CN102762340B

CN102762340B - Polishing pad and manufacture method thereof

Info

Publication number: CN102762340B
Application number: CN201080063912.3A
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: 2016-12-14
Anticipated expiration: 2030-12-20

Abstract

The present invention relates to the polishing pad with porous polishing layer, the method manufacturing this polishing pad, and the method using this polishing pad in glossing.Described polishing pad includes compliant layers and porous polishing layer, and described compliant layers has the first and second opposite sides, and described porous polishing layer is arranged on the first side of described compliant layers.Described porous polishing layer includes cross-linked network, and it includes thermosetting adhesive composition and radiation curable component, wherein said radiation curable component and described thermosetting adhesive composition covalent bonding in described cross-linked network.Described porous polishing layer also includes that the polymer particle being dispersed in described cross-linked network, wherein said polymer particle include at least one in thermoplastic polymer or thermosetting polymer.Described porous polishing layer the most also includes the closed pore being dispersed in described cross-linked network.

Description

Polishing pad and manufacture method thereof

Cross-Reference to Related Applications

This application claims the U.S. Provisional Patent Application No. of December in 2009 submission on the 22nd The U.S. Provisional Patent Application No. 61/422,442 of 61/288,982 and 2010 on December submission in 13, Rights and interests, the full content of these patent applications is incorporated herein to quote mode as proof.

Background technology

In the manufacture process of semiconductor device and integrated circuit, by a series of deposition and erosion Carve step and process silicon chip repeatedly to form material layer and the apparatus structure of overlying.Quilt can be used The referred to as polishing technology of chemical mechanical planarization (CMP) stays after removing deposition and etching step Under surface irregularity (such as swell, have the region of not equal altitude, groove and ditch), target For obtaining, not there is cut and the smooth wafer surface of depression (being referred to as butterfly hole), i.e. whole In individual wafer surface, there is high level of homogeneity.

In typical CMP planarization technique, be there is hydraulic fluid in the substrate such as wafer etc In the case of overlay on polishing pad and carry out relative movement, described work relative to polishing pad Liquid is usually abrasive particle serosity in water and/or etch chemistries.Together with abrasive water The various CMP pad used are published in such as U.S. Patent number 5,257,478 (Hyde et al.)； 5,921,855 (Osterheld et al.)；6,126,532 (Sevilla et al.)；6,899,598(Prasad) With in 7,267,610 (Elmufdi et al.).Fixing abrasive polishing pad is known, such as United States Patent (USP) Being enumerated in number 6,908,366 (Gagliardi), wherein abrasive grain Chang Yicong pad surface extends The form of abrasive composites of precise forming be typically secured to the surface of pad.Recently, have from The polishing pad of multiple polishing elements that compressible bottom extends is described in international application published number In WO/2006057714 (Bajaj).Although multiple polishing pad is known and is used, But this area is still continually looking for the polishing pad for the novel of CMP with improvement, in particular for Wherein use bigger chip diameter, or need higher wafer surface flatness and polishing uniformly In the CMP of degree.

Summary of the invention

The invention provides porous polishing pad and the method manufacturing this polishing pad, described polishing pad Having polishing layer, described polishing layer has thermosetting adhesive composition and radiation curable component.Hole is by making Join in described polishing layer with polymer particle.In described porous polishing pad disclosed in the present application Hole be closed pore, it is generally of lower aperture compared with the hole of conventional heat cure polishing pad Unevenness and less aperture.Control aperture and distribution is the most favourable, such as, for throwing The polishing performance of light pad is the most favourable.

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

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

Porous polishing layer, it is arranged on the first side of described compliant layers, described porous polishing layer Including:

Cross-linked network, it includes thermosetting adhesive composition and radiation curable component, and wherein said radiation is solid Change component and described thermosetting adhesive composition covalent bonding in described cross-linked network；

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

Closed pore, it is scattered in described cross-linked network.In certain embodiments, described polishing pad Also include the supporting course between described compliant layers and described porous polishing layer.

On the other hand, the present invention provides a kind of method manufacturing polishing pad, and described method includes:

Offer includes heat-curable resin composition, radiation-curable resin composition and polymerization The compositions of thing particle；

Form hole in the composition；

Described compositions is positioned on supporting course；And

By compositions being exposed to radiation with at least partially curing described radiation curable resins group Compound, and described compositions is heated with at least partially curing described heat-curable resin composition, Thus on described supporting course, form porous polishing layer.In certain embodiments, described method is also Including on the surface that compliant layers is adhered to the described supporting course relative with described porous polishing layer.

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

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

Described polishing pad is relatively moved to denude the surface of described substrate about described substrate.

The exemplary embodiment of the polishing pad according to the present invention has can be used for multiple polishing Various features and characteristics in application.In certain embodiments, the polishing pad of the present invention can be especially Chemical mechanical planarization be applicable to the wafer used during manufacturing integrated circuit and semiconductor device (CMP).In certain embodiments, polishing pad described in the invention can provide in following advantage Some or all.

Such as, in certain embodiments, can be used for CMP according to the polishing pad of the present invention The hydraulic fluid of middle use is maintained at the boundary between the polished surface of pad and polished substrate surface At face, thus improve hydraulic fluid effectiveness in strengthening polishing.In other exemplary enforcement In example, can reduce or eliminate recessed in polishing process of wafer surface according to the polishing pad of the present invention Fall into and/or edge corrosion.In some exemplary embodiments, use in a cmp process according to this The polishing pad of invention can obtain wafer interior the polishing uniformity, the flatter polishing wafer table of improvement Face, derive from the increase of the edge crystal grain productivity of wafer and the working condition of the CMP of improvement And concordance.In a further embodiment, use can allow protecting according to the polishing pad of the present invention Process larger-diameter wafer while holding the surface evenness of desirable degree and produce to obtain high chip Rate, pad surface need carry out nursing one's health to keep the pre-treatment of the polishing uniformity of wafer surface more Multi-wafer or minimizing process the abrasion on time and pad conditioner device.

In the present invention:

The standard deviation of " aperture unevenness " finger-hole footpath meansigma methods is multiplied by divided by average pore size 100。

Term " polyurethane " refers to have more than one 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 series race, alicyclic Or aromatic group), biuret, allophanates, the appointing of urea diketone or isocyanurate-bond The polymer of meaning combination.

Term " (methyl) acrylate " refers to acrylate and methacrylate, and it can wrap Include urethane acrylate, methacrylate and acrylate and methacrylate Combination.

Term " polymerization " refers to the molecule having a structure in which, this structure includes spreading out from low Multiple repetitions of the unit of the molecule of relative molecular weight.Term " polymerization () " includes " few Poly-() ".

" one ", " a kind of " and " as described in " such term is not intended to refer to odd number Body, but include general category, object lesson therein can be used to explain use.Term " one Individual ", " a kind of " and " described " can exchange with term " at least one (at least one) " Use.

It is followed by phrase " at least one (individual) " and " the including at least one (individual) " enumerated Refer to include any one in listed items and two in listed items or more any group Close.

Except as otherwise noted, all numerical rangies all include between their end points and end points Non integer value.

Various aspects and advantage to the exemplary embodiment of the present invention are collected.More than send out Bright content is not intended to describe each diagram embodiment of the present invention or every kind of embodiment.Below The drawings and specific embodiments more particularly exemplify some embodiments of the present invention.

Accompanying drawing explanation

The exemplary embodiment of the present invention is further described with reference to the accompanying drawings, in the accompanying drawings:

Figure 1A and Figure 1B is cross sectional view and the vertical view of porous polishing pad in prior art respectively The microgram of figure；

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

Fig. 3 is the polishing pad with protrusion polishing element according to an alternative embodiment of the invention Side view；

Fig. 4 is that having of another embodiment according to the present invention protrudes the polishing pad polishing element Side view；

Fig. 5 A and Fig. 5 B is the example 2 that can be used for being formed the polishing layer according to the present invention respectively The cross sectional view of solidification compositions and the microgram of top view；

Fig. 6 A and Fig. 6 B is cross sectional view and the vertical view of the solidification compositions of comparative example 3 respectively The microgram of figure；

Fig. 7 A and Fig. 7 B is the example 15 that can be used for being formed the polishing layer according to the present invention respectively The cross sectional view of solidification compositions and the microgram of top view；And

Fig. 8 is the solidification compositions that can be used for being formed the example 11 of the polishing layer according to the present invention The microgram of cross sectional view.

The component that like reference numerals instruction in accompanying drawing is similar to.Accompanying drawing in the application by than Example is drawn, and in the accompanying drawings, the parts of polishing pad are by emphasize that the size of selected feature shows.

Detailed description of the invention

Typical CMP pad is made up of thermosetting (such as, the polyurethane) material with hole.Can Utilize such as micro-balloon, soluble fiber, gas trapping (such as, on the spot or non-produce on the spot) Described hole is generated with the multiple method of physics air capture.When using such methods, due to In polyreaction produce thermograde, molding produce table sheath core effect, the distribution of fiber, The dissolution rate of soluble fiber and polishing chemical reaction, the hole dimension in control pad, pore volume Can be challenging with pore size distribution.

Some commercially available CMP pad have generation in the curing process of isocyanate resin Perforate pad constructs.Fig. 1 show with trade name " S7 " can from PPG Industries(Pittsburgh, PA) cross sectional view of perforate CMP pad manufactured with commercial system obtained and top view.As Shown in Fig. 1, in this pad, the size in hole, shape and distribution are the most controlled.

The present invention relates to the porous polishing pad improved, be wherein usually formed and there is controlled dimensions with equal The closed pore of evenness.Multiple exemplary embodiments of the present invention explained below.The example of the present invention Property embodiment can carry out without departing from the spirit and scope of the present invention multiple amendment and Change.It will thus be appreciated that embodiments of the invention should not necessarily be limited by examples described below Embodiment, but should be by claims and any equivalent thereof are given controlling of being limited.

Include compliant layers 10a referring now to Fig. 2, porous polishing pad 2a and be arranged on described submissive Porous polishing layer 12a on layer side (that is, one first type surface).Optional supporting course 8a Between porous polishing layer 12a and compliant layers 10a, it can be used for the porous polishing pad of the present invention Some embodiments and methods in.Porous polishing layer includes cross-linked network, is scattered in cross-linked network In polymer particle and the closed pore that is scattered in cross-linked network.Compared in polishing process Remove the component of polishing pad with formed cavity (such as, by corrode or dissolve) polishing pad and Method, was exactly porous according to the polishing pad of the present invention before polishing starts.

Exemplary polymer particle in polishing layer can include thermoplastic polymer particles, thermosetting Property polymer particle and their mixture.Term " thermoplastic polymer " refers to not hand over Join and be substantially formed without the polymeric material of three-dimensional network.Term " thermosetting " refers to the most real The polymer of crosslinking in matter, wherein said polymer substantially has three-dimensional network.Real at some Executing in example, polymer particle can be selected as minimizing the particles sintering that heating causes and (that is, exist Minimal amount of creeping (plastic flow) is there is on the border of polymer particle, and the present invention's Seldom coalescence or not coalescence between the particle of the polymer particle in polishing pad).Real at some Execute in example, when the polymer particle of pad includes granular thermoplastic polymer, can be at granular thermoplastic Polishing pad is prepared below the fusion point of property polymer or weld point.In other embodiments, polymerization Thing particle includes thermosetting polymer.

Realize the present invention can polymer particle can be prepared by various methods (such as, condensation Reaction, the reaction of free radical initiation or combinations thereof).In another embodiment, polymer The IPN that the condensation reaction by progressively or simultaneously carrying out and Raolical polymerizable are formed can be included Network polymers.In the present invention, term " polymer network of IPN " (IPN) refers to Being the combination of netted two kind polymer, in described polymer, at least one occurs at another kind Synthesize the most immediately or cross-link.Generally in IPN, between two kinds of polymer, there is not induction Covalent bond.Therefore, in addition to mechanical mixture and copolymerization, IPN represents can be by different polymer at thing Another mechanism combined in reason.

Polymer particle can be prepared by various methods.In certain embodiments, bulky polymer Can be ground and be categorized as desired particle size range by low temperature.The shape of polymer particle can be rule Or irregular, and following shape can be included: ball, fiber, dish, thin slice and they Combination or mixing.In certain embodiments, polymer particle is substantially spherical.Term " base This is the most spherical " refer to that steradian is at least 0.75(in certain embodiments, at least 0.8,0.85,0.9, 0.95,0.96,0.97 or 0.98) particle.In certain embodiments, polymer particle is fine Dimension.Can be used for realizing the aspect ratio (that is, longest dimension is than shortest dimension) of the fiber of the present invention Generally at least 1.5:1, such as, at least 2:1,3:1,4:1,5:1,10:1,25:1,50:1, 75:1,100:1 or bigger.Can be used for the aspect ratio realizing the fiber of the present invention from 2:1 to In the range of 100:1,5:1 to 75:1 or 10:1 to 50:1.

In certain embodiments, the particle mean size of polymer particle is that at least 5(is in some embodiments In, at least 7,10,15,20,25,30,40 or 50) micron.In certain embodiments, The particle mean size of polymer particle is at most 500(in certain embodiments, at most 400,300, 200 or 100) micron.Described granularity is often referred to the diameter of particle；But, it is aspheric at particle In some embodiments of shape (such as, fiber), described granularity can refer to the full-size of particle. The particle mean size of polymer particle can be determined by conventional method.Such as, polymer particle is flat All granularities may utilize light scattering technique, as utilized by Beckman Coulter Incorporated system Make and determine from its commercially available Coulter LS Particle Size Analyzer.Want in this specification and right Asking in book, " granularity " refers to based on by utilizing Coulter Counter LS Particle Size Analyzer to carry out The diameter of the particle of the percent by volume that light scattering determines or full-size.In this light scattering technique In, regardless of the true form of particle, all by revolution hydraulic radius (hydrodynamic radius Of gyration) determine its granularity." averagely " granularity is the average of particle based on percent by volume Diameter.In certain embodiments, especially in the embodiment that particle is fiber, sieve according to routine The determination of selecting technology, fiber has and is up to about 600,500 or 450 microns of (30,35 or 40U. S.Mesh) maximum particle diameter.Such as, in certain embodiments, at least 97%, 98% or 99% Fiber by having opening of 600,500 or 400 microns (30,35 or 40U.S.Mesh) The screen cloth of mouth.

