sputter coating machine NJ) utilizes the routine techniques carbon-coated to LLC.Carry out optical imagery subsequently.

Instance 1

Prepare instance 1 through in the 50mL plastic beaker, placing 0.28g 5350D, 2.15 gram M1,1.83 gram PHP-75D, 1.27 gram D100 and 0.06 gram TPO-L.Beaker is placed Awatori-Rentaro AR-500Thinky Mixer, and (derive from Thinky Corporation, Tokyo Japan) and according to two process operation AR-500 mixes said component.Under the revolution of the rotation of 1000rpm and 1000rpm, continue to carry out in 5 minutes first step.After first step, carry out second step immediately, and under the revolution of the rotation of 30rpm and 2000rpm, continued for 15 seconds and carry out second step, thereby form resin compound.Resin compound is poured into by in the long by 19.5cm of the plating Ni of teflon-coated and the aluminum dipping form that the wide aluminium sheet of 9.2cm forms.Said mould is made up of the square array of diminishing cylindrical chamber.Chamber has the 7.8mm diameter at the top of said chamber, and having the 6.5mm diameter and the degree of depth in the bottom of said chamber is 1.8mm.Distance between the center of two chambers is about 11.7mm.A slice polyurethane film ST-1880 is used as backing.With said backing cutting written treaty 12cm * 10cm, and be placed on the zone of containing resin compound of mould.With 28cm length * 17cm wide * quartz plate that 3.5mm is thick is placed on the top of polyurethane backing, force resin to get into chamber and between chamber, form the thin base surface area of the thick resin compound of about 0.5mm.

Said mould, resin compound, backing and quartz plate (can be derived under the Fusion Systems Inc. (Gaithersburg, ' V ' bulb Maryland)) through coming UV cured resin mixture at two ultraviolet light modulations with about 157.5 watts/centimetre (400 watts/inch) work.Mould is with the said lamp of speed process of about 2.4 meters/minute (8 feet per minute clocks), and radiation arrives resin compound through quartz plate and polyurethane backing.To transfer to through temperature is set subsequently be to place two hours in 100 ℃ the air stream of baking oven for mould, partly solidified resin compound and polyurethane backing subsequently, with the said resin compound of heat cure.To solidify article and from mould, remove through spurring the polyurethane backing gently, thereby form the article with structuring polishing characteristic, instance 1.

Instance 2

1 prepares instance 2 as the instance, and difference is that the 0.58 gram 5350D, 2.15 that consists of of resin compound restrains M1,1.83 gram PHP-75D, 1.27 gram D100 and 0.06 gram TPO-L.

Instance 3

1 prepares instance 3 as the instance, and difference is, and carry out according to reversed and solidify, first heat cure, UV solidifies then.

Instance 4

2 prepare instance 4 as the instance, and difference is, and carry out according to reversed and solidify, first heat cure, UV solidifies then.

Comparative example C1

1 prepares comparative example C1 as the instance, and difference is, saves 5350D in the composition of resin compound.

Comparative example C2

C1 prepares comparative example C2 as the comparative example, and difference is that the composition of resin compound is 0.31 gram 5350D, 2.15 gram M1 and 3.65 gram PHP-75D, and only uses the heat cure of under 100 ℃, carrying out two hours, has omitted the UV curing schedule.

Comparative example C3

C2 prepares comparative example C3 as the comparative example, and difference is that the composition of resin compound is 0.65 gram 5350D, 2.15 gram M1 and 3.65 gram PHP-75D.

Instance 5

Prepare instance 5 through in the 500mL plastic beaker, placing 9.49 gram 5350D, 35.00 gram M1,29.69 gram PHP-75D, 20.63 gram D100 and 1.03 gram TPO-L.Beaker is placed Awatori-Rentaro AR-500Thinky Mixer, and said component is mixed according to the technology operation AR-500 of two steps.Under the revolution of the rotation of 1000rpm and 1000rpm, continue to carry out in 5 minutes first step.After first step, carry out second step immediately, and under the revolution of the rotation of 30rpm and 2000rpm, continued for 15 seconds and carry out second step, thereby form resin compound.

