CN105008614B - The manufacture method of hard sheet and hard sheet - Google Patents
The manufacture method of hard sheet and hard sheet Download PDFInfo
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- CN105008614B CN105008614B CN201480007963.2A CN201480007963A CN105008614B CN 105008614 B CN105008614 B CN 105008614B CN 201480007963 A CN201480007963 A CN 201480007963A CN 105008614 B CN105008614 B CN 105008614B
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- hardness
- hard sheet
- fibre
- macromolecular elastomer
- superfine fibre
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/22—Lapping pads for working plane surfaces characterised by a multi-layered structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/4383—Composite fibres sea-island
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/08—Cleaning articles
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Nonwoven Fabrics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The present invention provides a kind of hard sheet, the non-woven fabrics that it contains superfine fibre and the macromolecular elastomer being imparted in non-woven fabrics, the JIS D hardness of the hard sheet is more than 45, to the section of thickness direction equably 3 decile, and from any one face side by 3 deciles after each layer be set to the first top layer successively, when intermediate layer and the second top layer, determine the JIS D hardness of respective any 3 points of 6 points of totals in first top layer and the intermediate layer, use the D hardness for amounting at 6 points, the R% calculated by following formula is 0~20%, and make the total content of the ion that the pH of water changes be 400 μ g/cm3Hereinafter, wherein R (%)=(D maximum hardness-D hardness minimum value)/D hardness average value × 100.
Description
Technical field
The present invention relates to a kind of hard sheet, it is used preferably as the polishing layer of polishing pad, specifically, preferably as
For being polished to semiconductor wafer, semiconductor devices, silicon wafer, hard disk, glass substrate, optical goods or various metals etc.
The polishing layer of polishing pad use.
Background technology
Integrated circuit formed in semiconductor wafer is highly integrated and multilayer wiring.For such semiconductor die
Piece, it is desirable to flatness high.
As the polishing method for polishing semiconductor wafer, it is known to chemically-mechanicapolish polish (CMP).CMP is while drop
Plus polishing slurries (below, also referred to as slurry) containing abrasive grains, while being carried out to being polished substrate surface with polishing pad
The method of polishing.
Following patent documents 1~4 disclose the polishing being made up of the foam polymer precursor with hole-closing structure for CMP
Pad.Bi-component curable polyurethane is carried out pouring foaming formation and manufactured by foam polymer precursor.By foam polymer precursor
Its rigidity of the polishing pad of manufacture is more padded than the polishing of non-woven fabric type described later.It is therefore preferable that for requiring the half of flatness high
The polishing of conductor chip.
The rigidity of the polishing pad formed by foam polymer precursor is high.Therefore, the convex portion for being polished base material is optionally applied
Loading.As a result, available polishing velocity higher.But, burnishing surface is present in the abrasive grains that there occurs cohesion
In the case of, load optionally will be put on the abrasive grains of cohesion.Therefore, cut is easily produced on burnishing surface.It is special
When not being that the advanced low-k materials weak to base material or interfacial adhesion with copper wiring are polished, cut is easily produced
Or interface peel (referring for example to non-patent literature 1).In addition, in pouring foaming shaping, because macromolecular elastomer is easy not
Equably foam, therefore, polishing velocity when being polished flatness and the polishing of base material easily becomes uneven.And then, pass through
Abrasive grains or buffing are lentamente jammed in the closed pore of foam polymer precursor, and polishing velocity is slowly reduced.
Following patent documents 5~14 disclose a kind of polishing pad of non-woven fabric type, and it is the poly- ammonia of porous for solidifying wet type
Ester is infiltrated in obtained from non-woven fabrics.Because the flexibility of non-woven fabric type polishing pad is excellent, therefore polishing pad is easily deformed.Cause
This, it is difficult to the abrasive grains to condensing in burnishing surface optionally apply load, therefore are not likely to produce cut.But, due to nothing
Spin cloth type polishing pad soft, therefore, polishing velocity is low.Further, since non-woven fabric type polishing pad follows the surface for being polished base material
Shape and deform, therefore planarization performance is low, and the planarization performance is to make to be polished the flat characteristic of base material.
In addition, following patent documents 15~18 disclose a kind of non-woven fabrics containing superfine fibre with height planarization property
The polishing pad of energy.Such as patent document 15 discloses a kind of polishing pad formed by tablet, and it makes with polyurethane as principal component
Macromolecular elastomer be infiltrated in the nonwoven of the polyester superfine fibre beam obvolvent that average fineness is 0.0001~0.01dtex
In cloth.The document discloses such polishing pad compared with existing polishing pad, high-precision polishing is realized.
In the polishing pad of the non-woven fabrics of common use superfine fibre, it is widely used for entering the superfine fibre of chopped fiber
Non-woven fabrics obtained from the treatment of hand-manipulating of needle pierced holes.Such non-woven fabrics is because apparent density is low and voidage is high, therefore rigidity is low.
Therefore, because follow the surface configuration of burnishing surface and deform, therefore planarization performance is low.
Patent document 19 discloses a kind of polishing pad, and it contains the fiber pseudoconjugant formed by the fibre bundle of superfine single fiber
And macromolecular elastomer, a part for macromolecular elastomer is present in the inside of fibre bundle, and superfine single fiber has carried out boundling, removed
The volume ratio for going to the part in space is 55~95% scope.