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%).Granularity non-uniformity refers to that granulometry deviation is divided by average particle Degree is multiplied by 100.

In certain embodiments, polymer particle is essentially solid.In the application, term " base This is solid " mean that granular polymer is non-hollow, such as, polymer particle is not hollow micro-glue The form of capsule.But, in certain embodiments, essentially solid polymer particle can be containing prisoner The bubble obtained.

Suitably polymer particle include polyvinylchloride rope, polyethylene fluorides, polyethylene, Polypropylene, nylon, Merlon, polyester, poly-(methyl) acrylate, polyethers, polyamides Amine, polyurethane, polyepoxides, polystyrene, polyimides (such as, polyetherimide Amine), polysulfones and their mixture.In certain embodiments, the optional autohemagglutination of polymer particle (methyl) acrylate, polyurethane, polyepoxides and their mixture.

In certain embodiments, polymer particle includes water soluble particle.Exemplary available water Soluble particle includes by saccharide (such as, such as dextrin, cyclodextrin, starch, mannitol and breast Sugar polysaccharide), cellulose (such as, hydroxypropyl cellulose and methylcellulose), protein, Polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, poly(ethylene oxide), water soluble light-sensitive tree Fat, sulfonated polyisoprene, sulfonated polyisoprene copolymer and the combination in any of these materials The particle made.In certain embodiments, polymer particle includes cellulose.Implement at these In some of example, polymer particle includes methylcellulose.Although it is in these embodiments, poly- Polymer particle includes water soluble particle, but polymer particle can be in polishing when forming polishing layer Hole is formed in Ceng.Need not to dissolve in polishing process the hydraulic fluid of particle when forming hole.

In certain embodiments, polymer particle includes polyurethane, and it can be by, such as, below Prepared by material: include the resin of at least two isocyanate groups, and/or have at least two envelope The blocked isocyanate reactant of the isocyanate groups of end；With the second resin, it has with different At least two group that cyanate group reacts.

In certain embodiments, the first and second resins can mix, and is polymerized or solid Changing to form bulk polyurethane, it can be grated (such as, low temperature grinds) and optional subsequently Ground classification.In certain embodiments, polymer particle can be formed by following steps: by first Resin and the second mixed with resin are together；Described mixture is slowly poured into heating by agitation limit, limit Deionized water in (alternatively, in the case of there are co-solvent content and/or surfactant)； Separate the bulk material (such as, by filtering) formed；The bulk material of separation is dried with And alternatively dry granular polyurethane is classified.In another embodiment, there are Machine solvent (such as, alcohol, water-insoluble ether, side chain and straight-chain hydrocarbons, ketone, toluene, dimethylbenzene Mixture with them) in the case of, isocyanates and hydrogenous material can mix.

In certain embodiments, the first resin comprising at least two isocyanate groups is selected from Isocyanate functional monomer, isocyanate-functional prepolymers and combinations thereof.Exemplary conjunction Suitable isocyanate-monomer includes aliphatic polymeric isocyanate；Ethylenic unsaturated polyester isocyanates； Alicyclic polyisocyanate；Aromatic poly-isocyanate, the wherein not direct key of isocyanate groups Close and arrive aromatic ring, such as, α, α ' XDI；Aromatic poly-isocyanate, its Middle isocyanate groups is bonded directly to aromatic ring, such as, and phenylene diisocyanate；Halogenation, The carbodiimide modified of alkylation, alkoxylate, nitrification and these polyisocyanate, urea change Property and biuret modified derivant；And the dimerization of these polyisocyanate and trimerization product.

Exemplary aliphatic polyisocyanate includes ethylene diisocyanate, trimethylene two Carbimide. Ester, tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene two Carbimide .s Ester, nine methylene diisocyanates, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethyl Hexane diisocyanate, decamethylene diisocyanate, 2,4,4-trimethyl-cyclohexane two Carbimide. Ester, 1,6,1-hendecane triisocyanate, 1,3,6-hexa-methylene triisocyanate, 1,8-bis-isocyanide Acid esters-4-(isocyanatomethyl) octane, 2,5,7-trimethylene-1,8-diisocyanate-5- (isocyanatomethyl) octane, double (isocyanatoethyl)-carbonate, double (isocyanide Acid group close ethyl) ether, 2-isocyanatopropyl-2,6-two isocyanato-caproate, methyl Lysinediisocyanate, methyllysine triisocyanate and their mixture.

Exemplary suitable ethylenic unsaturated polyester isocyanates can include butene diisocyanate and 1,3-butadiene-1,4-diisocyanate.Exemplary suitable alicyclic polyisocyanate includes different Buddhist Your ketone diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, double (different Cyanate radical close methyl) hexamethylene, double (isocyanatocyclohexyl) methane, double (Carbimide. Root cyclization hexyl)-2,2-propane, double (isocyanatocyclohexyl)-1,2-ethane, 2-Carbimide. Root closes methyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo-[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo- [2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyano Close methyl-bicyclo-[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo-[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-Carbimide. Root close propyl group)-6-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane, 2-isocyanato- Methyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptan Alkane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl) -bicyclo-[2.2.1]-heptane and their mixture.

Wherein isocyanate groups is not bonded directly to the Exemplary aromatic adoption isocyanide of aromatic ring Acid esters includes double (isocyanatoethyl) benzene, α, α, α ', α '-tetramethylene diisocyanate, 1,3- Double (1-isocyanato--1-Methylethyl) benzene, double (isocyanatobutyl) benzene, double (different Cyanate radical close methyl) naphthalene, double (isocyanatomethyl) diphenyl ether, double (isocyanato- Ethyl) phthalate ester, sym-trimethylbenzene. triisocyanate, 2,5-bis-(isocyanatomethyl) furan Mixture with them.

Wherein isocyanate groups is bonded directly to the Exemplary aromatic adoption Carbimide. of aromatic ring Ester includes phenylene vulcabond, ethylphenylene diisocyanate, isopropyl phenylene two Isocyanates, dimethylphenylene diisocyanate, diethyl phenylene vulcabond, two Isopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene Diisocyanate, methyl naphthalene diisocyanate, diphenyl diisocyanate, adjacent dimethyl diamino Base biphenyl diisocyanate, 4,4'-methyl diphenylene diisocyanate, double (3-methyl-4-Carbimide. Root close propyl group) methane, double (isocyanatophenyi) ethylene, 3,3'-dimethoxy-diphenyl -4,4'-diisocyanate, triphenylmethane triisocyanate, polymerization 4,4'-diphenyl methane two are different Cyanate, naphthalene triisocyanate, diphenyl methane-2,4,4'-triisocyanate, 4-methyldiphenyl base Methane-3,5,2', 4', 6'-five isocyanates, diphenyl ether diisocyanate, double (isocyanato-benzene Base ether) ethylene glycol, double (isocyanatophenyi ether)-1,3-propylene glycol, benzophenone two Carbimide. Ester, carbazole diisocyanate, ethyl carbazole diisocyanate, dichloro carbazole diisocyanate and Their mixture.

In certain embodiments, the first resin including at least two isocyanate groups is selected from α, α '-XDI, α, α, α ' α '-tetramethylxylene diisocyanate, isophorone Diisocyanate, double (isocyanatocyclohexyl) methane, toluene di-isocyanate(TDI), 4,4'- Methyl diphenylene diisocyanate and their mixture.

In certain embodiments, first resin with at least two isocyanate groups can include Isocyanate-functional polyurethane prepolymer.Isocyanate-functional polyurethane prepolymer can pass through Prepared by multiple routine techniques.In certain embodiments, such as at least one polyhydric alcohol and such as of glycol At least one isocyanate functional monomer of diisocyanate monomer can be reacted to form together to be had The polyurethane prepolymer of at least two isocyanate groups.Exemplary suitable isocyanate-functional Monomer includes aforesaid isocyanate functional monomer.

The suitable isocyanate-functional polyurethane prepolymer that can be used for realizing the present invention can have The molecular weight of change on a large scale.In certain embodiments, isocyanate-functional polyurethane The number-average molecular weight (Mn) of prepolymer can be from 500 to 15000, or from 500 to 5000, It is according to such as utilizing the gel permeation chromatography (GPC) of polystyrene standard to determine.

The Exemplary polyols that can be used for preparing isocyanate-functional polyurethane prepolymer includes: Straight or branched alkyl polyols, as 1，2-ethandiol, 1,3-PD, 1,2-PD, Isosorbide-5-Nitrae- Butanediol, 1,3 butylene glycol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, Two-trimethylolpropane, erithritol, tetramethylolmethane and two-tetramethylolmethane；Poly alkylene glycol, Such as two-, three-and four ethylene glycols and two-, three-and tetrapropylene glycol；Cyclic alkyl polyhydric alcohol, Such as Pentamethylene. glycol, cyclohexane diol, phloroglucitol, cyclohexanedimethanol, hydroxypropyl Hexalin and hexamethylene diethanol；Aromatic polyol, such as dihydroxy benzenes, benzene triol, hydroxyl Benzyl alcohol and orcin；Bis-phenol, such as 4,4'-isopropylidene xenol (bisphenol-A), 4,4'- Oxo biphenol, 4,4'-dihydroxy benzophenone, 4,4'-thiodiphenol, phenolphthalein, double (4-oxybenzene Base) methane (Bisphenol F), 4,4'-(1,2-ethenylidene) bis-phenol and 4,4'-sulphonyl bis-phenol；Halogen Change bis-phenol, such as 4,4'-isopropylidene double (2,6-dibromophenol), 4,4'-isopropylidene double (2,6-bis- Chlorophenol) and 4,4'-isopropylidene pair (2,3,5,6-tetrachlorophenol)；Alkoxyl bis-phenol, such as alkane Epoxide 4,4'-isopropylidene xenol, its have as ethyoxyl, propoxyl group, α-butoxy and β- One or more alkoxy bases of butoxy radicals；And biscyclohexanol, it can be by making correspondence Bis-phenol hydrogenation and prepare, such as 4,4'-isopropylidene-biscyclohexanol, 4,4'-oxo biscyclohexanol, 4,4'-thio-bicyclo hexanol and double (4-hydroxy cyclohexylphenyl alcohol) methane.

Can be used for preparing other of suitable polyhydric alcohol of isocyanate-functional polyurethane prepolymer Example includes higher poly alkylene glycol, if number-average molecular weight (Mn) is from 200 to 2000 Gram/mol Polyethylene Glycol；With the acrylic resin of hydroxyl, as by (methyl) acrylate Those of combined polymerization formation with hydroxy-functional (methyl) acrylate, such as methacrylic acid Methyl ester and hydroxyethyl methylacrylate copolymer；And hydroxy-functionalized polyesters, as by glycol (as Butanediol) and the reaction of diacid or diester (adipic acid or diethylene adipate) formed that A bit.In certain embodiments, the polyhydric alcohol that can be used for realizing the present invention can have from 200 to 2000 Gram/mol number-average molecular weight.

In certain embodiments, isocyanate-functional polyurethane prepolymer can be by will be such as toluene The diisocyanate of diisocyanate reacts with the poly alkylene glycol such as poly-(oxolane) Preparation.

In certain embodiments, can there is catalyst in isocyanate-functional polyurethane prepolymer In the case of be prepared.In certain embodiments, based on polyhydric alcohol and isocyanate-functional list The gross weight of body, the amount of the catalyst of use can be less than 5 weight %, or less than 3 weight %, or Less than 1 weight %.In certain embodiments, exemplary suitable catalyst includes the Asia of organic acid Stannum adduct, as stannous octoate, dibutyltin dilaurate, dibutyl tin diacetate, Dibutyl tin mercaptides, dibutyl tin dimaleate, stannous methide diacetate, dimethyl Stannum dilaurate, 1,4-diazabicylo (2.2.2) octane and their mixture.Real at other Executing in example, catalyst can be the acetylacetonate of zinc octoate, bismuth or ferrum.Other exemplary conjunction Suitable catalyst includes tertiary amine, such as triethylamine, Tris(isopropylamine). and N, N-dimethyl benzylamine.

In certain embodiments, for can be used for preparing the polyurethane of polymer particle, have to First resin of few two isocyanate groups includes the NCO with at least two end-blocking The blocked isocyanate compounds of group.Term " isocyanate compound of end-blocking " refers to have different Cyanate group end and/or side end-blocking monomer or prepolymer, it can be converted into Kaifeng (i.e., Free) isocyanate groups and separation or free end-capping group.Any of above the most different The example of cyanate esters can be blocked.The exemplary non-fugitive end-blocking of the isocyanates of end-blocking Group includes: 1H-azoles, as 1H-imidazoles, 1H-pyrazoles, 3,5-dimethyl-1H-pyrazoles, 1H-1,2,3- Triazole, 1H-1,2,3-benzotriazole, 1H-1,2,4-triazole, 1H-5-methyl isophthalic acid, 2,4-triazole and 1H-3- Amino-1,2,4-triazole；Lactams, such as e-caprolactam and 2-Pyrrolidone；Morpholine, such as 3- Aminopropyl morpholine；With N-hydroxyl phthalimide.The example of blocked isocyanate compounds The fugitive end-capping group of property includes: alcohol, such as propanol, isopropanol, butanol, isobutanol, the tert-butyl alcohol And hexanol；Alkylidene ethylene glycol monoalkyl ether, such as ethylene glycol monoalky lether (such as, second Allyl diglycol single-butyl ether and ethylene glycol list hexyl ether) and propyleneglycoles monoalky lether (example As, propyleneglycoles monomethyl ether)；And ketoxime, such as methyl ethyl ketoxime.

