CN109957088A - Grinding pad and grinding pad urethane resin compositions - Google Patents
Grinding pad and grinding pad urethane resin compositions Download PDFInfo
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- CN109957088A CN109957088A CN201811581083.2A CN201811581083A CN109957088A CN 109957088 A CN109957088 A CN 109957088A CN 201811581083 A CN201811581083 A CN 201811581083A CN 109957088 A CN109957088 A CN 109957088A
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- grinding pad
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The present invention, which provides one kind, to be had high grinding rate and can get the grinding pad of the excellent grinding charge of high flatness (edge rounding is few) and its use urethane resin compositions.The grinding pad that the present invention uses, it is to contain the host agent (i) comprising carbamate prepolymer (A), with the hardening thing of the urethane resin compositions of curing agent (ii), carbamate prepolymer (A) is the product after the reacting of polyol component (a) and the composition of polyisocyanate (b) of the short-chain diol (a2) containing the polyalcohol (a1) and molecular weight less than 300 that are 300 or more comprising molecular weight, and there is isocyanate group in end, polyol component (a) includes the short-chain diol (a2) of 40 mass % or more and 90 mass % polytetramethylene glycol below and 1 mass % or more, the hardening thing is in 120 DEG C or more and 200 DEG C of ranges below with the peak value of tan δ, and in described 120 DEG C or more and 200 DEG C of ranges below Tan δ peak value be 0.18 or more.
Description
Technical field
The present invention relates to a kind of grinding pad and grinding pad urethane resin compositions.
Background technique
The present invention is more particularly directed to a kind of optical lens, glass substrate, silicon wafer, semiconductor devices etc. of can be preferably used as
The manufacturing method and grinding method of grinding pad, grinding pad in grinding.
(hard disk drives for optical lens, liquid crystal display (liquid crystal display, LCD) glass substrate, hard disk
Dynamic device (hard disk drive, HDD)) with requiring high-caliber grinding effect in glass substrate, silicon wafer, semiconductor devices etc.
Rate is non-scratch resistance.
Especially in the semiconductor devices, as the integrated level of semiconductor circuit increased dramatically, constantly promote with height
Miniaturization or multilayer wiring for the purpose of densification, and require higher levels of surface and the Gao Yan in turn of machined surface
Grind efficiency.In addition, with the enlargement of liquid crystal display, also requiring machined surface in the liquid crystal display glass substrate
Higher levels of surface and high grinding efficiency.High levelization is realized in the requirement of the surface of such machined surface,
And then the grinding efficiency etc. in attrition process requires performance to further increase.
Therefore, in the manufacturing process of optical lens or semiconductor devices or LCD, as can be formed with excellent flat
The grinding method on the surface of property, is widely used chemical mechanical milling method, so-called CMP (Chemical Mechanical
Polishing) method.
In the CMP method, supply makes abrasive grains (polishing particles) be scattered in alkalinity molten when being typically employed in attrition process
Slurry (lapping liquid) in liquid or acid solution is come the free abrasive grains mode ground.That is, grinding charge (machined surface) is sharp
It is planarized with the mechanism of the abrasive grains in slurry, with the chemical action of alkaline solution or acid solution.Herein, adjoint
To the high levelization for the flatness that machined surface requires, grinding precision or grinding efficiency etc. required by CMP method grind performance, specifically
It is improved for the requirement of high grinding rate, non-scratch resistance, high flatness.As the free abrasive grains mode for using the CMP method
Grinding pad, such as propose that one kind is difficult to produce by control hardness or abrasion or the specific parameter such as slack time or coefficient of elasticity
The big grinding pad (referring to patent document 1, patent document 2) of the raw grinding rate scratched.
In addition, such as the finishing of the carbamate grinding pad with specific composition ethylene glycol list phenyl ether
(dressing) property (shear rate) is excellent (referring to patent document 3).In addition, the Polyester for example using used raw material is more
The compatibility of first alcohol and polyether system polyalcohol and the grinding rate of the carbamate grinding pad that forms macroscopical phase separation structure is big
And excellent in stability (referring to patent document 4, patent document 5).
In addition, for example defining the grinding speed of the grinding pad of raw material composition to specific bubble diameter or storage coefficient of elasticity
Degree is big, and running-in period (break in time) is excellent (referring to patent document 6).
As described, it is strongly required a kind of high grinding for meeting high levelization required by High-precision from industrial circle
Rate, low scratch resistance and high flatness grinding pad, and various trials are carried out, but actual conditions are not find yet.
Existing technical literature
Patent document
1 Japanese Patent Laid-Open 2014-111296 bulletin of patent document
Patent document No. 5710353 bulletins of 2 Japan Patent
3 Japan Patent of patent document 5738731 wide reports
Patent document No. 5623927 bulletins of 4 Japan Patent
5 Japan Patent of patent document 5623927 wide reports
6 Japan Patent of patent document 5393434 wide reports
Summary of the invention
Problem to be solved by the invention
Project to be solved by this invention is that providing one kind has high grinding rate and can get high flatness (edge
Rounding is few) grinding pad of excellent grinding charge.
Technical means to solve problem
The inventors of the present invention people has carried out making great efforts research in order to solve the problem, as a result, it has been found that, by being made soft chain
The composition of section and the ratio of hard segment are set as particular range and in Measurement of Dynamic Viscoelasticity, under specific temperature range
With tan δ peak value person more than particular value, it is possible to provide there is high grinding rate and can get high flatness (edge rounding is few)
The grinding pad of excellent grinding charge, so as to complete the present invention.
That is, grinding pad of the invention is containing the host agent (i) comprising carbamate prepolymer (A) and curing agent (ii)
Urethane resin compositions hardening thing, the carbamate prepolymer (A) be containing comprising molecular weight be 300 with
On polyalcohol (a1) and molecular weight less than 300 short-chain diol (a2) polyol component (a) and polyisocyanate (b) conduct
Product after at least part of reaction of raw material, and there is isocyanate group in end, the polyol component (a) is with 40
Quality % or more and 90 mass % containing ratios below include polytetramethylene glycol, and the containing ratio of the short-chain diol (a2) exists
In the polyol component (a) be 1 mass % or more, the hardening thing will measure frequency be set as 1Hz dynamic viscoelastic survey
In fixed, there are the peak value of tan δ, and described 120 DEG C or more and 200 DEG C or less in 120 DEG C or more and 200 DEG C of ranges below
Range in tan δ peak value be 0.18 or more.
The effect of invention
Grinding pad of the invention can be that with high grinding rate and can get the excellent quilt of high flatness (edge rounding is few)
The grinding pad of abrasive material.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (scanning of the section (sliced surfaces) of the grinding pad of embodiment 1
Electron microscope, SEM) image.
Fig. 2 is scanning electron microscope (SEM) image of the section (sliced surfaces) of the grinding pad of comparative example 1.
Fig. 3 is the Measurement of Dynamic Viscoelasticity chart of the grinding pad of embodiment 3.
Fig. 4 is carried out using surface of the spectral interference laser displacement gauge to the silicon wafer of the grinding pad grinding through embodiment 3
The distribution map of the height of measurement.