Utilizing width is the resin compound coating of doctor knife coater about 28cm * 28cm of preparation on the thick backing of 26mm of 60 mils (1.52mm) for about 21 inches (53cm) and gap; Said backing is through (deriving from Lubrizol Advanced Materials with thermoplastic polyurethane (TPU) ESTANE 58887-NAT02; Inc. (Cleveland, OH)) forms on the separate paper liner, being extruded into film under 182 ℃.

Resin compound after the coating and backing place 12 inches * 12 inches (on inch aluminium sheet that (6.35mm) is thick of 30.5cm * 30.5cm) * 0.25.36 blocks of magnet that 0.375 inch (9.6mm) diameter * 0.125 inch (3.2mm) is thick are installed in the aluminium sheet groove behind.36 grooves are arranged according to square array, and the distance between the center of groove is about 5cm.The diameter of groove and the degree of depth are respectively 9.8mm and 4.3mm.On resin compound coating top, arrange the woven wire of special teflon coating, its about 41cm * 30cm, and thick be about 1.6mm, it has the circular hole of hexagonal array, the about 6.2mm of the diameter of each circular hole, and the distance between the center is about 8mm.Magnetic attraction between the magnet in silk screen and the aluminium sheet makes that silk screen is compelled to pass the resin compound coating, thereby between woven wire and backing, stays the thin base surface area of coating.As the instance 1 carry out coating UV solidify, difference is not use quartz plate.Utilize subsequently picture in instance 1 description operation carry out heat cure.

After from baking oven, taking out, woven wire is removed from the resin that solidifies, and forms the pad surface that has texture on the polyurethane backing that is attached to original paper backing.Remove paper, thereby expose the opposite side of polyurethane backing.Utilize the thick transfering adhesive of 127 μ m (deriving from the 3M Adhesive Transfer Tape 9672 of 3M company); The polyurethane backing that will have the pad surface of texture manually is laminated on the thick a slice urethane foam in about 30cm * 30cm * 0.0625 inch (1.59mm) and (derives from American Flexible Products; Inc. (Chaska; Minnesota) Rogers " PORON " urethane foam, part #4701-50-20062-04).The die-cut pad that has the 23cm diameter of 18mm diameter centre bore from the layer compound, thus the pad with structuring polishing characteristic of the present invention, instance 5 formed.

Comparative example C4

C5 prepares comparative example C4 as the instance, and difference is that the composition of resin compound is 10.48 gram 5350D, 35.00 gram M1 and 59.38 gram PHP-75D, and only uses the heat cure of under 100 ℃, carrying out two hours, has omitted the UV curing schedule.

Utilize method of testing 2 and 3; The hardness of practical measuring examples 1-5 and comparative example C1-C4, aperture mean value, aperture standard deviation, pore diameter range, aperture unevenness and porosity.The result is shown in the following table 1.

Table 1. hardness, aperture and porosity data

* do not have measurable aperture data, C1 does not have the hole like comparative example.

Instance 6

1 prepares instance 6 as the instance, and difference is that the 0.28 gram 5150D, 2.15 that consists of of resin compound restrains M1,1.83 gram PHP-75D, 1.27 gram D100 and 0.06 gram TPO-L.

Illustrative examples I-1

1 prepares illustrative examples I-1 as the instance, and difference is that the 0.28 gram 5070D, 2.15 that consists of of resin compound restrains M1,1.83 gram PHP-75D, 1.27 gram D100 and 0.06 gram TPO-L.

Instance 7

1 prepares instance 7 as the instance, and difference is that the amount of 5350D is 0.05g.

Instance 8

1 prepares instance 8 as the instance, and difference is that the amount of 5350D is 0.14 gram.

Instance 9

1 prepares instance 9 as the instance, and difference is that the amount of 5350D is 0.93 gram.

Illustrative examples I-2

1 prepares illustrative examples I-2 as the instance, and difference is that the amount of 5350D is 1.31 grams.