While not wishing to be bound by any theory, it is believed that, there is at least two Carbimide. First resin of ester group includes that the isocyanate material of end-blocking may result in and is formed in following position Covalent bond: (a) granular polyurethane particle at least some of between；And/or (b) is at grain At least some of and the cross-linked network of shape polyurethane at least some of between.In some embodiments In, the isocyanate compound of end-blocking can be according to a certain amount of existence, and described amount makes based on free Total molar equivalent of the isocyanate groups of isocyanates and end-blocking, the isocyanide of the first resin end-blocking The amount of acid esters group is at least 5 moles of %, or at least 10 moles of %, or less than 40 moles of % or Less than 50 moles of %.

Second resin with at least two group reacted with isocyanate groups is selected from many Plant material.In certain embodiments, the second resin has selected from hydroxyl, sulfydryl, primary amine, secondary Amine and the functional group of combinations thereof.Exemplary suitable second resin includes aforesaid polynary Alcohol.

In certain embodiments, can have at least two that can react with isocyanate groups Second resin of group includes polyamine.Exemplary polyamine includes polyethylene polyamine (ethyleneamine), as 1，2-diaminoethane (EDA), diethylenetriamines (DETA), Trien (TETA), TEPN (TEPA), five ethylidene hexylamines (PEHA), Piperazine, diethylene diamine (DEDA) and 2-amino-1-ethyl piperazidine.Other is exemplary the most poly- Amine includes one or more isomers of dialkyltoluene diamidogen, such as 3,5-dimethyl-2,4-toluene two Amine, 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 is selected from methylene dianiline (MDA), trimethylene Glycol two (para-aminobenzoate) and amine end-capped oligomeric and prepolymer.

In certain embodiments, suitable polyamine is selected from based on 4,4'-methylene-bis-(dialkyl group Aniline) (such as 4,4'-methylene-bis-(2,6-dimethylaniline), 4,4'-methylene-bis-(2,6- Diethylaniline), 4,4'-methylene-bis-(2-ethyl-6-monomethylaniline .), 4,4'-methylene-bis- (2,6-diisopropyl aniline), 4,4'-methylene-bis-(2-isopropyl-6-monomethylaniline .), 4,4'- Those of methylene-bis-(2,6-diethyl-3-chloro aminobenzen) and their mixture.

In certain embodiments, by the first resin and the bag including at least two isocyanate groups Including can be with the second resin-made of at least two group of isocyanate-reactive for granular polyurethane Can perform in the presence of a catalyst.Suitably catalyst includes above in relation to isocyanates The preparation of functionalized polyurethane prepolymer list those.

In certain embodiments, can be used for preparing the isocyanate groups of granular polyurethane and optional The isocyanate groups of end-blocking and the molar equivalent ratio of isocyanate-reactive group be from 0.5:1.0 to 1.5:1.0, such as, 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 be by the second tree with less than the amount required in Chemical Calculation mode Fat prepares cross-linked polyurethane so that amino-formate bond or urea bond by with unnecessary isocyanates Reaction.In other embodiments, difunctional compound is changed to trifunctional compound will cause more The chemical crosslinking of thermal-stable.

Some available granular polyurethanes are commercially available, such as with trade name " DAIMIC-BEAZ " Derive from Dainichiseika Color & Chemicals Mfg.Co., Ltd.Advanced Polymers Group(Tokyo, Japan) granular polyurethane, its be divided into " UCN-5350D ", " UCN-5150D " and " UCN-5070D " grade；Obtain with trade name " ART PEARL " From Negami Chemical Industrial Co., Ltd.(Nomi-city, Japan) polyurethane grain Son；And such as with trade name " TEXIN " derive from Bayer Corporation based on fat The thermoplastic polyurethane of adoption ether.

In certain embodiments, the suitable polymer particle that can be used for realizing the present invention includes grain Shape polyepoxides.Such as, granular polyepoxides can be by having at least two epoxy radicals Group the first resin and have can with the epoxide group of described epoxide react at least two Prepared by the product of the second resin of individual group.

In certain embodiments, including the first resin and second resin of at least two epoxide group Can mix, and be polymerized or be cured to form bulk polyepoxides, it subsequently may be used It is grated (such as, low temperature grinds) and classifies alternatively.In certain embodiments, can lead to Cross following steps and form granular polyepoxides: by epoxy functional material and hydrogen functional material Mix, gained mixture is slowly poured in the deionized water of heating by Jiao Ban limit, limit, Separate formed bulk material (such as, by filter), the bulk material of separation is dried with And alternatively dry granular polyepoxides is classified.

In certain embodiments, can be used for realizing the suitable epoxy functional material bag of the present invention Include epoxide-functional monomer, epoxy-functional prepolymer and combinations thereof.Exemplary suitably Epoxide-functional monomer comprises the steps that aliphatic polyepoxide, such as 1,2,3,4-bicyclic oxygen butane, 1,2,7,8-diepoxyoctane；Alicyclic polyepoxides, such as 1,2,4,5-bicyclic oxygen hexamethylenes Alkane, 1,2,5,6-bicyclic oxygen cyclooctane, 7-oxa--bicyclo-[4.1.0] heptane-3-carboxylic acid 7-oxa--two Ring [4.1.0] hept-3-ylmethyl ester, 1,2-epoxy radicals-4-oxa-base-hexamethylene and 2,3-(glycidyl) Hexamethylene；Aromatic polyepoxide compound, such as double (4-hydroxyphenyl) methane diglycidyl ether； Hydrogenated bisphenol A diepoxide and their mixture.Can be used in the present invention is epoxy functionalized Monomer is generally reacted by polyhydric alcohol and epihalohydrin (such as, epoxychloropropane) to be prepared.Can Include that the application is previously with respect to isocyanate-functional for preparing the polyhydric alcohol of epoxy functional monomers Change prepolymer preparation enumerate those.The available class of epoxide-functional monomer includes by bis-phenol and ring Those (such as, 4,4'-isopropylidene xenol and epoxychloropropane of the reaction preparation of oxygen chloropropane Reaction, thus prepare 4,4'-isopropylidene xenol diglycidyl ether).

In certain embodiments, can be used for preparing the epoxy-functional prepolymer of specific epoxide Can be by polymer polyatomic alcohol be prepared with epichlorohydrin reaction.Exemplary suitable polymerization Thing polyhydric alcohol can include poly alkylene glycol, such as Polyethylene Glycol and PolyTHF；Polyester polyols Alcohol；Polyurethane polyol；Poly-((methyl) acrylate) polyhydric alcohol；Mixing with them Thing.

In some embodiments of the invention, epoxy-functional prepolymer can include epoxy-functional Poly-((methyl) acrylate) polymer, it can be by (methyl) acrylate monomer and ring Oxygen functionalization free radical polymerizable monomer (such as, glycidyl (methyl) acrylate) Preparation.Suitably epoxy-functional prepolymer can have the molecular weight of broad range.Real at some Executing in example, the gel permeation chromatography (GPC) according to such as utilizing polystyrene standard determines, The molecular weight of epoxy-functional prepolymer can be from 500 to 15000 grams/mol, or from 500 to 5000 grams/mol.

Second resin with at least two group that can react with epoxide can include hydroxyl At least one of base, sulfydryl, carboxylic acid, primary amine or secondary amine.In certain embodiments, the second tree Fat can include the polyhydric alcohol that the application had previously enumerated.In other embodiments, the second resin can wrap Include the polyamine that the application had previously enumerated.In certain embodiments, suitable polyamine can include having Polvamide prepolymer selected from least two amine groups of primary amine, secondary amine and combinations thereof.Close Suitable exemplary polyamides prepolymer can include such as deriving from trade name " VERSAMID " Cognis Corporation, Coating & Inks Division(Monheim, Germany) that A bit.

In certain embodiments, by including the first resin of at least two epoxide group and including energy Second resin-made of at least two group enough reacted with epoxide can for granular epoxide Perform in the presence of a catalyst.Exemplary suitable catalyst includes tertiary amine, such as three second Amine, Tris(isopropylamine)., three tert-butyl amines, Tetrafluoroboric acid and N, N-dimethyl benzylamine.Implement at some In example, catalyst can add in the second resin before mixing with epoxy functional materials.At some In embodiment, the first resin based on mixing and the gross weight of the second resin, the catalyst of use Amount can be less than 5 weight %, or less than 3 weight %, or less than 1 weight %.

For preparing epoxide group and the epoxide of the reactant of particulate crosslinked polyepoxides The molar equivalent ratio of reactive group is usually from 0.5:1.0 to 2.0:1.0, such as, from 0.7:1.0 To 1.3:1.0 or from 0.8:1.0 to 1.2:1.0.

In certain embodiments, there is at least two isocyanate groups or at least two epoxy radicals First resin and/or second resin of group can include known conventional additives alternatively.These The example of additive include heat stabilizer, antioxidant, releasing agent, Static dyes, pigment, Such as alkoxyl phenol benzoate and the softening agent of poly-(alkylene glycols) dibenzoate with such as second The surfactant of olefinic oxide/propylene oxide block copolymerization surfactant.Implement at some In example, the first resin based on mixing and the gross weight of the second resin, the amount of these additives can Amount to up to 10 weight %, or up to 5 weight %, or up to 3 weight %.

Other polymer particle that can be used for realizing the present invention includes thermoplastic poly (methyl) propylene Acid esters, it such as can derive from ROHM America with trade name " ROHADON ", Incorporated(Lawrenceville, Georgia), and with trade name " ART PEARL " Derive from Negami Chemical Industrial Co., Ltd..Other that can be used for realizing the present invention gathers Polymer particle includes such as deriving from Dow Chemical with trade name " METHOCEL " Company(Midland, Michigan) cellulose granules.

The amount alterable of polymer particle present in the polishing pad according to the present invention.Interesting Be, it is found that utilize in certain embodiments the amount of the polymer particle that particular technology mixes with It is unexpected that mode affect the porosity of gained polishing layer.Such as, it is found that when using knot When closing the blender of revolution and rotation, compared with the particle levels of up to 15 weight %, up to 20 The particle levels of weight % provides less hole.But, other hybrid technology can provide different knots Really.In certain embodiments, based on granular polymer and the gross weight of cross-linked network, described poly- The amount that polymer particle exists is at least 1 weight %, or at least 2.5 weight %, or at least 5 weight %.In certain embodiments, based on polymer particle and the gross weight of cross-linked network, described polymerization The amount that thing particle exists is up to 25 weight %, or up to 20 weight %, or less than 20 weight %.

In certain embodiments, it is the embodiment of fiber including polymer particle, based on polymer Particle and the gross weight of cross-linked network, the amount that described polymer particle exists is up to 10 weight %, Or up to 5 weight %, or less than 5 weight %.Advantageously, even if based on polymer particle and friendship The amount of polymer particle of the gross weight of networking network in the case of up to 2 weight %, fibers form Polymer particle available porosity levels also can be provided.In some of these embodiments, Polymer particle is water-soluble fibre (such as Methyl cellulose cellulose fiber).Such as the table 1 in example Shown in table 2, compare with Methyl cellulose cellulose fiber and obtain by the spherical polyurethane particles of equivalent weight Obtain higher levels of porosity.Fig. 8 (showing of the cross sectional view of the solidification compositions of example 12 Micro-figure) with Fig. 7 A and Fig. 7 B(be respectively example 15 solidification compositions cross sectional view and The microgram of top view) between visual comparison demonstrate with 2 weight % fibers (Fig. 8) and use 10 weight % particles (Fig. 7 A and Fig. 7 B) can obtain the porosity of phase same level.

Such as, in polishing process, in order to improve on whole cross-linked network particle distribution equal Evenness and in order to keep pad surface hardness, mix reduced levels particle identical to obtain Porosity is probably favourable.

Polishing pad according to the present invention includes polishing layer, and this polishing layer includes polymer particle and friendship Networking network, and cross-linked network includes containing thermosetting adhesive composition and radiation curable component.Multiple suitably Polymer can be used for forming cross-linked network.In certain embodiments, thermosetting adhesive composition includes poly-ammonia At least one of ester, polyepoxides or urethane-modified polyepoxides.

Generally, in the presence of polymer particle, form the cross-linked network of the present invention.Implement at some In example, heat-curable resin composition and radiation-curable resin composition can be reacted to form friendship Networking network, the most described curable compositions is in the case of there is polymer particle.

In certain embodiments, based on polymer particle and the gross weight of cross-linked network, the application Disclosed polishing layer can include at least 75 weight %, or at least 80 weight %, or at least 85 weights The cross-linked network of amount %.In certain embodiments, based on polymer particle and the gross weight of cross-linked network Amount, described cross-linked network can be with up to 99 weight % in described polishing layer, or up to 95 weight %, or up to the amount existence of 90 weight %.

Cross-linked network can be prepared by conventional polymerization process method.In certain embodiments, crosslinking Network can pass through condensation reaction, radical initiation reaction or combinations thereof and be formed.Real at some Executing in example, thermosetting adhesive composition can include the thermal curable resin group by including polyurethane prepolymer The polyurethane that the condensation reaction of compound and polyamine is formed.In certain embodiments, radiation curing group Divide and can include by the carbamate-diacrylate in the case of there is light trigger or ammonia Carbamate-polyacrylate that the polyreaction of carbamate-dimethylacrylate is formed Or carbamate-polymethacrylates.In certain embodiments, cross-linked network be by by Walk the heat cure carrying out or carrying out simultaneously and the IPN network polymerization of radiation curing polyreaction formation Thing.In certain embodiments, radiation curable component (in certain embodiments, polyacrylate or Polymethacrylates) close heat cure group by carbamate or urea bond conjunction radicals covalent bonds Point.

Can be used for realizing the suitable heat-curable resin composition of the present invention and can include monomer, pre- Polymers and their mixture.In certain embodiments, heat-curable resin composition can contain Catalyst, cross-linking agent, firming agent, solvent and other conventional additives known in the art.