Fig. 5 is the Measurement of Dynamic Viscoelasticity chart of the grinding pad of comparative example 7.
Fig. 6 is carried out using surface of the spectral interference laser displacement gauge to the silicon wafer of the grinding pad grinding through comparative example 7
The distribution map of the height of measurement.
Specific embodiment
Grinding pad of the invention is the ammonia containing the host agent (i) comprising carbamate prepolymer (A) and curing agent (ii)
The hardening thing of carbamate resin combination, the hardening thing will measure in the Measurement of Dynamic Viscoelasticity that frequency is set as 1Hz,
With the peak value of tan δ in 120 DEG C or more and 200 DEG C of ranges below, and in described 120 DEG C or more and 200 DEG C of ranges below
Tan δ peak value be 0.18 or more.Think, in Measurement of Dynamic Viscoelasticity, since there are the peak values, therefore implies described
Existing in hardening thing, there is specific viscoelastic fine domain by the presence in the fine domain, may achieve in the present invention
The high flatness of high grinding rate and grinding charge.In the present invention, the fine domain can be by by polyol component (a)
Composition is set as particular one and generates.
It is described will measure frequency be set as 1Hz Measurement of Dynamic Viscoelasticity in, the peak value of tan δ be preferably in 120 DEG C with
In upper and 180 DEG C of ranges below, more preferably in 110 DEG C or more and 170 DEG C of ranges below.
The peak value of the tan δ is preferably 0.20 or more, and more preferably 0.25 or more, and then preferably 0.3 or more, the upper limit
It is not particularly limited, may be, for example, 1 hereinafter, can also be in turn 0.8 or less.
In the host agent (i), the carbamate prepolymer (A) is polyol component (a) and polyisocyanate (b)
After reaction product (by polyol component (a) and polyisocyanate (b) be set as raw material it is at least part of react after life
At object), and there is isocyanate group in end.
The polyol component (a) may include one or more kinds of polyalcohol, and including at least molecular weight is 300 or more
Polyalcohol (a1) (hereinafter, sometimes referred to simply as " polyalcohol (a1) ") and molecular weight less than 300 short-chain diol (a2) (hereinafter,
Sometimes referred to simply as " short-chain diol ").
The polyalcohol (a1) can form soft chain segment in grinding pad obtained.The quantity of the polyalcohol (a1) is average
Molecular weight is preferably 700 or more, more preferably 1,100 or more, and then preferably 00 or more Isosorbide-5-Nitrae, and preferably 8,000 hereinafter,
More preferably 5,000 hereinafter, be preferably 3,000 hereinafter, particularly preferably 2 in turn, and 500 or less.
In the present specification, number average molecular weight can utilize gel permeation chromatography (GPC (gel permeation
Chromatography) method), it is measured using polystyrene as standard sample.In addition, comprising two or more polynary
In the case that alcohol is as the polyalcohol (a1), the number average molecular weight of the polyalcohol (a1) can be based on the number of each polyalcohol
Average molecular weight and mass ratio are measured, is calculated as weighted average.
The number of hydroxyl contained in the polyalcohol is preferably two or more and five or less.
The polyalcohol (a1) includes polyether polyol (a1-1).As the polyether polyol (a1-1), can enumerate logical
The polyoxy sub alkyl polylol crossing the ring-opening polymerisation of cyclic ether and obtaining can also contain reactive hydrogen with more than two to use
The one or more of the compound of the base of atom winner as initiator.
The carbon atom number of the cyclic ether is preferably 2~10, and more preferably 2~6, and then preferably 2~4.The ring-type
Hydrogen atom contained in ether can replace through halogen atom.As the cyclic ether, one or more can be used, such as can arrange
It lifts: ethylene oxide, propylene oxide, 1,2- epoxy butane, 2,3- epoxy butane, styrene oxide, epichlorohydrin, tetrahydrofuran, alkane
Base tetrahydrofuran etc..
As the initiator, one or more can be used, such as can enumerate: ethylene glycol, diethylene glycol, the third two
There are two reactive hydrogens for the tool such as alcohol, trimethylene, 1,3 butylene glycol, 1,4- butanediol, 1,6-HD, neopentyl glycol, water
The compound of atom；Glycerol, two glycerol, trimethylolethane, trimethylolpropane, hexanetriol, monoethanolamine, diethanol amine,
There are three the compounds etc. of above active hydrogen atom for the tool such as triethanolamine, ethylenediamine, pentaerythrite, granulated sugar.
The polyether polyol (a1-1) includes at least polytetramethylene glycol.Contained in the polyol component (a)
The number average molecular weight of polytetramethylene glycol is 300 or more, preferably 1,100 or more, more preferably 1,300 or more, and
Preferably 4,000 hereinafter, more preferably 3, and 000 hereinafter, be preferably 2,500 or less in turn.Flat comprising two or more quantity
In the case where the different polytetramethylene glycol of average molecular weight, the number average molecular weight of polytetramethylene glycol can be based on each poly-
The number average molecular weight and mass ratio of tetramethylene glycol, calculate as weighted average.
In the polyol component (a), the containing ratio of polytetramethylene glycol is 40 mass % or more, preferably 50 matter
% or more, more preferably 60 mass % or more are measured, and are 90 mass % hereinafter, preferably 85 mass % are hereinafter, more preferably 80
Quality % or less.
In the polyalcohol (a1), the containing ratio of polytetramethylene glycol is preferably more than 50 mass %, and more preferably 60
Quality % or more, and then preferably 70 mass % or more, particularly preferably 75 mass % or more, and be 100 mass % or less.It is special
Not You Xuanwei polyalcohol (a1) be polytetramethylene glycol.
The polyether polyol (a1-1) also may include polyoxypropylene polyol.The quantity of the polyoxypropylene polyol is flat
Average molecular weight is 300 or more, and preferably 400 or more, and preferably 5,000 hereinafter, more preferably 2, and 000 hereinafter, in turn preferably
It is 1,000 or less.Comprising the different polyoxypropylene polyol of two or more number average molecular weights, polyoxy third
The number average molecular weight of alkene polyalcohol can number average molecular weight and mass ratio based on each polyoxypropylene polyol, as
Weighted average calculates.
The number of hydroxyl contained in the polyoxypropylene polyol be 2 or more, preferably 3 or more, and preferably 5 with
Under, more preferably 4 or less.
Comprising polyoxypropylene polyol, in the polyalcohol (a1), relative to polytetramethylene glycol 100
Mass parts, the content of polyoxypropylene polyol are preferably 5 mass parts or more, and it is more than more preferably 10 mass parts, and preferably 50
Below the mass, more preferably 40 below the mass, and then preferably 30 below the mass.
In the polyalcohol (a1), the containing ratio of the polyether polyol (a1-1) is preferably 80 mass % or more, more excellent
90 mass % or more, and then preferably 95 mass % or more are selected as, the upper limit is 100 mass %.
It also may include other polyalcohols (a1-2) in the polyalcohol (a1) in addition to the polyether polyol (a1-1).
As other described polyalcohols (a1-2), one or more can be used, such as can enumerate: polyester polyol, polycarbonate
Polyalcohol, polybutadiene polyol, polyacrylic polyols, polyisoprene polyol etc..