The FESEM of instance 6-9 (method of testing 1) result shows that they have acceptable porosity level.The FESEM of illustrative examples I-1 and I-2 (method of testing 1) result shows that they have the low-porosity level.

Instance 10

5 prepare instance 10 as the instance, and difference is following change.The 0.62 gram A15LV, 23 that consists of of resin compound restrains P-250,15.83 gram PHP-75D, 22 gram D100,1.1g TPO-L and 0.68 gram DC5604.Said component is placed and in the 500ml plastic containers, is mixed.

Make the silk screen that has resin compound and TPU backing two with the ultraviolet lamps (can derive from ' V ' bulb of Fusion Systems Inc.) of about 157.5 watts/centimetre (400 watts/inch) work under through coming UV cured resin mixture.Resin compound is with the said lamp of speed process of about 2.4 meters/minute (8 feet per minute clocks), and radiation is through resin compound.To place the top of said silk screen subsequently with the polyester film release liner that trade name " 3M SCOTCHPAK 1022Release Liner " can derive from the fluoropolymer coating of 3M company, and partly solidified resin compound.With the assembly upset, make the polyurethane backing be positioned at the top, and the polyester film/silk screen of fluoropolymer coating/partly solidified resin compound is positioned at the bottom subsequently.Whole assembly passes through same UV curing process for the second time, and this moment, quartz plate was positioned at the backing top.After the second time, UV solidified completion; The polyester film of quartz plate and fluoropolymer coating removed and silk screen/partly solidified resin compound/back lining components transferred to temperature is set is to place two hours in the baking oven crossed of 100 ℃ air communication, with the heat reactive resin mixture.After cool to room temperature, make the 23cm diameter pad of band 18mm diameter centre bore, described in instance 5, obtain instance 10.

Instance 11

10 prepare instance 11 as the instance, and difference is that the weight of A15LV is 1.25 grams.

Instance 12

10 prepare instance 12 as the instance, and difference is that the weight of A15LV is 3.20 grams.

Instance 13

10 prepare instance 13 as the instance, and difference is that the weight of A15LV is 6.76 grams.

Instance 14

Prepare instance 14 through in the 650mL plastic beaker, placing 6.88 gram A15LV, 127.78 gram P-250,6.11 gram TPO-L and 3.51 gram DC5604.Through container being placed Awatori-Rentaro AR-500Thinky Mixer and, thereby said component is mixed with the revolution operation of the rotation of 1000rpm and 1000rpm AR-5004 minute.Container is taken out from mixer and 87.29 gram PHP-75D and 122.22 are restrained in the D100 adding containers.Mixture is through two mixed in step technologies.Under the revolution of the rotation of 1000rpm and 1000rpm, continue to carry out in 4 minutes first step.After first step, carry out second step immediately, and under the revolution of the rotation of 30rpm and 2000rpm, continued for 15 seconds and carry out second step, thereby form resin compound.

Utilizing width is the doctor knife coater of 60 mils (1.52mm) for about 21 inches (53cm) and gap; The resin compound coating of preparation about 21 inches * 23 inches (53.3cm * 58.4) on the thick backing of 4 mils (102 μ m); Said backing through on 4 mil polyester release liner of routine with TPU, " ESTANE 58309-022 " is extruded into form of film and forms under 210 ℃.

Resin compound after the coating and backing place 24 inches * 24 inches (on inch aluminium sheet that (6.35mm) is thick of 61.0cm * 61.0cm) * 0.25.113 blocks of magnet that 0.375 inch (9.6mm) diameter * 0.125 inch (3.2mm) is thick are installed in the aluminium sheet groove behind.Groove is the linear array that comprises 15 row.In in the said row eight row, every row has 8 grooves, and in the row of 7 in the said row, every row has 7 grooves.Be spaced apart 4mm between the row, and be spaced apart 7.5mm between the groove in the delegation.The first row groove (near the edge of plate) has eight grooves; Second row has seven grooves.Continue this pattern that replaces until the tenth five-element with eight grooves.The groove of the row of even-numbered is arranged such that they are also placed in the middle between the groove of corresponding adjacent lines.The diameter of groove and the degree of depth are respectively 9.8mm and 4.3mm.Use can be handled the adhesive tape of high temperature so that magnet is fixed in the groove.On resin compound coating top, arrange the woven wire of special teflon coating; Its about 24 inches * 24 inches (61.0cm * 61.0cm), and thickly be about 1.6mm, it has the circular hole of hexagonal array; The about 6.2mm of the diameter of each circular hole, and the distance between the center is about 8mm.Magnetic attraction between the magnet in silk screen and the aluminium sheet makes that silk screen is compelled to pass the resin compound coating, thereby between woven wire and backing, stays the thin base surface area of coating.