In certain embodiments, heat-curable resin composition includes: the first resin, and it has At least two isocyanate groups (it is alternatively the isocyanate groups of end-blocking) or at least two Epoxide group；And second resin, it has and can rise instead with isocyanates and/or epoxide At least two group (such as, oh group, amino group, carboxyl group or thiol group) answered.

Can be used for preparing exemplary suitable first and second resins of thermosetting adhesive composition to be selected from point The most in this application with reference to the previously described isocyanates (including prepolymer) of granular polyurethane, Isocyanates, polyhydric alcohol and the polyamine of end-blocking.Such as, when the first and second resin combination, Use end-blocking isocyanates can the beginning of delay gelatinizing effect, it can allow the more time to use In the first and second resins are mixed with polymer particle.

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

In certain embodiments, including radiation curable resins and include that there is at least two isocyanide First resin of acid esters group and there is at least two base that can react with isocyanate groups The compositions of the thermal curable resin of the second resin of group can farther include catalyst.Exemplary Suitably catalyst may be included in the application what the preparation with reference to granular polyurethane previously enumerated Those (such as, the tertiary amine such as triethylamine and Organometallic compounds such as dibutyl tin dilaurate Thing).In certain embodiments, catalyst can mix before the first and second mixed with resin In two resins.In certain embodiments, the first resin based on mixing and the gross weight of the second resin Amount, catalyst can be according to less than 5 weight %, or less than 3 weight %, or less than 1 weight % Amount exists.Isocyanate groups in the first resin and the second resin and optional end-blocking respectively The molar equivalent ratio of isocyanate groups and isocyanate-reactive group can be from 0.5:1.0 To 2.0:1.0, such as, from 0.7:1.0 to 1.3:1.0 or from 0.8:1.0 to 1.2:1.0.

In certain embodiments, thermosetting adhesive composition can be by having at least two epoxide group First resin with there is at least two group (such as, the hydroxyl that can react with epoxide Group, amino group, carboxyl group or thiol group) the second resin reaction prepare.Example Property suitably has the first resin of at least two epoxide group and the second resin include any those For preparing the epoxide of granular polyepoxides, polyamine and polyhydric alcohol, such as the application first Described in before.

In certain embodiments, including radiation curable resins and including for preparing polycyclic epoxide The compositions of the thermal curable resin of the first and second resins of thermosetting adhesive composition may also include epoxy Compound ring opening catalyst.Exemplary suitable catalyst for the open loop of epoxide includes appointing What those described above (such as, such as tertiary amine and the Tetrafluoroboric acid of three tert-butylamines).At some In embodiment, catalyst can add in the second resin before the first and second mixed with resin. In certain embodiments, based on the first resin and the gross weight of the second resin, epoxide open loop Catalyst can be according to less than 5 weight %, or less than 3 weight %, or less than the amount of 1 weight % is deposited ?.Epoxide group in the first resin and the second resin and epoxide reaction group respectively Molar equivalent ratio can be from 0.5:1.0 to 2.0:1.0, 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, thermal curable resin can include conventional additives.Exemplary properly Conventional additives include in the application with reference to preparing granular polyurethane and granular polyepoxides Those additives of previously describing of preparation in any additive, as releasing agent, dyestuff and Softening agent.In certain embodiments, gross weight based on cross-linked network, the total amount of additive can According to less than 10 weight %, or less than 5 weight %, or less than the amount of 3 weight % exists.Conventional Additive can add in the such as first resin or in the second resin.

Porous polishing pad according to the present invention includes the polishing layer with radiation curable component.Radiation Curing component includes polyacrylate, polymethacrylates, polyvinylether, ethene polymers Or polyepoxide.In certain embodiments, radiation curable component includes polyacrylate or poly- At least one of methacrylate.Radiation curable component can by include at least two acrylate, Methacrylate, vinyl (such as, vinyl group, allyl group or styrene group) Or prepared by the radiation curable resins of epoxide group.In certain embodiments, radiation-hardenable tree Fat includes at least two acrylate or methacrylic acid ester group.

In certain embodiments, radiation curable resins can include having at least two (methyl) The multifunctional isocyanide that (methyl) of acrylate modified isocyanate groups is acrylate modified Acid esters material, it can be such as to have end and/or the polyurethane prepolymer (example of side isocyanate groups As, above in association with granular polyurethane preparation describe those polyurethane prepolymers) with have different (methyl) of polyisocyanate reactant functional group (such as, hydroxyl, amine groups or sulfydryl group) The product of acrylate.

Exemplary suitable hydroxyl or amino-functional (methyl) acrylate include hydroxyalkyl propylene Acid esters and methacrylate, such as 2-hydroxyethylmethacry,ate (HEA), 2-methyl-prop Olefin(e) acid hydroxyl ethyl ester (HEMA), 2-acrylate, 3-acrylate (HPA), 2-Hydroxypropyl methacrylate, 3-Hydroxypropyl methacrylate, 1,3-dihydroxy third Base acrylate, 2,3-dihydroxypropyl acrylate and methacrylate, 2-hydroxyethyl third Acrylamide and Methacrylamide, 2-hydroxybutyl (methyl) acrylate, 4-hydroxybutyl (first Base) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 1,4-butanediol one (methyl) acrylate, 2-hydroxy alkyl (methyl) acryloyl phosphate ester, 4-hydroxy-cyclohexyl (methyl) acrylate, 1,6-HD one (methyl) acrylate, neopentyl glycol one (first Base) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (first Base) acrylate；N-alkyl-N-hydroxyethyl acrylamide and Methacrylamide, hydroxyl second Base-β carboxyethyl acrylate, hydroxyl ethylhexyl acrylate, hydroxy octyl methacrylate, Polypropylene glycol methacrylate, propylene glycol methacrylate, caprolactone acrylate, T-Butylaminoethyl methacrylate and their mixture.Many in these can pass through business Industry approach obtains, such as can hydroxyethylmethacry,ate and acrylate can be from Dow Chemical (Midland, Mich.) and Osaka Organic Chemical Industry Ltd. (Osaka, Japan) is commercially available.Available hydroxybutyl acrylate can be from Osaka Organic Chemical Industry Ltd. is commercially available.Available hydroxyl polyester acrylate can be with trade name " TONE MONOMER M-100 " derives from Dow Chemical Company and with trade name " VISCOAT 2308 " derives from Osaka Organic Chemical Industry Ltd..Can use Hydroxy polyethers acrylate can derive from Bayer Chemicals with trade name " ARCOL R-2731 " (Pittsburgh,Pa.)。

(methyl) acrylate group can be located at the sidepiece on prepolymer, end or sidepiece end Have.In certain embodiments, prepolymer is blocked by (methyl) acrylate group.Such as, Generally in the case of there is excess isocyanate, can be by having isocyanate-reactive official (methyl) acrylate that can roll into a ball reacts with polyisocyanate prepolymer prepares radiation-hardenable Resin.In certain embodiments, there is (methyl) acrylic acid of isocyanate-reactive functional group Ester reacts with a certain amount of isocyanate-functional prepolymers so that isocyanate-functional pre-polymerization On thing from about 10% to about 80%, from about 20% to about 70% or different to about 60% from about 30% Cyanate group and (methyl) acrylate reactions with isocyanate-reactive functional group.

There are some (first of the acrylate modified isocyanate groups of at least two (methyl) Base) acrylate modified multiple functionalized isocyanate material is commercially available, such as with trade name " DESMOLUX D100 ", " DESMOLUX VPLS 2396 " and " DESMOLUX XP2510 " derive from Bayer Materials Science(Pittsburgh, PA) isocyanates ammonia Urethane acrylate.

Compositions including radiation-hardenable composition and heat curable composition the most also includes light Initiator or the combination of multiple light trigger.Available light trigger includes: such as, and " α cracks Type " light trigger, it includes such as Benzoinum, Benzoinum acetal (such as dimethyl benzyl Ketone), benzoin ether (such as benzoin ethyl ether, benzoin isobutyl propyl group ether and benzoin isobutyl butyl Ether), hydroxyalkylphenyl ketone (such as 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- Phenyl acrylate-1-ketone and 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl acrylate-1-ketone), benzoyl ring Hexanol, Dialkoxy acetophenones derivant (such as 2,2-diethoxy acetophenone), acyl phosphine aoxidize Thing (such as, double (2,4,6-trimethylbenzoyl)-phosphniline oxides, double (2,6-dimethoxies Base benzoyl)-(2,4,4-tri-methyl-amyl) phosphine oxide and 2,4,4-trimethylbenzoyl two Phosphniline oxide), methylsulfanylphenyl morpholone (such as 2-methyl isophthalic acid-4(methyl mercapto) and benzene Base-2-morpholine-1-acetone) and morpholino phenyl amino ketones；Based on benzophenone, thiaxanthone, benzyl, Camphorquinone and ketocoumarin take hydrogen light trigger by force, it includes light trigger and coinitiator； Mixture with them.In certain embodiments, light trigger be acyl phosphine oxide (such as, Double (2,4,6-trimethylbenzoyl)-phosphniline oxides, double (2,6-Dimethoxybenzoyl) -(2,4,4-tri-methyl-amyl) phosphine oxide and 2,4,4-trimethyl benzoyl diphenyl phosphine oxide).

Exemplary available commercially available light trigger can be by following trade name " IRGACURE 369”、“IRGACURE 819”、“IRGACURE CGI 403”、“IRGACURE 651”、“IRGACURE 1841”、“IRGACURE 29594”、“DAROCUR 1173 ", " DAROCUR 4265 " and " CGI1700 " obtain, all these be available from Ciba Specialty Chemicals(Ardsley,N.Y.).Light trigger preferably provides according to being enough to The amount of the photopolymerization of ideal rate exists.This amount will partly depend on light source, to be exposed to radiation The thickness of the layer of energy and light trigger extinction coefficient under described wavelength.Generally, light draws Sending out agent component will be with at least about 0.01 weight %, at least about 0.1 weight %, at least about 0.2 weight %, the amount of at most about 10 weight % or at most about 5 weight % exists.

Radiation-hardenable composition and heat curable composition can be used for preparing disclosed in the present application The compositions of porous polishing pad closely mixes.In certain embodiments, based on described compositions Gross weight, described compositions comprises at least about 10(in certain embodiments, at least about 15, 20,25,30 or 40) radiation-hardenable composition of weight % and at most about 85(are at some In embodiment, at most about 80,75,70,65,60,55 or 50) weight % radiation-curable solid Change compositions.In certain embodiments, gross weight based on described compositions, described compositions Including 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 at most about 90(are in some embodiments In, at most about 85,80 or 75) heat curable composition of weight %.

In certain embodiments, including heat-curable resin composition, radiation curable resins group The described compositions of compound and polymer particle also includes surfactant.Similarly, one In a little embodiments, including cross-linked network (including thermosetting adhesive composition and radiation curable component), divide Cloth polymer particle in described cross-linked network and the closed pore being distributed in described cross-linked network Porous polishing layer also includes the surfactant being distributed in described cross-linked network.Can be used for realizing The example of the surfactant of the present invention includes anion surfactant, cation surface activating Agent, nonionic surfactant, amphoteric surfactant (such as, amphion surface activity Agent) and combinations thereof thing.Can include containing each of in the surfactant of these types Fluorine compounds, organosilicon and surfactant based on hydrocarbon.

Exemplary available cationic surfactant includes aliphatic ammonium salt.Exemplary available Anion surfactant include carboxylate (such as, soap and alkyl ether carboxy acid salt), Sulfonate (such as, alkylbenzenesulfonate, alkylnaphthalene sulfonate and alpha-alkene sulfonate), sulfur Hydrochlorate (such as, higher alcohol sulfate salt and alkyl ether sulfate) and phosphate (such as, alkane Based phosphates).Exemplary available nonionic surfactant include polyoxyethylene alkyl ether, Ether-ether class (such as, the polyoxyethylene ether of glyceride), esters (such as, polyethylene glycol fatty Acid esters, glyceride, sorbitan ester) and organosilicon glycol copolymer, as with commodity Name " DABCO " be available from Air Products(Allentown, Pennsylvania) those. Surfactant may be present in compositions or in polishing layer, such as, throw based on compositions or porous The gross weight of photosphere, surfactant according at most 10(in certain embodiments, at most 4,3 Or 2) amount of weight % exists.In certain embodiments, based on compositions or porous polishing layer Gross weight, surfactant exists according to the amount of at least 1 weight %.The invention provides a kind of system The method making polishing pad described herein.Described method includes: including described thermal curable Shape in the compositions of resin combination, described radiation-curable resin composition and polymer particle Pore-forming.In certain embodiments, the step in hole is formed in the composition by by described group Compound mixing realizes.Available multiple technologies mix, and such as, utilize machine mixer Or hand operated mixing.In certain embodiments, hybrid technique (and machine mixer) can include Both rotation and revolution.The filling of granularity and polymer particle can affect the hole of gained polishing layer Degree, as mentioned above.

In certain embodiments, including heat-curable resin composition, radiation curable resins group The described compositions of compound and polymer particle can mix and be placed on supporting course.? Open mold (such as, not top or not capping) on supporting course top can be used for forming institute Need the polishing layer of shape.Mixture can be distributed in the mold uniformly to fill out by mechanical means Fill described mould.Suitably mechanical means can include that low pressure molds or uses hold-down roller.