As the polyester polyol, one or more can be used, such as can enumerate: making the polyalcohol of low molecular weight
The polyester polyol reacted and obtained with polycarboxylic acid；Make the cyclic ester compounds such as 6-caprolactone carry out ring-opening polymerization and
The polyester polyol of acquisition；The polyester polyol etc. for being copolymerized these and obtaining.
As the polyalcohol of the low molecular weight, one or more can be used, for example, can enumerate molecular weight be 50 with
It is upper and less than 300 polyalcohol, such as can enumerate: ethylene glycol, propylene glycol, 1,4-butanediol, 1,6- hexylene glycol, diethylene glycol,
The aliphatic polyols such as neopentyl glycol, 1,3 butylene glycol；Cyclohexanedimethanol etc. has the polyalcohol of ester ring type structure；Bisphenol-A
And Bisphenol F etc. has the polyalcohol of aromatic ring.Wherein, preferably 1,6- hexylene glycol, neopentyl glycol.
As the polycarboxylic acid in the manufacture that can be used for the polyester polyol, one or more, example can be used
It can such as enumerate: succinic acid, adipic acid, decanedioic acid, dodecanedicarboxylic acid aliphatic polycarboxylic acid；Terephthalic acid (TPA), isophthalic diformazan
The aromatic multi-carboxy acids such as acid, phthalic acid, naphthalene dicarboxylic acids；These acid anhydride or carboxylate etc..
The polycarbonate polyol is that carbonic acid and carbonic ester and polyalcohol is made to carry out esterification and winner.As institute
Polyalcohol is stated, one or more can be used, such as can enumerate: 1,3-PD, 1,4-butanediol, 1,6- hexylene glycol, two
Ethylene glycol, polyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol etc..
As polybutadiene polyol, can enumerate to polybutadiene addition alkylene oxide (such as ethylene oxide, propylene oxide
Deng) and the polyalcohol etc. of acquisition.
As polyacrylic polyols, it can enumerate and acrylate and vinyl compound etc. are copolymerized and obtained more
First alcohol etc..
As polyisoprene polyol, can enumerate to polyisoprene addition alkylene oxide (such as ethylene oxide, epoxy third
Alkane etc.) and the polyalcohol etc. of acquisition.
In the polyol component (a), the containing ratio of polyalcohol (a1) is preferably 60 mass % or more, more preferably 70 matter
Measure % or more, and preferably less than 100 mass %, more preferably 99 mass % or less.
The short-chain diol (a2) can form hard segment in grinding pad obtained.As the short-chain diol (a2),
One or more of the glycol of molecular weight less than 300 can be used, such as can enumerate: ethylene glycol, diethylene glycol, 1,2- third
Glycol, 1,3- propylene glycol, 2- methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3 butylene glycol, 1,4- fourth
Glycol, neopentyl glycol (2,2- dimethyl -1,3- propylene glycol), 2- isopropyl -1,4- butanediol, 3- methyl -2,4-PD, 2,
4- pentanediol, 1,5- pentanediol, 3- methyl-1,5- pentanediol, 2- methyl -2,4-PD, 2,4- dimethyl -1,5- penta 2
Alcohol, 2,4- diethyl -1,5- pentanediol, 1,5- hexylene glycol, 1,6-HD, 2- ethyl -1,3- hexylene glycol, 2- ethyl -1,6-
Hexylene glycol, 1,7- heptandiol, 3,5- heptandiol, 1,8- ethohexadiol, 2- methyl-1,8- ethohexadiol, 1,9- nonanediol, the 1,10- last of the ten Heavenly stems
The aliphatic diols such as glycol, cyclohexanedimethanol (such as 1,4 cyclohexane dimethanol), cyclohexanediol (such as 1,3- hexamethylene two
Alcohol, 1,4- cyclohexanediol), the ester ring types glycol such as bis- (4- hydroxy-cyclohexyl)-propane of 2- etc..
Wherein, the short-chain diol (a2) is preferably aliphatic diol, particularly preferably diethylene glycol.
In the polyol component (a), the containing ratio of the short-chain diol (a2) is 1 mass % or more, preferably 5 matter
% or more, more preferably 10 mass % or more, and then preferably 15 mass % or more are measured, and preferably 50 mass % are hereinafter, more
Preferably 40 mass % hereinafter, be preferably 30 mass % or less in turn.
In the polyol component (a), the containing ratio of the polyalcohol (a1) and the short-chain diol (a2) is preferably 80
Quality % or more, more preferably 90 mass % or more, and then preferably 95 mass % or more, the upper limit are 100 mass %.
It also may include it in the polyol component (a) in addition to the polyalcohol (a1) and the short-chain diol (a2)
His polyalcohol (a3).As other described polyalcohols (a3), can enumerate: trimethylolethane, trimethylolpropane, hexitol
Class, pentose alcohols, glycerol, polyglycereol, pentaerythrite, dipentaerythritol, tetra methylol propane equimolecular quantity less than 300 simultaneously have
The polyalcohol etc. of three or more hydroxyls.
As the polyisocyanate (b), one or more can be used, such as can enumerate: hexamethylene diisocyanate
Ester, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate etc. have the polyisocyanate of ester ring type structure；4,
4'- methyl diphenylene diisocyanate, 2,4'- methyl diphenylene diisocyanate, carbon imidodicarbonic diamide modified diphenylmethane two
The virtues such as isocyanates, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate
Fragrant adoption isocyanates；Hexamethylene diisocyanate, lysine diisocyanate, xylene diisocyanate, tetramethyl two
The aliphatic polymeric isocyanates such as toluene di-isocyanate(TDI).In these, high rigidity with regard to grinding pad and further can more it mention
For high grinding rate, preferably aromatic poly-isocyanate, and preferably toluene di-isocyanate(TDI) or diphenyl methane two is different
Cyanate, particularly preferably toluene di-isocyanate(TDI).
Hydroxyl contained in isocyanate group contained in the polyisocyanate (b) and the polyol component (a)
Equivalent proportion (NCO/OH) is preferably 1.3 or more, and more preferably 1.5 or more, and preferably 6.5 hereinafter, more preferably 4 hereinafter, special
It You Xuanwei 3 or less.The molar ratio (NCO/OH) is bigger, can more reduce the viscosity of carbamate prepolymer (A), grind
Make stability of flow in the manufacture of pad and improve Combination, to be easy to promote quality.In addition, the molar ratio (NCO/OH) is more
Small, the viscosity of carbamate prepolymer (A) more rises, and can extend pot life.
The carbamate prepolymer (A) is after the polyol component (a) is reacted with the polyisocyanate (b)
Product (product after urethane reaction).It the polyalcohol (a1), short-chain diol (a2) and optionally uses
There is no particular restriction for the reaction sequence of other polyalcohols (a3) and the polyisocyanate (b), can make the polyalcohol (a1), institute
It states short-chain diol (a2) and other described polyalcohols (a3) for optionally using and the polyisocyanate (b) carries out instead simultaneously
It answers, after the polyalcohol (a1) can also be made to be reacted with the polyisocyanate (b), makes the product and short-chain diol obtained
(a2) and optionally other polyalcohols (a3) used are reacted.