Defer to the curing process cured resin mixture the same with instance 10.After from baking oven, taking out, woven wire is removed from the resin that solidifies, and forms the pad surface that has texture on the polyurethane TPU backing that is attached to original polyester backing.Utilize the thick transfering adhesive of 127 μ m (deriving from " the 3M ADHESIVE TRANSFER TAPE 9672 " of 3M company), the polyester release liner that the pad of being with texture is surperficial manually is laminated on the thick a slice polyurethane foam of about 21in * 23in (53.3cm * 58.4) * 0.0787inch (2mm).The pad of die-cut 20.0 inches (50.8cm) diameters from the layer compound, thus the pad with structuring polishing characteristic of the present invention, instance 14 formed.

Comparative example C5

10 prepare comparative example C5 as the instance, and difference is, saves A15LV in the composition of resin compound.

Comparative example C6

10 prepare comparative example C6 as the instance; Difference is; The 1.44 gram A15LV, 23 that consist of of resin compound restrain P-250,47.50 gram PHP-75D and 0.68 gram DC5604, and only use the heat cure of under 100 ℃, carrying out two hours, have omitted the UV curing schedule.

Comparative example C7

C6 prepares comparative example C7 as the comparative example, and difference is, saves A15LV in the composition of resin compound.

Instance 15

5 prepare instance 15 as the instance, and difference is that the 7.58 gram 5350D, 28.00 that consist of of resin compound restrain M1,23.75 gram PHP-75D, 16.50 gram D100,0.83 gram TPO-L and 0.77 gram DC5604.

Comparative example C8

15 prepare comparative example C8 as the instance; Difference is; The 8.39 gram 5350D, 28.00 that consist of of resin compound restrain M1,47.50 gram PHP-75D and 3.5g DC5604, and only use the heat cure of under 100 ℃, carrying out two hours, have omitted the UV curing schedule.

Utilize method of testing 2 and 3; The hardness of practical measuring examples 10-15 and comparative example C5-C8, aperture mean value, aperture standard deviation, pore diameter range, aperture unevenness and porosity.The result is shown in the following table 2.

Table 2. hardness, aperture and porosity data

" embodiment " who mentions in the whole specification, " some embodiment ", " one or more embodiment " or " embodiment "; No matter, all mean the special characteristic, structure, material or the characteristic that combine this embodiment to describe and be included at least a embodiment among the certain exemplary embodiment of the present invention at the preceding term " exemplary " that whether comprises of term " embodiment ".Therefore, whole specification occur everywhere may not be meant the same embodiment among the certain exemplary embodiment of the present invention like " in one or more embodiments ", " in certain embodiments ", " in one embodiment " or phrases such as " in an embodiment ".In addition, concrete characteristic, structure, material or characteristics can any suitable mode be attached among one or more embodiment.

Though this description details certain exemplary embodiment, should be appreciated that those skilled in the art after understanding foregoing, can be easy to imagine altered form, variations and the equivalents of these embodiment.Therefore, should be appreciated that the present invention should not be subject to the above exemplary embodiment that illustrates undeservedly.Especially, used like the application, the statement of the number range of carrying out through end points is intended to be included in all included in this scope numerical value (comprising 1,1.5,2,2.75,3,3.80,4 and 5 as 1 to 5).In addition, all used numbers of the application all are considered to modified by term " about ".In addition, all publications that the application quotes and full patent texts are incorporated the application into to quote mode as proof, just as by especially and each publication or the patent pointed out individually, all incorporate into to quote mode as proof.