The method manufacturing polishing pad disclosed by the invention also includes by compositions is exposed to radiation With at least partially curing radiation-hardenable composition, and described compositions is heated with at least partly Solidify described thermal curable resin, thus form polishing layer.Radiation is typically ultraviolet radiation (i.e., Radiating in the range of about 200nm to about 400nm).At least partially curing described compositions Required amount of radiation will depend upon which multiple factor, including being such as exposed to the angle of radiation, combination The amount of polymerizable groups in the thickness of thing, described compositions and the type of light trigger and amount. Generally, wavelength from the UV light source direct projection of about 200nm to 400nm just on conveyor system The compositions transmitted, described conveyor system provides the warp of the radiation absorption distribution being suitable to compositions Cross the speed in UV source.Available UV light source include such as ultrahigh pressure mercury lamp, high voltage mercury lamp, in Pressure mercury lamp, low intensity fluorescence lamp, metal halide lamp, microwave lighting lamp, xenon lamp, include example Such as excimer laser and the laser beam sources of argon ion laser and combinations thereof.With Rear described compositions is placed in baking oven, such as, be up to about 180 DEG C, be up to about 150 DEG C, height Reach about 135 DEG C or up to about 120 DEG C (such as from 80 DEG C to 120 DEG C, 80 DEG C to 110 DEG C or 90 DEG C to 100 DEG C) high temperature under continue for some time (such as, from 30 minutes to 24 hours). It is exposed to radiation and heat can be performed by any order or perform simultaneously.In certain embodiments, cruelly Reveal to the execution radiated prior to being exposed to heat.

The polishing pad of the present invention can have one or more work surface, wherein in the application, and " work Make face " refer to the face of the polishing pad contacted with by the surface of polished article.In some embodiments In, can be silicon chip by polished article.In certain embodiments, the work surface of polishing pad can Have such as the surface character of groove, groove, eyelet and combinations thereof.These surface character The one or more of following characteristic can be improved: (1) is at the work surface of described pad and polished thing The motion of the polishing slurries between the surface of product；(2) grinding-material is from the institute of polished article State surface to remove and transmit；Or the polishing of (3) polishing pad or planarization efficiency.

Surface character can be added by multiple method in the work surface of polishing pad.In some embodiments In, the work surface of pad can be mechanically changed by grinding or cutting.In other embodiments In, surface character can be added in the work surface of pad in a molding process, such as, by for mould At least one inner surface of tool provides raised features, and described raised features can be in the forming process of pad Middle stamp to pad work surface in.Surface character can be distributed in polishing according to random or uniform pattern On the whole work surface of pad.Example surface characteristic pattern can include spiral type, circle, square, Reticule and waffle-like pattern.

In certain embodiments, according to the present invention or polishing pad constructed in accordance include from The separation polishing element that supporting course is prominent.Referring now to Fig. 3, it is shown that the embodiment of polishing pad 2, It includes that multiple polishing element 4, each polishing element 4 are fixed to optional supporting course 8.Polishing Pad 2 also includes compliant layers 10.Generally, the polishing layer including the polishing element separated is one continuous Layer, although this and not shown in FIG. 3.Between the polishing element separated, thin film can have The most most 0.01,0.02 or the thickness of 0.03mm.In other embodiments, including separation The polishing layer of polishing element can have in interruption, the such as thin film between the polishing element separated There is interruption.Owing to polishing element 4 is fixed to illustrate on the supporting course in embodiment and thin Film layer (not shown) is between polishing element 4, and therefore polishing element 4 polishes relative to other One or more transverse movement of element 4 is restricted, but polishing element 4 is generally hanging down Directly can self-movement on the axis of the polished surface 14 of each polishing element 4.As it can be seen, Each polishing element 4 is generally of substantially throughout multiple holes 15 of whole polishing element 4 distribution.

In the embodiment shown in fig. 3, polishing element 4 is illustrated as such as by being directly bonded to It is fixed on supporting course 8 on first major opposing side of supporting course 8.Polishing element 4 can directly mould Be cured on supporting course 8.In other embodiments, polishing element 4 may be connected to supporting course 8 Go up or utilize binding agent to be directly connected in compliant layers 10.In these embodiments, porous polishing Layer is typically discontinuity layer.In the specific embodiment shown in Fig. 3, it is shown that optional pressure-sensitive viscous Mixture layer 12 is adjacent with compliant layers 10, relative with supporting course 8, described pressure sensitive adhesive layer 12 Can be used for the polishing block being fixed to by polishing pad 2 in CMP planarization equipment (not shown in Fig. 3) Plate (not shown in Fig. 3).

With reference to Fig. 4, it is shown that the another exemplary embodiment of polishing pad 2', shown polishing pad 2' Including: compliant layers 30, it has the first major opposing side and second master relative with the first major opposing side Face；Multiple polishing elements 24, each polishing element 24 has for by each polishing element 24 It is fixed to the base surface area 25 of the first major opposing side of compliant layers 30；And optional guide plate 31, It has the first first type surface and second first type surface relative with the first first type surface, described guide plate 31 It is arranged to be arranged on the first major opposing side of compliant layers 30 the plurality of polishing element 24, And the first first type surface of described guide plate 31 is away from compliant layers 30.

As shown in Figure 4, each polishing element 24 is basic from the first first type surface edge of guide plate 31 On be perpendicular to described first major opposing side first direction extend.At the specific embodiment shown in Fig. 4 In, each in porous polishing element 24 is also illustrated as having substantially throughout whole polishing unit Multiple holes 15 of part 24 distribution.It addition, in the specific embodiment shown in Fig. 4, it is shown that three Individual polishing element 24, and all polishing elements 24 are all shown as and include porous polished surface 23 He The porous polishing element in hole 15, described hole is substantially distributed throughout whole polishing element 24.So And, it will be appreciated that any amount of polishing element 24 can be used, and porous polishes element Quantity may be selected to be few to one polishing element, the most all polishing elements, or appointing between the two What quantity.

Optional polishing composition distribution layer 28 is additionally illustrated by Fig. 4.In glossing, Optional polishing composition distribution layer 28 contributes to being distributed to hydraulic fluid and/or polishing slurries On single polishing element 24.Multiple holes 26 are led described in also can being arranged to extend through at least To plate 31 and described optional polishing composition distribution layer 28, as shown in Figure 4.Real at some Executing in example, guide plate 31 also is used as polishing composition distribution layer.

As shown in Figure 4, in certain embodiments, each polishing element 24 has base surface area 25, And each polishing element 24 is by the second first type surface of corresponding base surface area 25 with guide plate 31 Joint and be fixed on the first major opposing side of compliant layers 30.Each polishing element 24 is at least A part stretches in the hole 26 of correspondence, and each polishing element 24 is also through corresponding hole 26 And stretch out from the first first type surface of guide plate 31.Therefore, guide plate 31 is described many Individual hole 26 for guiding transversely arranged on supporting course 30 of polishing element 24, the most also with often Individual base surface area 25 engages to be fixed on supporting course 30 each corresponding polishing element 24.

As a result, in polishing process, polishing element 24 is along being basically perpendicular to supporting course 30 Freely displacement independently on the direction of the first major opposing side, still keeps fixing by guide plate 31 simultaneously In compliant layers 30.In certain embodiments, this can allow to use immalleable polishing element, Such as, there is the porous in the hole being substantially distributed on polished surface or be only distributed near polished surface Polishing element.

In the specific embodiment shown in Fig. 4, polishing element 24 utilizes and is arranged in compliant layers 30 With the optional adhesive phase 34 of the interface between guide plate 31 is additionally secured to compliant layers 30 On first major opposing side.But, other method of attachment can be used, including utilizing the hottest and pressure Polishing element 24 is directly connected in compliant layers 30.

In the most unshowned associated exemplary embodiment, multiple holes may be disposed to the battle array in hole Row, its mesopore 26 include main aperture and the undercut area of guide plate 31 at least partially, and Undercut area forms shoulder, and described shoulder engages with corresponding polishing element base surface area 25, from And keep polish element 24 and without polishing the binding agent between element 24 and compliant layers 30.

Additionally, the second optional adhesive phase 36 can be used optional polishing composition distribution layer 28 It is fixed on the first first type surface of guide plate 31, as shown in Figure 4.Further, shown in Fig. 4 In specific embodiment, it is shown that optional pressure sensitive adhesive layer 32 is disposed adjacent with supporting course 30, Relative with guide plate 31, described pressure sensitive adhesive layer can be used for polishing pad 2 ' is fixed to CMP Polishing platen (not shown in Fig. 4) in polissoir (not shown in Fig. 4).

Guide plate and/or distribution layer also can be used in combination with the embodiment shown in Fig. 3, at Fig. 3 In shown embodiment, porous polishing element 4 does not have base surface area.There is guide plate In the case of removable supporting course 8, and porous polishing element can such as to utilize binding agent to be fixed to soft In concordant 10.

Intercept along the direction being roughly parallel to polished surface 14 and 23 through polishing element 4 and 24 Polishing element 4 and 24 shape of cross section can differ widely according to intended application.Although figure 3 and Fig. 4 show the cylindrical polishing element 4 and 24 with generally circular cross section, but Other shape of cross sections can also, and be probably preferably in certain embodiments.Such as, may be used By circle, ellipse, triangle, square, rectangle, hexagon and trapezoidal cross sectional shape.

For having the cylindrical polishing element 4 and 24 of circular cross section, polish element 4 and 24 Cross-sectional diameter along the direction being roughly parallel to polished surface 14 and 23 can be about 50 μm to about 20mm, this cross-sectional diameter is about 1mm to about 15mm in certain embodiments, and at other In embodiment, this cross-sectional diameter is about 5mm to about 15mm(or the most about 5mm to about 10mm).Polish element for having the non-cylindrical of non-circular cross sections, can use and to specify Highly, the characteristic size such as width and length characterizes the size of polishing element.Exemplary at some In embodiment, characteristic size is optional is about 0.1mm to about 30mm.

In other exemplary embodiments, each polishing element 4 and 24 is along being typically parallel to polishing The cross-sectional area in the direction on surface 14 and 23 can be about 1mm²To about 1,000mm², at it His embodiment is about 10mm²To about 500mm², and be about in additionally other embodiment 20mm²To about 250mm²。

Polishing element (4 in Fig. 3,24 in Fig. 4) can be distributed in submissive with multiple patterns On the major opposing side of layer (10 in Fig. 3,30 in Fig. 4), described pattern depends on that expection should With, and described pattern can be regular or irregular.Polishing element can be located at compliant layers On the most whole surface, or the supporting course region not including polishing element can be there is.At some In embodiment, the average surface percentage of coverage of the compliant layers of polishing element is compliant layers first type surface The gross area about 30% to about 95%, this is by polishing the quantity of element, each polishing element The cross-sectional area of cross-sectional area and polishing pad determines.

In some exemplary embodiments, polishing pad is being roughly parallel to the side of polishing pad first type surface Cross-sectional area upwards is in the range of about 100cm²To about 300000cm², in other embodiments It is about 1000cm²To about 100000cm², and it is about 2000cm in additionally other embodiment² To about 50000cm²。

Before using polishing pad (2 in Fig. 3, the 2' in Fig. 4) for the first time in polishing operation, In some exemplary embodiments, each polishing element (4 in Fig. 3,24 in Fig. 4) along The direction of the first major opposing side being basically perpendicular to compliant layers (10 in Fig. 3,30 in Fig. 4) is prolonged Stretch.In other exemplary embodiments of the invention, each polishing element is including guide plate in the first direction The plane of (in Fig. 4 31) extend above the most about 0.25mm.In other exemplary reality Executing in example, each polishing element extends in a first direction and includes supporting course (in Fig. 3 10) The top at least about 0.25mm of plane.In other exemplary embodiment, polished surface (figure In 3 14,23 in Fig. 4) in polishing element (2 in Fig. 3,2 ' in Fig. 4) Height above base portion or bottom can be 0.25mm, 0.5mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, 5.0mm, 10mm or higher, depend on used polishing composition and selected For polishing the material of element.

Refer again to Fig. 4, throughout whole polishing composition distribution layer 28 and the hole of guide plate 31 The degree of depth of 26 and spacing can change according to the needs of concrete CMP.Polishing element 24 points The most relative to each other and polishing composition distribution layer 28 and guide plate 31 are maintained at planar orientation, And it is projected into polishing composition distribution layer 28 and the surface of guide plate 31.

In some exemplary embodiments, by polishing element, (4 in Fig. 3, in Fig. 4 24) at guide plate 31 and any polishing composition distribution layer (in Fig. 4 28) or supporting course (figure In 3 8) extend above produced volume space can be provided to divide for by polishing composition Cloth is to polishing composition distribution layer (in Fig. 4 28) or the table of supporting course (in Fig. 3 8) On face.Polishing element (4 in Fig. 3,24 in Fig. 4) highlights and is distributed at polishing composition Layer (in Fig. 4 28) or supporting course (in Fig. 3 8) top, overhang at least partly takes Certainly material behavior and polishing composition (hydraulic fluid and/or abrasive fluid) in polishing element exist On the surface of polishing composition distribution layer (in Fig. 4 28) or supporting course (in Fig. 3 8) Required flow behavior.

In certain embodiments can guide plate can be made of a variety of materials, such as polymer, Copolymer, polymer blend, polymer composites or combinations thereof.Generally preferably insulation And the polymeric material of liquid impermeable, and have been found that Merlon is especially useful.

The optional polishing composition distribution layer that can be used for some embodiments also can be by multiple polymers material Material is made.In certain embodiments, polishing composition distribution layer can comprise at least one hydrophilic Polymer.Preferably hydrophilic polymer include polyurethane, polyacrylate, polyvinyl alcohol, Polyoxyethylene methylene and combinations thereof.Polymeric material is preferably porous, more preferably includes bubble Foam, with during polishing operation, when compressing polishing composition distribution layer, it is provided that towards base The normal pressure at the end.In certain embodiments, preferably there is perforate or the porous of closed pore or foam Formed material.In certain embodiments, polishing composition distribution layer has about 10% to about Porosity between 90%.In alternative embodiment, polishing composition layer can comprise such as The hydrogel material of hydrophilic urethane etc, this hydrophilic material is absorbable preferably about 5 Weight % is to the water in the range of about 60 weight %, thus provides lubrication table during polishing operation Face.