The isocyanate group equivalent of the carbamate prepolymer (A) is preferably 200g/eq. or more, more preferably
250g/eq. or more, and preferably 800g/eq. is hereinafter, more preferably 600g/eq. or less.
The value that the isocyanate group equivalent (NCO equivalent) of the carbamate prepolymer (A) is expressed as follows: according to JIS-
Method specified in K-7301:2003, sample is dissolved in dry toluene, and excessive di-n-butyl amine aqueous solution is added and into
Row reaction, the value that the di-n-butyl amine progress back titration of remaining is found out using hydrochloric acid standard solution.
The viscosity (80 DEG C) of the carbamate prepolymer (A) is preferably 2,000mPas hereinafter, more preferably 1,
500mPas hereinafter, be preferably 1,200mPas hereinafter, may be, for example, 300mPas or more, and then can also be in turn
400mPas or more.
The viscosity (80 DEG C) of the carbamate prepolymer (A) can be measured at 80 DEG C of temperature using Brookfield viscometer.
The host agent (i) also may include other carbamate prepolymers other than the carbamate prepolymer (A).
The containing ratio of the carbamate prepolymer (A) is in carbamate prepolymer (A) and other carbamate prepolymers
It is preferably 70 mass % or more, more preferably 80 mass % or more, and then preferably 90 mass % or more in total, the upper limit is
100 mass %.
In addition, the host agent (i) can also include polyisocyanate in turn.As the polyisocyanate, conduct can be used
The polyisocyanate (b) and illustrate polyisocyanate, particularly preferably 4,4'- methyl diphenylene diisocyanate, toluene
The aromatic poly-isocyanates such as diisocyanate；Dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate etc. have
The polyisocyanate etc. of ester ring type structure.
The curing agent (ii), which is contained, contains work with what is reacted with isocyanate group possessed by the host agent (i)
The compound of the base ([NH] base and/or [OH] base) of property hydrogen atom.As the chemical combination with the base containing active hydrogen atom
Object can be used one or more, such as can enumerate: the aliphatic such as ethylenediamine, propane diamine, hexamethylene diamine, isophorone diamine
Or ester ring type amine compounds；Phenylenediamine, the chloro- 4,4'- diaminodiphenyl-methane of 3,3'- bis-, poly- amino-chloro-benzene methylmethane chemical combination
The aromatic amines compounds such as object；Ethylene glycol, diethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 3- methyl-1,5-
Pentanediol, bisphenol-A, the alkylene oxide addition product of bisphenol-A, polyether polyol, polyester polyol, polycaprolactone polyol, poly- carbonic acid
Ester polyol etc. has the compound of more than two hydroxyls；Polymer (the preferably dimer of the aromatic amines compound
~the tetramer)；And these mixture etc..
The mixture preferably includes the mixture of the polymer of the aromatic amines compound, in the mixture
In, the containing ratio of polymer is preferably 10 mass % or more, more preferably 20 mass % or more, and preferably 80 mass % with
Under, more preferably 70 mass % or less.
The mixture can also include polyalcohol (preferably polyether polyol) in turn.May include in the mixture is more
First alcohol is preferably polyether polyol (especially polyoxytetramethylene glycol), and the number average molecular weight of the polyalcohol is preferably
300 or more, and preferably 3,000 hereinafter, more preferably 2, and 000 hereinafter, be preferably 1,500 or less in turn.
The urethane resin compositions can also include auxiliary agent (iii) in turn.
Auxiliary agent contained in the urethane resin compositions (iii) preferably includes polyalcohol, the polyalcohol
It can be identical also different from the polyalcohol (a1) for forming the carbamate prepolymer (A).As the polyalcohol, can be used
One or more, such as the polyoxy sub alkyl polylol obtained by the ring-opening polymerisation of the cyclic annular monoether can be enumerated,
It can also be use the one or more of the compound with more than two bases containing active hydrogen atom as drawing
Send out agent and winner.
The containing ratio of the polyalcohol is preferably 50 mass % or more, more preferably 70 matter in the auxiliary agent (iii)
% or more, and then preferably 80 mass % or more are measured, the upper limit is 100 mass %.
The auxiliary agent (iii) can also be in turn comprising selecting composed by Free water, aftermentioned catalyst and aftermentioned infusion processed
At least one of group.
In the case where including auxiliary agent (iii) in the urethane resin compositions, relative to the carbamic acid
100 mass parts of ester prepolymer, the content of auxiliary agent (iii) may be, for example, 0.1 mass parts or more, and then can also be 1 mass parts or more,
Preferably 10 below the mass, and more preferably 5 below the mass.
It is achieved with the high grinding rate after grinding and can get that high flatness (edge rounding is few) is excellent to be ground
It, can be with isocyanide contained in the curing agent (ii) and the aftermentioned auxiliary agent (iii) optionally used for the grinding pad for grinding object
The ratio of the molal quantity of the isocyanate group of total molal quantity and host agent (i) of the base of perester radical reaction is ([with the curing agent
(ii) and optionally total molal quantity of the base of the isocyanate group reaction of the auxiliary agent (iii) used]/[carbamate pre-polymerization
The molal quantity of the isocyanate group of object (A)].Hereinafter referred to as " R value ") it is preferably 0.7~1.1, more preferably 0.8~1.
Relative to 100 mass parts of host agent (i), the amount of the curing agent (ii) is preferably 5 mass parts or more, more preferably
More than 10 mass parts, and preferably 50 below the mass, more preferably 30 below the mass.
Urethane resin compositions used in the present invention include the master containing the carbamate prepolymer (A)
The curing agent (ii) of agent (i) and the compound comprising that can be reacted with isocyanates also may include other as an essential component
Additive.Other described additives may be included in any of host agent (i), curing agent (ii) and the auxiliary agent (iii) optionally used
In person, if not reacting or evaporating with host agent (i) or curing agent (ii), host agent (i) or curing agent (ii) may be included in
In, but the additive for reacting or evaporating etc. is preferably contained in the auxiliary agent (iii) optionally used.
As other described additives, one or more can be used, such as can enumerate: water (reactive foaming agent),
Chemical foaming agent, physical blowing agent, catalyst, surfactant, abrasive grains, filler, pigment, thickener, antioxidant, ultraviolet light
Absorbent, surfactant, fire retardant, plasticiser etc..
Wherein, using the urethane resin compositions and the case where obtain grinding pad using Water blown method
Under, it is preferable to use the water as reactive foaming agent.In the case where foaming agent is water, relative to 100 matter of host agent (i)
Measure part, the content of water be preferably 0.01 mass parts or more and 1 below the mass.
As the foaming agent other than water, it is possible to use chemical foaming agent or physical blowing agent.As chemical foaming agent, exist
Azodicarbonamide (azodicarbonamide, ADCA), the N of organic system, N'- dinitropentamethylenetetramine (N, N'-
Dinitropentamethylene tetramine, DPT), 4,4'- oxobenzenesulfonyl hydrazide (4,4'-
Oxybisbenzenesulphonyl hydrazide, OBSH) or the bicarbonate of inorganic system, carbonate, bicarbonate with have
The combination etc. of machine hydrochlorate.As physical blowing agent, the pentamethylene or pentane of hydrocarbon system there are the HFC-245fa of chlorofluorocarbons system,
HFC-365mfc, HCFO-1233zd, HFO-1336mzz etc..As long as the amount of foaming agent is with the side of the grinding pad density as target
Formula is suitable for adjustment.