Various exemplary embodiments are illustrated.These and other embodiment belongs in the scope of following claims.

Claims

1. polishing pad, it comprises:

Compliant layers, it has the first and second relative sides; And

Polymer particle, it is dispersed in the said cross-linked network; And

Closed pore, it is dispersed in the said cross-linked network.

2. polishing pad according to claim 1, it also comprises the supporting course that places between said compliant layers and the said porous polishing layer.

3. polishing pad according to claim 1 and 2; Wherein said heat cure component comprises at least a of polyurethane or polyepoxide, and wherein said radiation curable component comprises at least a in polyacrylate, polymethacrylates, polyvinylether, ethene polymers or the polyepoxide.

4. polishing pad according to claim 1 and 2, wherein said heat cure component and said polymer particle comprise polyurethane independently of one another, and wherein said radiation curable component comprises at least a in polyacrylate or the polymethacrylates.

5. according to each described polishing pad of claim 1 to 4, wherein said polymer particle is covalently bound at least a in said heat cure component or the said radiation curable component in the said cross-linked network.

6. polishing pad according to claim 4, wherein said polyacrylate or polymethacrylates are covalently bound to said heat cure component through carbamate or urea linking group.

7. method of making polishing pad, said method comprises:

In said composition, form the hole;

Said composition is positioned on the supporting course; And

8. method according to claim 7, this method also comprise compliant layers adhesively are attached on the surface of the said supporting course relative with said porous polishing layer.

9. according to claim 7 or 8 described methods; Wherein said heat-curable resin composition comprises first resin with at least two isocyanate groups or at least two epoxide groups and has at least two second resin in hydroxyl, amino, carboxyl or the mercapto groups, and wherein said radiation-hardenable composition comprises at least two in acrylic acid ester, methacrylate, vinyl or the epoxide group.

10. method according to claim 9; Wherein said first resin has at least two isocyanate groups; Wherein said second resin has at least two oh groups or at least two amino groups; Wherein said radiation-hardenable composition comprises at least two acrylic acid ester or methacrylate based group, and wherein said radiation-hardenable composition also comprises at least one isocyanate groups or oh group.

11. according to each described method of claim 7 to 10, wherein said composition also comprises surfactant.

12. according to each described method of claim 7 to 11, wherein said hole is a closed pore.

13. according to described polishing pad of aforementioned arbitrary claim or method, the hardness that wherein said porous polishing layer is measured through method of testing 2 is at least 40 Shore D hardness.

14. according to described polishing pad of aforementioned arbitrary claim or method, the particle mean size of wherein said polymer particle is in 5 microns to 500 microns scope.

15. according to described polishing pad of aforementioned arbitrary claim or method, wherein said polymer particle is a substantially spherical.

16. according to described polishing pad of aforementioned arbitrary claim or method, wherein said polymer particle is a fiber.

17. according to described polishing pad of aforementioned arbitrary claim or method, wherein said polymer particle exists with the maximum 20 weight % based on the gross weight of said porous polishing layer.

18. according to described polishing pad of aforementioned arbitrary claim or method, the aperture unevenness in wherein said hole is 75% to the maximum.

19. according to described polishing pad of aforementioned arbitrary claim or method, the average pore size in wherein said hole is in 5 microns to 100 microns scope.

20. according to described polishing pad of aforementioned arbitrary claim or method, wherein said polishing layer comprises from the polishing element of the outstanding separation of said supporting course or said compliant layers.

21. according to described polishing pad of aforementioned arbitrary claim or method, the one deck at least in wherein said supporting course or the compliant layers includes at least a of machine silicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyolefin or polyurethane.

22. according to described polishing pad of aforementioned arbitrary claim or method, at least a portion of wherein said polishing pad is transparent.

23. a finishing method, it comprises:

With the surface of substrate with according to claim 1 to 6 each or contact as each the said porous polishing layer of each described polishing pad of claim 13 to 22 of dependent claims of claim 1 to 6; And