In some exemplary embodiments, polishing composition distribution layer can be basic by polishing composition On be evenly distributed on the whole substrate surface being polished, so can provide more uniform Polishing.Polishing composition distribution layer include alternatively as spoiler, groove (not shown in accompanying drawing), The flow blocking element of hole etc is to regulate polishing composition flow velocity in polishing process.Separately In outer exemplary embodiment, polishing composition distribution layer can include various different material layer, with Just the polishing composition flow velocity needed for obtaining at the different depth of polished surface.

In some exemplary embodiments, it is limited to one or more the including in polishing element Core region in polishing element or cavity, but this arrangement is optional.At some In embodiment, as described in International Patent Application Publication No. WO 2006/055720, polish element Core can include detect pressure, conductivity, electric capacity, eddy current etc. sensor.

In some embodiments of polishing pad disclosed by the invention and/or its manufacture method, supporting course Including flexible and submissive material.Supporting course is typically thin film, and its offer includes thermal curable tree The surface that the compositions of oil/fat composition and radiation-curable resin composition can be cured thereon. During porous polishing layer includes some exemplary embodiments of polishing element wherein, polishing element can Be formed as polishing element together with supporting course and be fixed to the integrated sheet material of supporting course, described polishing Element include at least partially porous polish element.

While polishing pad is used, supporting course is also used for protecting compliant layers to exempt from into polishing and combines Water in thing or other fluid.The normally liquid impermeable of supporting course (but permeable material Can be used together with optional barrier layer, to stop or suppression fluid permeability is in supporting course). In some exemplary embodiments, supporting course comprises selected from polymers set forth below material: have Machine silicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyurethane, polyolefin with And combinations thereof.Supporting course also can comprise multiple other materials, such as filler, granule, fibre Dimension, reinforcing agent etc..In certain embodiments, supporting course is transparent.

Supporting course can be such as by by material (such as, organosilicon, natural rubber, styrene-fourth Diene rubber, neoprene, polyurethane, polyolefin and combinations thereof) it is extruded into thin film system Become.In certain embodiments, described material is with trade name " ESTANE 58887-NAT02 " It is available from Lubrizol Advanced Materials, Inc.(Cleveland, OH) or with trade name " PELLETHANE " (such as, " PELLETHANE 2102-65D ") is available from Dow Chemical(Midland, MI) polyurethane.The commercially available thin film that can be used as supporting course includes Such as with trade name " ST-1882 ", " ST-1035 ", " SS-3331 ", " SS-1495L " " ST-1880 " is available from Stevens Urethane(Easthampton, Massachusetts) Polyurethane film.

In some embodiments of polishing pad disclosed by the invention and/or its manufacture method, compliant layers Including flexible and submissive material, such as compliant rubber or polymer.Compliant layers generally can be compressed To provide towards the normal pressure of polished surface, and can such as help to provide polishing pad and polished Substrate surface between contact uniform.In some exemplary embodiments, compliant layers is by pressing The polymeric material of contracting is (such as, by such as natural rubber, synthetic rubber or thermoplastic elastic system The foamed polymer material become) make.Closed pore porous material is available.In some embodiments In, compliant layers includes polyurethane, and can be such as polyurathamc or polyurethane insulating dipping Felt.The thickness of compliant layers can be such as in the range of 0.2 to 3mm.Porous is thrown wherein Photosphere includes in some exemplary embodiments of polishing element, and polishing element can be together with compliant layers Be formed as polishing element and be fixed to the integrated sheet material of compliant layers (can be porous compliant layers), institute That states polishing element includes that porous polishes element at least partially.

In some exemplary embodiments, compliant layers comprises selected from polymers set forth below material: Organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, polyolefin, polyurethane And combinations thereof.Supporting course also can comprise multiple other materials, such as filler, granule, Fiber, reinforcing agent etc..In certain embodiments, compliant layers be fluid impermeable (but It is that permeable material can be used in combination with supporting course described above).

Suitable commercially available compliant layers includes such as (such as having with trade name " PORON " The description of product of 4701-60-20062-04,4701-50-20062-04,4701-40-20062-04) Be available from Rogers Corp.(Rogers, CT) microvoid polyurethane.Other suitable compliant layers Including being such as available from Rodel, Incorporated(Newark, DE with trade name " SUBA IV ") Polyurethane insulating dipping polyester felt and be available from trade name " BONDTEX " Rubberite Cypress Sponge Rubber Products, Inc.(Santa Ana, CA) bonding Rubber sheet.

In some embodiments of polishing pad disclosed by the invention and/or its manufacture method, described throwing Light pad can include the window extending through described pad along the direction being perpendicular to polished surface, or can Use clear layer and/or transparent polishing member, thus allow the optical end point of polishing process to monitor, Such as the description in International Patent Application Publication No. WO 2009/140622 (Bajaj et al.).

The term " clear layer " used above is intended to the layer including having transparent region, described Territory, area pellucida can be made up of the material identical or different with the remainder of this layer.Exemplary at some In embodiment, polishing element, supporting course, compliant layers or polishing layer or a region of supporting course In at least one can be transparent, maybe can by material apply heat and/or pressure and be made into For transparent.In certain embodiments, transparent material can be at the opening in being suitably disposed at layer Cast in (such as, utilize mould), with create transparent region (such as, polishing layer, Hold in layer or compliant layers).In certain embodiments, there are the feelings of preforming window in polishing layer Solidify under condition, to create transparent region in polishing layer.In certain embodiments, whole supporting Layer and/or compliant layers can be made up of materials described below, and this material is for being used by end point detecting device Energy in the range of wavelengths of interest be transparent maybe can be made as transparent.For transparent element, Suitable transparent materials in layer or region includes (such as) transparent polyurethane.

Additionally, as used above, term " transparent " is intended to include for being filled by end-point detection Put the element of energy substantial transparent, layer and/or the region in the range of the wavelengths of interest of use. In some exemplary embodiments, end point detecting device utilizes one or more electromagnetic energy source to send out The form of penetrating is ultraviolet light, visible ray, infrared light, microwave, radio wave, combinations thereof etc. Deng radiation.In certain embodiments, term " transparent " refer to be irradiated to transparent element, At least about 25%(of the energy of the relevant wavelength on layer or region such 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%) pass through from it.

In some exemplary embodiments, supporting course is transparent.In certain embodiments, throw Photosphere is transparent.Including some exemplary embodiments of the embodiment shown in figure 3 above In, at least one polishing element is transparent.In certain embodiments, supporting course is transparent, At least some of (such as, polish element) of polishing layer is transparent, and in compliant layers There is the hole alignd with the transparent part of polishing layer.

In the other exemplary embodiment including embodiment shown in figure 4 above, at least one It is transparent for planting polishing element, and shown adhesive phase and compliant layers are also transparent.Separately In outer exemplary embodiment, compliant layers, guide plate, polishing composition distribution layer, at least one Plant polishing element or combinations thereof is transparent.

The method that the invention still further relates to use above-mentioned polishing pad in glossing, described method bag Include the surface making substrate to contact with the porous polishing layer of the polishing pad according to the present invention；With about institute State substrate and relatively move described polishing pad to denude the surface of described substrate.In some embodiments In, the porous polishing layer of polishing pad includes multiple polishing element, and at least some therein is porous 's.In some exemplary embodiments, hydraulic fluid can be provided pad interface and substrate Interface between surface.Suitably hydraulic fluid includes such as at U.S. Patent number 6,238,592 (Hardy et al.), 6,491,843 (Srinivasan et al.) and in International Patent Application Publication No. WO Those described in 2002/33736 (Her et al.).

In certain embodiments, the present invention's and/or prepared according to the methods of the invention polishing pad In polishing layer can have the average hole of at least 5 microns, at least 10 microns or at least 15 microns Footpath.In certain embodiments, the average pore size of polishing pad be at most 100,75,50,45 or 40 microns.Such as, average pore size can be from 5 to 100,5 to 75,5 to 50,5 to 40 Or in the range of 5 to 30 microns.(such as including at least one surface in certain embodiments In activating agent or embodiment that polymer particle is fiber), the average pore size of polishing pad can be to Many 30,25 or 20 microns.The diameter of the usual finger-hole in described aperture.But, it is aspheric in hole In the embodiment of shape, aperture can the full-size of finger-hole.In certain embodiments, aperture is not The uniformity is in the range of 40% to 75%, or in the range of 40% to 60%.One In a little embodiments, the unevenness in aperture be at most 75%, 70%, 65%, 60%, 55% or 50%.By contrast, the comparative example compositions including heat curable composition can have more than 80%, The aperture unevenness of 90% or 100%.In certain embodiments, according to the polishing pad of the present invention In polishing layer porosity can in the range of 5% to 60%, or from 5% to 55%, In the range of 10% to 50% or 10% to 40%.

Control according to the aperture in the polishing layer of the present invention and heat curable composition in a comparative example In the difference in aperture shown by Fig. 5 A, Fig. 5 B, Fig. 6 A and Fig. 6 B.Fig. 5 A and figure 5B is respectively the cross section of the solidification compositions described in the example 2 in examples section below and shows Figure and the microgram of top view.As a comparison, Fig. 6 A and Fig. 6 B is consolidating of comparative example 3 respectively Change cross sectional view and the microgram of top view of compositions.Example 2 and comparative example 3 both Utilize 10 weight % polymer particle preparations and mix in the same manner.But, example 2 leads to Both overshoot solidification and heat cure solidify, and comparative example 3 only carries out solid by heat cure Change.Microgram shows that the hole of the boring ratio comparative example 3 in example 2 is better controled over.With In lower example the data in table 1 also support compared with comparative example 3, example 2 exists less Size range, relatively low aperture unevenness and higher hardness.

On the premise of being undesirably bound by theory, it is believed that to aperture and aperture unevenness Control may be relevant with the hardness of polishing layer.In certain embodiments, the hardness of porous polishing layer It it is the Shore D hardness of at least 40,45 or 50.Such as, described hardness can be according to following instance Described in method of testing 2 be measured.By contrast, including the ratio of heat curable composition Relatively example compositions can have the Shore D hardness less than 40.

Surfactant can be used in compositions disclosed by the invention and porous polishing layer, such as, Generally to reduce aperture and pore diameter range, and compare do not exist in the case of surfactant double Weight curing preferably improves pore size distribution.In other words, add surfactant can help to The more preferable control of the shape in pore-size distribution and size, density and hole is provided, then can be to uniformly The key metrics standard of performance (such as, clearance and in wafer the uniformity) plays actively work With.Fig. 7 A and Fig. 7 B(is the solidification group described in the example 15 in examples section below respectively The cross sectional view of compound and the microgram of top view) in microgram show interpolation surface live Pore diameter range and pore size distribution can be played positive role by property agent.Such as, with have equal number and Polymer particle does not also have the example 2 of surfactant to compare according to same way preparation, Example 15 exists less pore diameter range.

Embodiment selected by the present invention

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

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

Porous polishing layer, it is arranged on the first side of compliant layers, and described porous polishing layer includes:

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

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

In a second embodiment, the invention provides a kind of polishing pad according to first embodiment, Also include the supporting course being arranged between described compliant layers and described porous polishing layer.

In the third embodiment, the invention provides a kind of throwing according to first or second embodiments Light pad, wherein said thermosetting adhesive composition includes at least one of polyurethane or polyepoxide, and And wherein said radiation curable component includes polyacrylate, polymethacrylates, polyethylene At least one in ether, ethene polymers or polyepoxides.

In the fourth embodiment, the invention provides a kind of throwing according to first or second embodiments Light pad, wherein said thermosetting adhesive composition and described polymer particle include polyurethane independently of one another.

In the 5th embodiment, the invention provides a kind of according in first to fourth embodiment The polishing pad of any one, wherein said polymer particle is covalently bound in described cross-linked network At least one of described thermosetting adhesive composition or described radiation curable component.

In the sixth embodiment, the invention provides a kind of according in the first to the 5th embodiment The polishing pad of any one, wherein radiation curable component includes polyacrylate or polymethylacrylic acid At least one of ester.

In the 7th embodiment, the invention provides a kind of polishing pad according to sixth embodiment, Wherein said polyacrylate or polymethacrylates are by amino-formate bond or urea linker Group is covalently bound to described thermosetting adhesive composition.

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

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

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

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

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

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

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

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

In the 16th embodiment, the invention provides a kind of throwing according to arbitrary previous embodiment Light pad, wherein polishing element each has the far-end away from supporting course, and wherein said far-end Removable being perpendicular to polish on the axis of the polished surface of element.

In the 17th embodiment, the invention provides a kind of according to the 15th or the 16th enforcement The polishing pad of example, also includes the guide plate wherein with multiple opening, the polishing unit of described separation Part is each prominent through one of the plurality of opening.

In the 18th embodiment, the invention provides a kind of according to the 15th to the 17th enforcement The polishing pad of any one in example, wherein polishing element is fixed in compliant layers by binding agent.

In the 19th embodiment, the invention provides a kind of throwing according to arbitrary previous embodiment Light pad, wherein said compliant layers include organosilicon, natural rubber, SBR styrene butadiene rubbers, At least one of neoprene, polyolefin or polyurethane.

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

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

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

In the 23rd embodiment, the invention provides a kind of method manufacturing polishing pad, institute The method of stating includes:

Form hole in the composition；

Described compositions is positioned on supporting course；And

By compositions being exposed to radiation with at least partially curing described radiation curable resins group Compound, and described compositions is heated with at least partially curing described heat-curable resin composition, Thus on supporting course, form porous polishing layer.

In the 24th embodiment, the invention provides a kind of according to the 23rd embodiment Method, also include being adhesively bonded to compliant layers relative with described porous polishing layer described in Hold on the surface of layer.

In the 25th embodiment, the invention provides a kind of according to the 23rd or the 20th The method of four embodiments, it is different that wherein said heat-curable resin composition includes having at least two Cyanate group or the first resin of at least two epoxide group and there is hydroxyl, amino, carboxylic Second resin of at least two in base or mercapto groups, and wherein said radiation-hardenable group Compound includes at least two in acrylate, methacrylate, vinyl or epoxide group.