As the catalyst, one or more can be used, such as can enumerate: N, N- dimethylamino ether, three
Ethylenediamine, dimethylethanolamine, triethanolamine, N, N, N', the tertiary amines such as N'- tetramethyl hexamethylene diamine, N- methylimidazole
Catalyst；Metallic catalysts such as tin dilaurate dioctyl tin etc..In these, so that it may for the foaming of form stable, preferably
Triamine catalyst, more preferably N, N- dimethylamino ether.
Using the catalyst, so that it may be formed for stable foaming, relative to the host agent (i) 100
Mass parts, the content of the catalyst be preferably 0.001 mass parts or more and 5 below the mass.
As the surfactant, silicone surfactant can be enumerated, one or more can be used.For example, it is beautiful to enumerate east
" beautiful silicone (Toray Silicone) SH-193 in east " of the manufacture of DOW CORNING (Toray Dow Corning) limited liability company,
" beautiful silicone (Toray Silicone) SH-192 in east ", " beautiful silicone (Toray Silicone) SH-190 in east " etc..
Using the surfactant, so that it may be stably formed for fine bubble, relative to the host agent
(i) 100 mass parts, the content of the surfactant be preferably 0.001 mass parts or more and 5 below the mass.
As the method for using the urethane resin compositions and manufacturing grinding pad, such as can enumerate with lower section
Method: by the host agent (i), the curing agent (ii) and optionally the auxiliary agent (iii) that uses is mixed and is injected into mold,
Make its foaming, harden and obtain foaming and molding object, then take out the foaming and molding object from mould, and being sliced is sheet to make
It makes.
Most cases using auxiliary agent (iii) be to curing agent (ii) using the chloro- 4,4'- diaminomethane of 3,3'- bis- (3,
3'-dichloro-4,4'-diaminomethane, MBOCA) and carry out Water blown the case where.Conduct when about Water blown is anti-
The adding purpose of the water of answering property foaming agent, because host agent (i) and water react, therefore can not be added in host agent (i).In addition,
It when being added to the MBOCA of dissolution, evaporates, therefore can not add at 100 DEG C or more.Thus, it is preferably the adding purpose of water auxiliary agent
(iii)。
In the case where including auxiliary agent (iii) in the urethane resin compositions, relative to the host agent (i)
100 mass parts, the content of auxiliary agent (iii) may be, for example, 0.1 mass parts or more, so can also to be more than 1 mass parts, preferably 10
Below the mass, more preferably 8 below the mass.
As the method for mixing the urethane resin compositions, using the auxiliary agent (iii),
It preferably prepares in advance polyalcohol or the well-mixed auxiliary agent such as water or catalyst or surfactant (iii).For example, can enumerate with
Lower method: the host agent (i), the curing agent (ii) and auxiliary agent (iii) are put into each different tank of mixing casting machine
In, the host agent (i) is heated up to preferably 40 DEG C~80 DEG C, the curing agent (ii) is heated up to preferably 40 DEG C~120
DEG C, auxiliary agent (iii) is heated up to 30 DEG C~70 DEG C, and utilize mixing casting machine by each mixing.
In addition, in the case where not using the auxiliary agent (iii), as long as other additives are added to required host agent (i)
Or in curing agent (ii), preferably it is added in curing agent (ii).Preparing in advance has with isocyanate group progress instead
Water or catalyst or whole bubble have been sufficiently mixed in the compound for the base ([NH] base and/or [OH] base) containing active hydrogen atom answered
The curing agent (ii) of agent etc..For example, following methods can be enumerated: the host agent (i), the curing agent (ii) to be put into mixing and pour
In each different tank of note machine, the host agent (i) is heated up to preferably 40 DEG C~80 DEG C, the curing agent (ii) is heated
To preferably 30 DEG C~70 DEG C, and utilize mixing casting machine by each mixing.
As the method by urethane resin compositions manufacture grinding pad, following methods can be enumerated: made described
Urethane resin compositions in mould harden and obtain foaming hardening thing (preferably in mold) by foaming, and then solid after progress
Change.Optionally, it by foaming hardening thing obtained and then can also form.Specifically, will be described using the mixing casting machine
After urethane resin compositions mixing, each ingredient is sprayed from mixing in casting machine, mixture obtained is injected into
Be heated up in 40 DEG C~120 DEG C of mold in advance, cover the lid of the mold, for example, 50 DEG C~130 DEG C at a temperature of foam
Hardening 10 minutes~10 hours, to obtain foaming hardening thing.Later, foaming hardening thing obtained is taken out, preferably 100
DEG C~solidify after progress under conditions of 120 DEG C and 8 hours~20 hours.The foaming hardening thing obtained in this way is sliced,
To can be made into grinding pad of the invention.
The thickness of the grinding pad can be suitable for decision depending on the application, such as the range of preferably 0.6mm~3mm.
In addition, manufacturing the other methods of grinding pad as the urethane resin compositions are used, such as can arrange
Lift following methods: obtain using inflation (gas loading) method make the host agent (i) containing micro air bubble host agent (i') (with
Under, slightly it is denoted as " host agent (i') containing micro air bubble "), the host agent (i') containing micro air bubble and curing agent (ii) will be contained
Carbamate composition is mixed and is injected into mould, make its harden and obtain the molding containing micro air bubble, then by this at
Shape object takes out from mould, and being sliced is sheet.
As the method for obtaining the host agent (i') containing micro air bubble by the host agent (i), such as can enumerate to the host agent
(i) non-reactive gas such as nitrogen, carbonic acid gas, helium, argon are imported, and mechanically import the method for bubble.
As the method for mixing the carbamate composition, for example, by the host agent (i') containing micro air bubble,
And the curing agent (ii) is put into each different tank of mixing casting machine, and the host agent (i') containing micro air bubble is added
Temperature is heated up to preferably 40 DEG C~120 DEG C to preferably 40 DEG C~80 DEG C, by the curing agent (ii), and utilizes mixing casting machine
By each mixing.
Then, each ingredient is sprayed from mixing casting machine, mixture obtained is injected into and is heated up to 40 DEG C in advance
In~120 DEG C of mold, cover the lid of the mold, for example, 50 DEG C~130 DEG C at a temperature of foam and harden 10 minutes~
10 hours, to obtain foaming and molding object.Later, foaming and molding object obtained is taken out, preferably at 100 DEG C~120 DEG C and 8
Hour~solidify after progress under conditions of 20 hours.
Secondly, obtaining grinding pad and being sliced the foaming and molding object with thickness appropriate for sheet.After slice
The thickness of grinding pad can be suitable for depending on the application determining, for example, the range of 0.6mm~3mm.
In addition, manufacture the other methods of grinding pad as the carbamate composition is used, for example, can enumerate with
Lower method: when being mixed the host agent (i) and curing agent (ii) using mixing casting machine, mixing machine portion is imported and is mixed non-
The mixture of mechanical foaming (mechanical froth) shape is injected into mould by reactant gas, it is made to harden and be sent out
Foam forming object then takes out the foaming and molding object from mould, and being sliced is sheet.
In turn, the other methods of grinding pad are manufactured as the urethane resin compositions are used, such as can arranged
It lifts following methods: making the plastic sphere in the host agent (i) or curing agent (ii) containing 20 μm~120 μm of diameter of hollow form
Two solution of host agent, curing agent are mixed and harden it and obtain and contain hollow plastics ball by (microballoon (microballoon))
The molding of body, then slice is sheet.
The grinding pad of the invention has high grinding rate, and can get high flatness (edge rounding is few), to optics
Lens, liquid crystal display (LCD) glass substrate, hard disk (HDD) glass substrate, recording device glass plate, optics are with thoroughly
The attrition process of the high grinding rate of the requirement of mirror, silicon wafer, semiconductor devices etc. and high-caliber flatness (edge rounding) and
It says useful.Especially to Vickers hardness be 1500 it is below be ground the grinding of material for it is useful, specifically to silicon wafer or
It is useful for the grinding of glass.
Vickers hardness is one kind of the index of penetration hardness, and the rigid body made of diamond (pressure head) indentation is tested
Object is judged using the area of the impression formed at this time.As test method, there are JIS-Z-2244.It is various to be ground
Rough Vickers hardness it is substantially as described below.
Silicon carbide (SiC): 2300~2500, sapphire: 2300, silicon: 1050, quartz glass: 950, various glass: 500
~700.
As the grinding method for using grinding pad of the invention, such as in the case where the grinding of silicon wafer, can enumerate with
Lower method etc. (utilizes the CMP polishing of free abrasive grains): slurry is added dropwise on grinding pad, and (weakly alkaline colloidal silica is water-soluble
Liquid), and make to be ground body and be crimped on the pad being adapted with slurry, make the platen for being pasted with pad operating (rotation) come into
Row grinding.
Embodiment
Hereinafter, embodiment is enumerated to carry out more specific description to the present invention.
In embodiment, the number average molecular weight of polyalcohol (a1) is surveyed using gel permeation chromatography (GPC method)
It is fixed.
Measurement device: high speed GPC device (" HLC-8220GPC " of the manufacture of Tosoh limited liability company) tubing string: will be following
Tubing string (be Tosoh limited liability company manufacture) be connected in series and use.
" TSKgel G5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (Differential refractometer)
Tubing string temperature: 40 DEG C
Eluat: tetrahydrofuran (tetrahydrofuran, THF)
Flow velocity: 1.0mL/min
Injection rate: 100 μ L (tetrahydrofuran solution that sample solution concentration is 0.4 mass %)
Standard sample: calibration curve is made using standard polystyren below.
(standard polystyren)
" the TSKgel standard polystyren A-500 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren A-1000 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren A-2500 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren A-5000 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-1 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-2 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-4 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-10 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-20 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-40 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-80 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-128 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-288 " of Tosoh limited liability company manufacture
" the TSKgel standard polystyren F-550 " of Tosoh limited liability company manufacture
(1~synthesis example of synthesis example 4 compares synthesis example 1~compare synthesis example 3, compare synthesis example 5~and compares synthesis example 9:
Carbamate prepolymer (A1)~carbamate prepolymer (A4), carbamate prepolymer (A'1)~carbamate
Prepolymer (A'3), carbamate prepolymer (A'5)~carbamate prepolymer (A'9) synthesis)
The loading table 1 into 5 liters of four round flask for having nitrogen ingress pipe, cooling condenser, thermometer, blender
Shown in polyisocyanate (b), and start to stir.Then, it is packed into polyalcohol (a1) shown in simultaneously mixture table 1, in nitrogen environment
Under with 80 DEG C carry out 3 hours react.Then, make short-chain diol shown in table 1 (a2) anti-at 80 DEG C when paying attention to fever
It answers 3 hours, to obtain isocyanate group terminal carbamate ester prepolymer (A1)~isocyanic acid of NCO equivalent shown in table 1
Ester group terminal carbamate ester prepolymer (A4), isocyanate group terminal carbamate ester prepolymer (A'1)~isocyanate group
Terminal carbamate ester prepolymer (A'3), isocyanate group terminal carbamate ester prepolymer (A'5)~isocyanate group end
Carbamate prepolymer (A'9).
(synthesis example 5)
The loading table 1 into 5 liters of four round flask for having nitrogen ingress pipe, cooling condenser, thermometer, blender
Shown in polyisocyanate (b), and start to stir.Then, it is packed into polyalcohol (a1) shown in simultaneously mixture table 1, in nitrogen environment
Under with 80 DEG C carry out 3 hours react.Then, make short-chain diol shown in table 1 (a2) anti-at 80 DEG C when paying attention to fever
It answers 3 hours, to obtain NCO equivalent: 371 isocyanate group terminal carbamate ester prepolymer.Then, in order to which oneself is obtained
Isocyanate group terminal carbamate ester prepolymer remove free TDI (unreacted TDI), and then at implementation thin-film distillation
Reason, to obtain NCO equivalent: 435 isocyanate group terminal carbamate ester prepolymer (A5).
(comparing synthesis example 4)
In the same manner as synthesis example 5, NCO equivalent: 380 isocyanate group terminal carbamate ester prepolymer is obtained.Then,
In order to remove free TDI (unreacted TDI) from isocyanate group terminal carbamate ester prepolymer obtained, and then implement
Thin-film distillation processing, to obtain NCO equivalent: 438 isocyanate group terminal carbamate ester prepolymer (A'4).
[table 1]
※ carbamate prepolymer (A5) implements thin-film distillation processing
In 1~table of table 2,
Polytetramethylene glycol 1 (also referred to as " PTMG1000 ") indicates that (number average molecular weight is polytetramethylene glycol
1,000),
Polytetramethylene glycol 2 (also referred to as " PTMG2000 ") indicates that (number average molecular weight is polytetramethylene glycol
2,000),
Polytetramethylene glycol 3 (also referred to as " PTMG650 ") indicates that (number average molecular weight is polytetramethylene glycol
650),
Polyoxypropylene polyol 1 (" EL430 " of the manufacture of Asahi Glass carbamate) indicates polyoxypropylene polyol (hydroxyl
Number is 3, number average molecular weight 430),
Polyoxypropylene polyol 2 (" EL410NE " of the manufacture of Asahi Glass carbamate) indicates polyoxypropylene polyol (hydroxyl
Radix is 4, number average molecular weight 410),
Polyoxypropylene polyol 3 (" EL3030 " of the manufacture of Asahi Glass carbamate) indicates polyoxypropylene polyol (hydroxyl
Radix is 3, number average molecular weight 3,000),
Polyoxypropylene polyol 4 (" EL1030 " of the manufacture of Asahi Glass carbamate) indicates polyoxypropylene polyol (hydroxyl
Radix is 3, number average molecular weight 1,000),
Polyoxybutylene glycols 1 (also referred to as " PBG2000 ") indicate polyoxybutylene glycols (number average molecular weight 2,000),
Polybutylene adipate 1 (also referred to as " BGAA2000 ") indicates the polyester polyols comprising 1,4- butanediol and adipic acid
Alcohol (hydroxyl value 2, number average molecular weight 2,000),
Polybutylene adipate 2 (also referred to as " BGAA1000 ") indicates the polyester polyols comprising 1,4- butanediol and adipic acid
Alcohol (hydroxyl value 2, number average molecular weight 1,000),
Polyisocyanate (T80) indicate TDI (2,4/2,6 ratios of the isomers be 80/20),
Polyisocyanate (T100) indicates 2,4-TDI.