In the 26th embodiment, the invention provides a kind of according to the 25th embodiment Method, wherein said first resin has an at least two isocyanate groups, and wherein said second Resin has at least two oh group or at least two amino group, wherein said radiation-curable solid Change compositions and include at least two acrylate or methacrylic acid ester group, and wherein said Radiation-hardenable composition also includes at least one isocyanate groups or oh group.

In the 27th embodiment, the invention provides a kind of according to the 26th embodiment Method, wherein said radiation-hardenable composition is aliphatic, isocyanate-functional amino first Acid esters acrylate or methacrylate.

In the 28th embodiment, the invention provides a kind of according to the 23rd to the 20th The method of any one in seven embodiments, before being additionally included in formation porous polishing layer, by opening Mould is positioned on supporting course in described compositions.

In the 29th embodiment, the present invention has carried a kind of for according to the 23rd to the 20th The method of any one in eight embodiments, wherein said hole is closed pore.

In the 30th embodiment, the invention provides a kind of according to the 23rd to the 29th The method of any one in embodiment, wherein said compositions also includes surfactant.

In the 31st embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in embodiment, wherein said porous polishing layer is measured by method of testing 2 Hardness be at least 40 Shore D hardness.

In the 32nd embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in one embodiment, the particle mean size of wherein said polymer particle is from 5 Micron is in the range of 500 microns.

In the 33rd embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in two embodiments, wherein said polymer particle is substantially spherical.

In the 34th embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in three embodiments, wherein said polymer particle is fiber.

Implementing in a kind of example the 35th, the present invention provides according to the 23rd to the 30th The method of any one in four embodiments, wherein said polymer particle water soluble.

In the 36th embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in five embodiments, wherein said polymer particle is with based on porous polishing layer Gross weight most 20 weight % exist.

In the 37th embodiment, the present invention provides according to a kind of 23rd to the 30th The method of any one in six embodiments, the aperture unevenness in wherein said hole is up to 75%.

In the 38th embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in seven embodiments, the average pore size in wherein said hole is from 5 microns to 100 In the range of Wei meter.

In the 39th embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in eight embodiments, wherein said polishing layer include being fixed to supporting course and from The polishing element of the separation that supporting course is prominent.

In the 40th embodiment, the invention provides a kind of side according to the 39th embodiment Method, the polishing element of wherein said separation each has fixation ends and the far-end away from supporting course, And wherein said far-end is removable on the axis of polished surface being perpendicular to polishing element.

In the 41st embodiment, the invention provides a kind of according to the 23rd to the 30th The method of any one in eight embodiments, wherein said polishing layer includes from prominent the dividing of compliant layers From polishing element, wherein said polishing element each has the far-end away from supporting course, and Wherein said far-end is removable on the axis of polished surface being perpendicular to polishing element.

In the 42nd embodiment, the invention provides a kind of according to the 29th to the 40th The method of any one in one embodiment, also includes the guide plate wherein with multiple opening, institute The polishing element stating separation is each prominent through one of the plurality of opening.

In the 43rd embodiment, the invention provides a kind of according to the 29th to the 40th The method of any one in two embodiments, wherein said supporting course include organosilicon, natural rubber, At least one of SBR styrene butadiene rubbers, neoprene, polyolefin or polyurethane.

In the 44th embodiment, the invention provides a kind of according to the 23rd to the 40th The method of any one in three embodiments, wherein said polishing pad is transparent at least partially.

In 45 embodiments, the invention provides a kind of finishing method, comprising:

By the surface of substrate and according to the polishing pad of any one in the first to the 22nd embodiment Porous polishing layer contact；And

Described polishing pad is moved to grind the surface of described substrate relative to described substrate.

In the 46th embodiment, the invention provides a kind of according to the 45th embodiment Method, also includes providing work to the interface between described porous polishing layer and described substrate surface Fluid.

Illustrate the exemplary polishing according to the present invention by combining following limiting examples now Pad.

Example

Method of testing 1:FESEM

Utilize according to conventional program and be available from Hitachi High-Technologies Corporation The Hitachi S-4500 FESEM of (Tokyo, Japan) obtains the scanning electron microscopy to article Figure (top view and cross sectional view).By utilizing the cutting of sharp razor blade to obtain article Cross section.Before SEM checks, utilize routine techniques that sample sputters coating Au/Pd successively. The image of both the cross section of acquisition article and top.

Method of testing: 2: durometer

Utilization is available from Rex Gauge Company, the type of Inc., Buffalo Grove, Illinois Number it is that 1500 Shore D hardness set testers carry out durometer measurement.In table 1, the value of report is The meansigma methods of five measurement results, each measurement result is that the different polishing features for example are entered Row.

Method of testing 3: determine aperture by optical microscope

Aperture averaging value, aperture standard deviation (standard deviation), pore diameter range (are observed Maximum sized hole deducts the hole of the minimum dimension observed), aperture unevenness (aperture mark Quasi-deviation is multiplied by 100 divided by average pore size) and porosity (image includes the measured area in hole The gross area divided by image is multiplied by 100) determination real by utilizing the graphical analysis of optical imagery Existing, described optical imagery utilizes and is available from Nikon Instruments, Inc.(Elgin, IL) MM-40 Nikon measuring microscope combines and is available from Media Cybernetics(Bethesda, MD) Image-pro plus analyze software obtain.

Before optical imagery, prepare sample in such a way.Three polishing features are by from thing Cut on product and pass through to utilize with trade name " 3M SCOTCH-WELD Epoxy Potting Compound/Adhesive DP270 CLEAR " be available from 3M company (St.Paul, Minnesota) perfusion compound is sealed in and is available from Buehler Ltd.(41, Lake Bluff, In the Phenolic ring form of 2.5cm external diameter × 2.2cm internal diameter Illinois).It is built in ring Characteristic use in epoxy resins is available from Ecomet 3 grinder-polisher of Buehler Ltd. and uses six Process finishing polish, downward pressure: 4.25psi(29.3kPa), the head of all six step Portion and platen rotating speed: 120rpm.In all cases, mark sand paper or polishing pad are by using Contact adhesive (psa) is installed on the platen of Ecomet 3.

Step 1: public from 3M with trade name " 3M WETORDRY PSA Disc 21366 " Department obtains the 240Grit abrasive disk of 8 inch diameters, and milling time is 3 minutes, and wherein water is for grinding Mill fluid.

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

Step 3: with trade name " TEXMET 1500Polishing Pad ", 40-8618 can obtain From the 8 inch diameter pads of Buehler Ltd., utilize and be available from Allied High Tech Products, Inc.(Rancho Dominguez, California) 15 μm grade polycrystalline diamond suspensions 90-30035 is as polishing fluids, and polishing time is 6 minutes.

Step 4: with trade name " TEXMET 1500Polishing Pad ", 40-8618 can obtain From the 8 inch diameter pads of Buehler Ltd., utilize and be available from Allied High Tech Products, Inc. 6 μm grade polycrystalline diamond suspension 90-30025 are as polishing fluids, polishing time It it is 6 minutes.

Step 5: with trade name " TEXMET 1500Polishing Pad ", 40-8618 can obtain From the 8 inch diameter pads of Buehler Ltd., utilize and be available from Allied High Tech Products, Inc. 3 μm grade polycrystalline diamond suspension 90-30020 are as polishing fluids, polishing time It it is 6 minutes.

Step 6: with trade name " TEXMET 1500Polishing Pad ", 40-8618 can obtain From the 8 inch diameter pads of Buehler Ltd., utilize and be available from Allied High Tech Products, Inc. 1 μm grade polycrystalline diamond suspension 90-30015 is as polishing fluids, polishing time It it is 6 minutes.

After polishing, the polished surface of feature followed by being available from Denton Vacuum, LLC(Moorestown, NJ) sputtering coating machine utilize routine techniques be coated with carbon.Carry out subsequently Optical imagery.

Example 1

By place in 50mL plastic beaker 0.28g 5350D, 2.15 grams of M1,1.83 grams PHP-75D, 1.27 grams of D100 and 0.06 gram of TPO-L prepare example 1.Beaker is placed in Awatori-Rentaro AR-500Thinky Mixer (derive from Thinky Corporation, Tokyo, Japan) and in two steps described component is mixed by process operation AR-500 suddenly.? Continue under the rotation of 1000rpm and the revolution of 1000rpm to perform first step in 5 minutes.? Second step it is immediately performed after first step, and at the rotation of 30rpm and 2000rpm Revolution is lower to be continued within 15 seconds, to perform second step, thus forms resin compound.Resin is mixed Compound is poured into and is formed by the aluminium sheet wide by 19.5cm length and 9.2cm of the plating Ni of teflon-coating Aluminum dipping form in.Described mould is made up of the square array of diminishing cylindrical chamber.Chamber exists The top of described chamber has 7.8mm diameter, has 6.5mm diameter in the bottom of described chamber And the degree of depth is 1.8mm.Distance between the center of two chambers is about 11.7mm.By a piece of poly- Urethane thin film ST-1880 is used as backing.Described backing is cut into about 12cm × 10cm, and puts Put on the region containing resin compound of mould.28cm length × 17cm width × 3.5mm is thick Piezoid be placed on the top of Polyurethane backings, force resin into chamber and chamber it Between form the thin base surface area of resin compound thick for about 0.5mm.

Make described mould, resin compound, backing and piezoid at two with about 157.5 watts/li The ultraviolet light modulation that rice (400 watt/inch) works (is available from Fusion Systems Inc. ' V ' bulb of (Gaithersburg, Maryland)) under by come UV solidify mixed with resin Thing.Mould through described lamp, radiates warp with the speed of about 2.4 ms/min (8 feet/min) Cross piezoid and Polyurethane backings arrives resin compound.With rear mold, partially cured resin Mixture and Polyurethane backings are subsequently transferred to the air by arranging the baking oven that temperature is 100 DEG C Stream is placed two hours, with resin compound described in heat cure.By pulling polyurethane to carry on the back gently Curing item is removed from mould by lining, thus forms the article with structuring polishing feature, Example 1.

Example 2

As example 1 equally prepares example 2, difference is, consisting of of resin compound 0.58 gram of 5350D, 2.15 grams of M1,1.83 grams of PHP-75D, 1.27 grams of D100 and 0.06 gram TPO-L。

Example 3

As example 1 equally prepares example 3, difference is, performs solid according to reversed sequence Change, first heat cure, then UV solidification.

Example 4

As example 2 equally prepares example 4, difference is, performs solid according to reversed sequence Change, first heat cure, then UV solidification.

Comparative example C1

As example 1 equally prepares comparative example C1, difference is, the group of resin compound Compound saves 5350D.

Comparative example C2

As comparative example C1 equally prepares comparative example C2, difference is, resin compound Compositions be 0.31 gram of 5350D, 2.15 grams of M1 and 3.65 grams of PHP-75D, and only make It is used at 100 DEG C the heat cure carried out two hours, eliminates UV curing schedule.

Comparative example C3

As comparative example C2 equally prepares comparative example C3, difference is, resin compound Compositions be 0.65 gram of 5350D, 2.15 grams of M1 and 3.65 grams of PHP-75D.

Example 5

By place in 500mL plastic beaker 9.49 grams of 5350D, 35.00 grams of M1,29.69 Gram PHP-75D, 20.63 grams of D100 and 1.03 grams of TPO-L prepare example 5.Beaker is placed in In Awatori-Rentaro AR-500Thinky Mixer, and process operation under the two-step Described component is mixed by AR-500.Rotation and the public affairs of 1000rpm at 1000rpm Turn lower to continue to perform first step in 5 minutes.It is immediately performed second step after the first step, And continue to perform second step in 15 seconds under the rotation of 30rpm and the revolution of 2000rpm Suddenly, thus form resin compound.

Utilize width to be about 21 inches (53cm) and gap is 60 mils (1.52mm) Doctor knife coater prepares the resin compound coating of about 28cm × 28cm on backing thick for 26mm, Described backing is by deriving from thermoplastic polyurethane (TPU) ESTANE 58887-NAT02( Lubrizol Advanced Materials, Inc.(Cleveland, OH)) at 182 DEG C antiseized It is extruded into thin film on paper gasket pad and is formed.

Resin compound after coating and backing be placed in 12 inches × 12 inches (30.5cm × On the aluminium sheet that 30.5cm) × 0.25 inch (6.35mm) is thick.By 0.375 inch of (9.6mm) diameter 36 blocks of Magnet that × 0.125 inch (3.2mm) is thick are installed in aluminium sheet groove behind. 36 grooves arrange according to square array, and the distance between the center of groove is about 5cm.Groove Diameter and the degree of depth be respectively 9.8mm and 4.3mm.Resin compound coating top is arranged The metal gauze of teflon coating, its about 41cm × 30cm, and thick about 1.6mm, it has The circular hole of hexagonal array, the diameter of each circular hole about distance between 6.2mm, and center is About 8mm.It is mixed that the magnetic attraction between Magnet in silk screen and aluminium sheet makes silk screen be forced through resin Compound coating, thus between metal gauze and backing, leave the thin base surface area of coating.As real Example 1 equally performs the UV solidification of coating, and difference is not use piezoid.Profit subsequently Heat cure is carried out by the operation as describing in example 1.

After taking out from baking oven, metal gauze is removed from the resin of solidification, and formation is attached to Band veined pad surface on the Polyurethane backings of original paper backing.Remove paper, thus expose Go out the opposite side of Polyurethane backings.The transfering adhesive utilizing 127 μ m-thick (derives from 3M company 3M Adhesive Transfer Tape 9672), by with veined pad surface polyurethane carry on the back Lining hand-layup is to a piece of amino of about 30cm × 30cm × 0.0625 inch (1.59mm) thickness On formic acid esters foam (derive from American Flexible Products, Inc.(Chaska, Minnesota) Rogers " PORON " urethane foam, part # 4701-50-20062-04).The die-cut 23cm with 18mm diameter center hole from laminates The pad of diameter, thus form the pad with structuring polishing feature of the present invention, example 5.