(1~embodiment of embodiment 5,1~comparative example of comparative example 9)
By 1~synthesis example of synthesis example 5, compare synthesis example 1~compare isocyanate group end ammonia obtained in synthesis example 9
Carbamate prepolymer (A1)~isocyanate group terminal carbamate ester prepolymer (A5), isocyanate group terminal carbamate
Ester prepolymer (A'1)~isocyanate group terminal carbamate ester prepolymer (A'9) temperature is adjusted to 80 DEG C, is set as host agent (i).
Secondly, curing agent (MBOCA) to be melted to trip temperature adjusting of going forward side by side at 120 DEG C, it is set as curing agent (ii).In turn, at 35 DEG C
Temperature adjusting is carried out to seasoning liquid shown in table 3, is set as auxiliary agent (iii).
Secondly, after being packed into the host agent (i) of number shown in table 4 into reaction vessel and temperature being adjusted to 80 DEG C, later
35 DEG C of C liquid of number shown in 3~table of input table 4, the curing agent (ii) of 120 DEG C of number shown in input table 4, stands immediately
Stirred 20 seconds using high-speed mixer.Make through mixed host agent (i)/curing agent (ii)/auxiliary agent (iii) mixed liquor 6000
Part flows into temperature and is adjusted in 60 DEG C of 500mm × 500mm × 40mm mold, covers the lid of mold, keeps 1 at 60 DEG C
After hour, ingot shape expansion-molded article is taken out.In turn, ingot shape expansion-molded article obtained is carried out 16 hours at 100 DEG C
After solidify.
Ingot shape expansion-molded article obtained is cut into thickness 1.5mm using slicer, obtains the grinding pad (P1) of sheet
~grinding pad (P5), grinding pad (P'1)~grinding pad (P'8).By the density of grinding pad obtained, hardness, frequency will be measured
It is set as 120 DEG C~200 DEG C of tan δ peak temperature, tan δ value, grinding rate and edge in the Measurement of Dynamic Viscoelasticity of 1Hz
Rounding evaluation result is shown in table in 5.
(6~embodiment of embodiment 8,10~comparative example of comparative example 11)
The temperature of isocyanate group terminal carbamate ester prepolymer shown in table 4 is adjusted to 80 DEG C, is set as host agent
(i).Temperature adjusting is carried out to seasoning liquid shown in table 3 (B1, B2) at 40 DEG C, is set as curing agent (ii).Secondly, holding to reaction
The host agent (i) of number shown in table 4 is packed into device and after temperature is adjusted to 80 DEG C, 40 DEG C of number shown in input table 4
Seasoning liquid (B1, B2) is stirred 20 seconds using high-speed mixer immediately.Make the mixing through mixed host agent (i)/curing agent (ii)
6000 parts of liquid flow into temperature and are adjusted in 60 DEG C of 500mm × 500mm × 40mm mold, the lid of mold are covered, at 60 DEG C
After lower holding 1 hour, ingot shape expansion-molded article is taken out.In turn, 16 are carried out to ingot shape expansion-molded article obtained at 80 DEG C
The rear solidification of hour.
Ingot shape expansion-molded article obtained is cut into thickness 1.5mm using slicer, obtains the grinding pad (P6) of sheet
~grinding pad (P8), grinding pad (P'9)~grinding pad (P'10).By the density of grinding pad obtained, hardness, frequency will be measured
It is set as 120 DEG C~200 DEG C of tan δ peak temperature, tan δ value, grinding rate and edge in the Measurement of Dynamic Viscoelasticity of 1Hz
Rounding evaluation result is shown in table in 5.
Tan δ peak temperature, tan δ value, the measuring method (evaluation method) of grinding rate and edge rounding are as described below.
[measuring method of tan δ peak temperature and tan δ value]
It is analyzed according to following sequences and according to JIS K 7244 using dynamic viscoelastic using the grinding pad of thickness 1.5mm
It measures tan δ peak temperature (also referred to as " loss coefficient peak temperature ") (DEG C), evaluates the viscoplasticity of the grinding pad of 1.5mm thickness.
Using viscoplasticity spectrometer, (model: DMS6100, SII nanosecond science and technology (SII Nano Technology) share has
The manufacture of limit company), under conditions of -100 DEG C~200 DEG C of temperature range, 5 DEG C/min of heating rate, frequency 1Hz, with stretching die
Formula is measured the storage coefficient of elasticity (E') and loss resilience coefficient (E ") of the grinding pad.
In the case where E "/E' is set as tan δ, maximum value will be become in 120 DEG C or more and 200 DEG C range tan δ below
Temperature be set as " tan δ peak temperature (DEG C) ", E "/E' under tan δ peak temperature is set as tan δ value.
Determination condition:
(sample size) 5mm × 60mm × 1.5mm
(span) 20mm
(dependent variable) 0.05%
[evaluation method of grinding rate]
The grinding pad obtained in Examples and Comparative Examples is attached to the single side of double faced adhesive tape, and the platen of grinder is pasted
Another single side for investing double faced adhesive tape measures grinding rate using device below, condition, calculating formula.
Grinder: FAM 18GPAW (wound skill (Speed Fam) company manufactures platen diameter=457m water-cooled)
Grinding condition:
(pad pre-treatment) carries out finishing processing (planarization of pad and dressing) using diamond truer (#100), until with
The heading line off that red pencil is described on pad surface with the interval 2cm in length and breadth.Water supply is 200ml/min
(grinding object) 4 inches of silicon single crystal wafer thickness: 540 μm
(silicon wafer method for supporting) ceramic block/(grinder is cooling for micro- porous waste pad (suede pad) (water absorption) silicon wafer
Water) 20 DEG C
" N6501 " dilution of this (Nitta Haas) limited liability company of (slurry) colloidal silica solution secondary rainbow Daxad manufacture
20 times
(slurry flow) 100ml/min (circulating)
(platen revolving speed) 50rpm (involves rotary)
(grinding pressure) 30kPa
(milling time) 20 minutes
(grinding rate) is calculated according to the weight difference of the polyurethanes grinding pad of grinding front and back.
That is, grinding rate (μm/min)=(weight of the silicon wafer after weight (the g)-grinding of the silicon wafer before grinding
(g)) × 10000/ (density (g/cm of monocrystalline silicon3Area (the cm of) × silicon wafer2) × milling time (min))
Density=2.329g/cm of monocrystalline silicon3
Area=20.4cm of silicon wafer2
[evaluation method of edge rounding]
After grinding rate evaluation, carry out refinishing processing in 1 hour using diamond truer (#100).Later,
It is ground body instead of new, is ground under following grinding conditions.Spectral interference laser displacement gauge is utilized after grinding
Measurement is ground body height.
Grinding condition:
(grinding object) 4 inches of silicon single crystal wafer thickness: 540 μm
(silicon wafer method for supporting) ceramic block/wax/silicon wafer
20 DEG C of (grinder cooling water)
" N6501 " dilution of this (Nitta Haas) limited liability company of (slurry) colloidal silica solution secondary rainbow Daxad manufacture
20 times
(slurry flow) 100ml/min (circulating)
(platen revolving speed) 50rpm (involves rotary)
(grinding pressure) 30kPa
(milling time) 60 minutes
Laser displacement gauge condition:
(machine) SI-F10/KS-1100 (manufacture of Keyemce (Keyence) limited liability company)
(measuring point) 101 × 101=10201 point (is measured until being attached at ceramic block)
(analysis software) KS analyzer (Keyemce (Keyence) limited liability company)
(edge rounding evaluates place) passes through the line segment (diameter) in silicon wafer center portion
(evaluation of edge rounding) is evaluated by the height at maximum height-position 2mm from left end.
[table 3]
In table 3,
Polyoxypropylene polyol 3 (" EL3030 " of the manufacture of Asahi Glass carbamate) indicates polyoxypropylene polyol (hydroxyl
Radix is 3, number average molecular weight 3,000),
Aromatic series amino chlorphenyl methane mixture indicates to include the chloro- 4,4- tetramethyl triaminotriphenyl methane NH2 (MBOCA) of 3,3'- bis-
With the mixture of its polymer and polyether polyol (Ahew: 189),
Ka Te (TOYOCAT) ET in Dongyang is manufactured by Tosoh limited liability company, indicates bis- (dimethyl aminoethyl) ethers
(70%) with the mixture of dipropylene glycol (30%),
SH-193 is manufactured by beautiful DOW CORNING (the Toray Dow Corning) limited liability company in east, indicates silicone surfactant.
[table 4]
In table 4, MBOCA indicates chloro- 4, the 4- tetramethyl triaminotriphenyl methane NH2 of 3,3'- bis-.
[table 5]
The grinding pad of 1~embodiment of embodiment 8 is grinding pad of the invention, has high grinding rate, and can get Gao Ping
The grinding charge of smooth property excellent (edge rounding is few).
1~comparative example of comparative example 3, comparative example 5, the tan δ value of comparative example 7 are small, comparative example 4, comparative example 7, comparative example 9, ratio
It is low compared with the tan δ peak temperature of example 10, the containing ratio of polytetramethylene glycol contained in the polyol component (a) of comparative example 6
Low, comparative example 8 cannot be considered in terms of high grinding rate and high flatness without tan δ peak temperature.
In addition, the section of grinding pad of the invention is as shown in Figure 1, fluff, and confirm specific viscous in the presence of having
The fine domain of elasticity.On the other hand, the section of the grinding pad of comparative example is as shown in Fig. 2, smooth.Fig. 3 is the grinding of embodiment 3
The Measurement of Dynamic Viscoelasticity chart of pad.Fig. 4 is the silicon using spectral interference laser displacement gauge to the grinding pad grinding through embodiment 3
The distribution map for the height that the surface of chip is measured.Fig. 5 is the Measurement of Dynamic Viscoelasticity chart of the grinding pad of comparative example 7.Fig. 6
It is the height being measured using surface of the spectral interference laser displacement gauge to the silicon wafer of the grinding pad grinding through comparative example 7
Distribution map.
Claims (7)
1. a kind of grinding pad, for the amino containing the host agent (i) comprising carbamate prepolymer (A) and curing agent (ii)
The hardening thing of formate resin composition, the grinding pad are characterized in that:
The carbamate prepolymer (A) is the polyalcohol (a1) and molecular weight less than 300 for being 300 or more comprising molecular weight
The polyol component (a) of short-chain diol (a2) reacted with polyisocyanate (b) after product, and end have isocyanates
Base,
The polyol component (a) includes polytetramethylene glycol with 40 mass % or more and 90 mass % containing ratios below,
The containing ratio of the short-chain diol (a2) is 1 mass % or more in the polyol component (a),
The hardening thing will measure in the Measurement of Dynamic Viscoelasticity that frequency is set as 1Hz, below at 120 DEG C or more and 200 DEG C
With the peak value of tan δ in range, and
Described 120 DEG C or more and the tan δ in 200 DEG C of ranges below of peak value is 0.18 or more.
2. grinding pad according to claim 1, wherein
The short-chain diol (a2) of the molecular weight less than 300 is diethylene glycol.
3. grinding pad according to claim 1 or 2, wherein
The polyalcohol (a1) is polytetramethylene glycol, and in the polyol component (a), polytetramethylene glycol contains
Rate is 60 mass % or more.
4. grinding pad according to any one of claim 1 to 3, wherein
The number average molecular weight of the polyalcohol (a1) is 1,100 or more.
5. grinding pad according to any one of claim 1 to 4, wherein
The polyisocyanate (b) is aromatic poly-isocyanate.
6. grinding pad according to any one of claim 1 to 5, wherein
The curing agent (ii) is aromatic amines compound.
7. a kind of grinding pad urethane resin compositions, to contain the host agent comprising carbamate prepolymer (A)
(i), with the urethane resin compositions of curing agent (ii), the feature of the grinding pad urethane resin compositions
It is:
The carbamate prepolymer (A) is less than containing the polyalcohol (a1) and molecular weight for being 300 or more comprising molecular weight
Product after the reacting of the polyol component (a) of 300 short-chain diol (a2) and the composition of polyisocyanate (b), and
End has isocyanate group,
The short-chain diol is diethylene glycol,
In the polyol component (a), the containing ratio of the short-chain diol (a2) is 1 mass % or more,
The polyol component (a) includes polytetramethylene glycol with 40 mass % or more and 90 mass % containing ratios below,
The number average molecular weight of the polyalcohol (a1) is 1,100 or more.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-249395 | 2017-12-26 | ||
| JP2017249395 | 2017-12-26 |
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| CN109957088A true CN109957088A (en) | 2019-07-02 |
| CN109957088B CN109957088B (en) | 2022-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811581083.2A Active CN109957088B (en) | 2017-12-26 | 2018-12-24 | Polishing pad |
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| JP (1) | JP7259311B2 (en) |
| CN (1) | CN109957088B (en) |
| TW (1) | TWI787420B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265138A (en) * | 2020-02-14 | 2021-08-17 | Dic株式会社 | Urethane resin composition and method for producing porous body |
| CN114346894A (en) * | 2020-09-29 | 2022-04-15 | Skc索密思株式会社 | Polishing pad and method for manufacturing semiconductor device using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102287235B1 (en) * | 2019-10-30 | 2021-08-06 | 에스케이씨솔믹스 주식회사 | Polishing pad with controlled crosslinking and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2019116616A (en) | 2019-07-18 |
| TW201930382A (en) | 2019-08-01 |
| JP7259311B2 (en) | 2023-04-18 |
| TWI787420B (en) | 2022-12-21 |
| CN109957088B (en) | 2022-04-26 |
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