Comparative example C4

As example C5 equally prepares comparative example C4, difference is, resin compound Compositions is 10.48 grams of 5350D, 35.00 grams of M1 and 59.38 grams of PHP-75D, and only Use the heat cure carried out at 100 DEG C two hours, eliminate UV curing schedule.

Utilize method of testing 2 and 3；Practical measuring examples 1-5 and the hardness of comparative example C1-C4, aperture Meansigma methods, aperture standard deviation, pore diameter range, aperture unevenness and porosity.Result is shown In table 1 below.

Table 1. hardness, aperture and porosity data

* there is no measurable pore size data, as comparative example C1 does not has hole.

Example 6

As example 1 equally prepares example 6, difference is, consisting of of resin compound 0.28 gram of 5150D, 2.15 grams of M1,1.83 grams of PHP-75D, 1.27 grams of D100 and 0.06 gram TPO-L。

Example I-1 is described

Equally prepare explanation example I-1 as example 1, difference is, the group of resin compound Become 0.28 gram of 5070D, 2.15 grams of M1,1.83 grams of PHP-75D, 1.27 grams of D100 and 0.06 gram of TPO-L.

Example 7

As example 1 equally prepares example 7, difference is, the amount of 5350D is 0.05g.

Example 8

As example 1 equally prepares example 8, difference is, the amount of 5350D is 0.14 Gram.

Example 9

As example 1 equally prepares example 9, difference is, the amount of 5350D is 0.93 Gram.

Example I-2 is described

Equally prepare explanation example I-2 as example 1, difference is, the amount of 5350D is 1.31 Gram.

FESEM (method of testing 1) result of example 6-9 shows that they have acceptable hole Degree level.Illustrate that FESEM (method of testing 1) result of example I-1 and I-2 shows that they have low Porosity levels.

Example 10

As example 5 equally prepares example 10, difference is following change.Mixed with resin Thing consist of 0.62 gram of A15LV, 23 grams of P-250,15.83 grams of PHP-75D, 22 grams of D100, 1.1g TPO-L and 0.68 gram of DC5604.Described component is placed and in 500ml plastic containers Mixing.

Make the silk screen with resin compound and TPU backing at two with about 157.5 watts/centimetre The ultra-violet lamp (being available from ' V ' bulb of Fusion Systems Inc.) that (400 watt/inch) works Under by come UV solidify resin compound.Resin compound with about 2.4 ms/min (8 feet/ Minute) speed through described lamp, radiation is through resin compound.Subsequently will be with trade name " 3M SCOTCHPAK 1022Release Liner " it is available from the fluoropolymer coating of 3M company Polyester film release liner is placed in the top of described silk screen, and partially cured resin compound.Subsequently Assembly is overturn so that Polyurethane backings is above, and the polyester of fluoropolymer coating Thin film/silk screen/partially cured resin compound is positioned at bottom.Whole assembly second time is through same UV curing process, now piezoid is positioned at backing top.After second time UV has solidified, The polyester film of piezoid and fluoropolymer coating is removed and by the resin of silk screen/partially cured Mixture/back lining components is transferred to arrange and is placed two in the baking oven that the air-flow that temperature is 100 DEG C passes through Hour, with heat reactive resin mixture.After cooling to room temperature, band 18mm diameter is manufactured The 23cm diameter pad of centre bore, as described in example 5, obtains example 10.

Example 11

As example 10 equally prepares example 11, difference is, the weight of A15LV is 1.25 gram.

Example 12

As example 10 equally prepares example 12, difference is, the weight of A15LV is 3.20 gram.

Example 13

As example 10 equally prepares example 13, difference is, the weight of A15LV is 6.76 gram.

Example 14

By place in 650mL plastic beaker 6.88 grams of A15LV, 127.78 grams of P-250, 6.11 gram TPO-L and 3.51 grams of DC5604 prepares example 14.By container is placed in In Awatori-Rentaro AR-500Thinky Mixer and with the rotation of 1000rpm and The revolution of 1000rpm runs AR-5004 minute, thus described component is mixed.Will Container takes out from mixer and is added by 87.29 grams of PHP-75D and 122.22 grams of D100 In container.Mixture is through two step hybrid techniques.Rotation and 1000rpm at 1000rpm Revolution under continue within 4 minutes, perform first step.It is immediately performed second after the first step Step, and under the rotation of 30rpm and the revolution of 2000rpm, continue to perform for 15 seconds the Two steps, thus form resin compound.

Utilize width to be about 21 inches (53cm) and gap is 60 mils (1.52mm) Doctor knife coater, prepares about 21 inches × 23 inches (53.3cm on the backing that 4 mils (102 μm) are thick × 58.4) resin compound coating, described backing is by 4 conventional mil polyester release liner On by TPU, " ESTANE 58309-022 " is extruded into form of film at 210 DEG C and is formed.

Resin compound after coating and backing be placed in 24 inches × 24 inches (61.0cm × On the aluminium sheet that 61.0cm) × 0.25 inch (6.35mm) is thick.By 0.375 inch of (9.6mm) diameter 113 blocks of Magnet that × 0.125 inch (3.2mm) is thick are installed in aluminium sheet groove behind.Groove In the linear array including 15 row.In eight row in described row, often row has 8 grooves, and In 7 row in described row, often row has 7 grooves.It is spaced apart 4mm between row, and one It is spaced apart 7.5mm between groove in row.The first row groove (near the edge of plate) has Eight grooves；Second row has seven grooves.Continue this pattern alternately until having eight Tenth five elements of groove.The groove of the row of even-numbered is arranged such that they are positioned at corresponding phase Between the groove of adjacent rows the most between two parties.Diameter and the degree of depth of groove are respectively 9.8mm and 4.3mm. Use can process the adhesive tape of high temperature to be fixed in groove by Magnet.In resin compound coating The metal gauze of layout teflon coating on top, its about 24 inches × 24 inches (61.0cm × 61.0cm), and thick about 1.6mm, it has the circular hole of hexagonal array, the diameter of each circular hole The about distance between 6.2mm, and center is about 8mm.Between Magnet in silk screen and aluminium sheet Magnetic attraction make silk screen be forced through resin compound coating, thus at metal gauze and backing Between leave the thin base surface area of coating.

Defer to the curing process solidification resin compound as example 10.Taking out from baking oven Afterwards, metal gauze is removed from the resin of solidification, forms the poly-ammonia being attached to virgin polyester backing Band veined pad surface on ester TPU backing.Utilize transfering adhesive (of 127 μ m-thick From " the 3M ADHESIVE TRANSFER TAPE 9672 " of 3M company), by textured Pad surface polyester release liner hand-layup to about 21in × 23in (53.3cm × 58.4) × In a piece of polyurethane foam that 0.0787inch (2mm) is thick.From laminates die-cut 20.0 inches (50.8cm) pad of diameter, thus form the pad with structuring polishing feature of the present invention, Example 14.

Comparative example C5

As example 10 equally prepares comparative example C5, difference is, resin compound Compositions is saved A15LV.

Comparative example C6

As example 10 equally prepares comparative example C6, difference is, resin compound Consist of 1.44 grams of A15LV, 23 grams of P-250,47.50 grams of PHP-75D and 0.68 gram of DC5604, And it is used only at 100 DEG C the heat cure carried out two hours, eliminates UV curing schedule.

Comparative example C7

As comparative example C6 equally prepares comparative example C7, difference is, resin compound Compositions in save A15LV.

Example 15

As example 5 equally prepares example 15, difference is, the composition of resin compound Be 7.58 grams of 5350D, 28.00 grams of M1,23.75 grams of PHP-75D, 16.50 grams of D100, 0.83 gram of TPO-L and 0.77 gram of DC5604.

Comparative example C8

As example 15 equally prepares comparative example C8, difference is, resin compound Consist of 8.39 grams of 5350D, 28.00 grams of M1,47.50 grams of PHP-75D and 3.5g DC5604, And it is used only at 100 DEG C the heat cure carried out two hours, eliminates UV curing schedule.

Utilize method of testing 2 and 3；Practical measuring examples 10-15 and the hardness of comparative example C5-C8, hole Footpath meansigma methods, aperture standard deviation, pore diameter range, aperture unevenness and porosity.Result It is shown in table 2 below.

Table 2. hardness, aperture and porosity data

" embodiment ", " some embodiments " that entire disclosure is mentioned, " one Or multiple embodiment " or " embodiment ", no matter whether include art term " embodiment " is front Language " exemplary ", be intended to combine special characteristic that this embodiment describes, structure, material, Or characteristic is included at least one embodiment in some exemplary embodiments of the present invention. Therefore, entire disclosure occur everywhere as " in one or more embodiments ", " In some embodiments ", the phrase such as " in one embodiment " or " in an embodiment " may not Refer to the same embodiment in some exemplary embodiments of the present invention.It addition, concrete feature, Structure, material or feature can be attached in one or more embodiment in any suitable manner.

Although this specification describes some exemplary embodiments in detail, it is to be understood that, ability The technical staff in territory, after understanding foregoing, may be easy to imagine the more reshaping of these embodiments Formula, variations and equivalents.It will thus be appreciated that the present invention should not be the most limited In exemplary embodiment illustrated above.Especially, as used in this application, carried out by end points The statement of numerical range be intended to be included in this in the range of included all numerical value (such as 1 to 5 Including 1,1.5,2,2.75,3,3.80,4 and 5).It addition, used herein is all Number is considered as being modified by term " about ".Additionally, all publications of quoting of the application and Full patent texts is incorporated herein to quote mode as proof, just as pointed out especially and individually each Publication or patent, be all incorporated to quoting mode as proof.

Various exemplary embodiments are explained.These and other embodiment is all attributed to Within the scope of claims below.

Claims

1. a polishing pad, comprising:

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

Cross-linked network, it includes preparing by heat-curable resin composition is carried out heat cure Thermosetting adhesive composition and by radiation-hardenable composition being exposed to radiation and the radiation prepared is solid Changing component, wherein said radiation curable component and described thermosetting adhesive composition are in described cross-linked network Covalent bonding；

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

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

Polishing pad the most according to claim 1, it also includes being placed in described compliant layers and institute State the supporting course between porous polishing layer.

Polishing pad the most according to claim 1, wherein said thermosetting adhesive composition includes poly-ammonia At least one of ester or polyepoxide, and wherein said radiation curable component includes polypropylene In acid esters, polymethacrylates, polyvinylether, ethene polymers or polyepoxide extremely Few one.

Polishing pad the most according to claim 1, wherein said thermosetting adhesive composition and described poly- Polymer particle includes polyurethane independently of one another, and wherein said radiation curable component includes gathering At least one in acrylate or polymethacrylates.

5. according to the polishing pad described in any one of Claims 1-4, wherein said polymer Described thermosetting adhesive composition that particle is covalently bound in described cross-linked network or described radiation curing group At least one in Fen.

Polishing pad the most according to claim 4, wherein said polyacrylate or poly-methyl Acrylate is covalently bound to described thermosetting adhesive composition by carbamate or urea linking group.

7., according to the polishing pad described in any one of Claims 1-4, wherein said porous is thrown The hardness that photosphere is measured by the Shore D hardness set tester using model to be 1500 is at least 40 Shore D hardness.

8. according to the polishing pad described in any one of Claims 1-4, wherein said polymer The particle mean size of particle is in the range of 5 microns to 500 microns.

9. according to the polishing pad described in any one of Claims 1-4, wherein said polymer Particle is substantially spherical.

10. according to the polishing pad described in any one of Claims 1-4, wherein said polymerization Thing particle is fiber.

11. according to the polishing pad described in any one of Claims 1-4, wherein said polymerization Thing particle exists with most 20 weight % of gross weight based on described porous polishing layer.

12. according to the polishing pad described in any one of Claims 1-4, wherein said hole Aperture unevenness is 75% to the maximum.

13. according to the polishing pad described in any one of Claims 1-4, wherein said hole Average pore size is in the range of 5 microns to 100 microns.

14. polishing pads according to claim 2, wherein said polishing layer includes from described The polishing element of the separation that supporting course or described compliant layers highlight.

15. polishing pads according to claim 2, in wherein said supporting course or compliant layers At least one of which include organosilicon, natural rubber, SBR styrene butadiene rubbers, neoprene, At least one of polyolefin or polyurethane.

16. according to the polishing pad described in any one of Claims 1-4, wherein said polishing Pad is transparent at least partially.

17. 1 kinds of finishing methods, comprising:

By the surface of substrate and the institute according to the polishing pad described in any one of Claims 1-4 State the contact of porous polishing layer；And

18. 1 kinds of methods manufacturing polishing pad, described method includes:

Offer includes heat-curable resin composition, radiation-hardenable composition and polymer beads The compositions of son；

Form hole in the composition；

Described compositions is positioned on supporting course；And

By described compositions being exposed to radiation with at least partially curing described radiation-hardenable group Compound, and described compositions is heated with at least partially curing described heat-curable resin composition, Thus on supporting course, form porous polishing layer.

19. methods according to claim 18, the method also includes by compliant layers adhesively It is attached on the surface of the described supporting course relative with described porous polishing layer.

20. methods according to claim 18, wherein said heat-curable resin composition Including have at least two isocyanate groups or at least two epoxide group the first resin and There is the second resin of at least two in hydroxyl, amino, carboxyl or mercapto groups, and its Described in radiation-hardenable composition include acrylate, methacrylate, vinyl or ring At least two in oxygen groups.

21. methods according to claim 20, wherein said first resin has at least two Individual isocyanate groups, wherein said second resin has at least two oh group or at least two Individual amino group, wherein said radiation-hardenable composition includes at least two acrylate or first Base acrylate group, and wherein said radiation-hardenable composition also includes that at least one is different Cyanate group or oh group.

22. according to the method described in any one of claim 18 to 21, wherein said combination Thing also includes surfactant.

23. according to the method described in any one of claim 18 to 21, wherein said hole are Closed pore.