In addition, patent document 20 discloses a kind of polishing pad, it is throwing in the polishing pad with polishing layer and basalis
Containing the intermediate layer that water absorption rate is less than 1% between photosphere and basalis, the difference of the D hardness of polishing layer and the D hardness in intermediate layer
It is less than 20.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2000-178374 publications
Patent document 2:Japanese Unexamined Patent Publication 2000-248034 publications
Patent document 3:Japanese Unexamined Patent Publication 2001-89548 publications
Patent document 4:Japanese Unexamined Patent Publication 11-322878 publications
Patent document 5:Japanese Unexamined Patent Publication 2002-9026 publications
Patent document 6:Japanese Unexamined Patent Publication 11-99479 publications
Patent document 7:Japanese Unexamined Patent Publication 2005-212055 publications
Patent document 8:Japanese Unexamined Patent Publication 3-234475 publications
Patent document 9:Japanese Unexamined Patent Publication 10-128674 publications
Patent document 10:Japanese Unexamined Patent Publication 2004-311731 publications
Patent document 11:Japanese Unexamined Patent Publication 10-225864 publications
Patent document 12:Japanese Unexamined Patent Application Publication 2005-518286 publications
Patent document 13:Japanese Unexamined Patent Publication 2003-201676 publications
Patent document 14:Japanese Unexamined Patent Publication 2005-334997 publications
Patent document 15:Japanese Unexamined Patent Publication 2007-54910 publications
Patent document 16:Japanese Unexamined Patent Publication 2003-170347 publications
Patent document 17:Japanese Unexamined Patent Publication 2004-130395 publications
Patent document 18:Japanese Unexamined Patent Publication 2002-172555 publications
Patent document 19:Japanese Unexamined Patent Publication 2008-207323 publications
Patent document 20:Japanese Unexamined Patent Publication 2011-200984 publications
Non-patent literature
Non-patent literature 1:" science (CMP サ イ エ Application ス) of CMP ", science forum of Co., Ltd. (Co., Ltd. サ
イ エ Application ス フ ォ ー ラ system), August in 1997 20 days, p.113~119
The content of the invention
The invention problem to be solved
The present invention provides a kind of polishing pad that rheological parameters' change with time is difficult with polishing velocity and polishing velocity high.Solution is asked
The method of topic
One aspect of the present invention is related to a kind of hard sheet, and it is included with the superfine of 0.0001~0.5dtex fiber numbers
The non-woven fabrics of fiber and the macromolecular elastomer being imparted in non-woven fabrics, the JIS-D hardness of the hard sheet is more than 45, to thickness
The section for spending direction equably carries out 3 deciles, and from any one face side by 3 deciles after each layer be set to the first table successively
When layer, intermediate layer and the second top layer, the JIS-D hardness of respective any 3 points of 6 points of totals in the first top layer and intermediate layer is determined, made
With the D hardness for amounting at 6 points, the R% calculated by following formula is 0~20%,
R (%)=(D maximum hardness-D hardness minimum value)/D hardness average value × 100,
Also, the total content for making the ion that the pH of water changes is 400 μ g/cm3Below.
In addition, another aspect of the present invention is related to a kind of polishing pad, it possesses above-mentioned hard sheet as polishing layer.
In addition, another aspect of the present invention is related to a kind of manufacture method of hard sheet, the method includes following operation:
(1) operation that superfine fibre occurs the long stapled fiber obvolvent piece of fiber type is prepared, the superfine fibre occurs
The long stapled fiber obvolvent piece of fiber type can be processed by superfine fibre and form the pole with below 0.5dtex fiber numbers
The non-woven fabrics of fine fibre, and the apparent density of the non-woven fabrics is 0.35g/cm3More than;
(2) first emulsion containing gelating agent and macromolecular elastomer is impregnated in fiber obvolvent piece, then make
One emulsion gel, then be thermally dried, the operation for thus solidifying macromolecular elastomer, the gelating agent contains and makes water
The ions that change of pH;
(3) superfine fibre treatment is carried out by there is fiber type to superfine fibre, is formed and containing non-woven fabrics and macromolecule
The operation of the first complex of elastomer;
(4) second emulsion containing gelating agent and macromolecular elastomer is impregnated in the first complex, then added
Heated drying, thus solidifies macromolecular elastomer, so that the operation of the second complex is formed, by second complex in thickness
Direction equably carries out 3 deciles, and from any one face side by 3 deciles after each layer be set to the first top layer, centre successively
When layer and the second top layer, the difference of the voidage in the first top layer and intermediate layer is less than 5%;
(5) the second complex is washed so that the total content of ion is 400 μ g/cm3Hereinafter, so as to obtain hard
The operation of sheet material;And
(6) in order that the case hardness of hard sheet is JIS-D hardness more than 45, will be answered selected from the first complex, second
At least one of fit and hard sheet carries out the operation of hot pressing.
The effect of invention
The present invention can obtain for obtain with polishing velocity and polishing velocity high not The book of Changes when the polishing pad that changes
Hard sheet.
Brief description of the drawings
[Fig. 1] is a constructed profile for implementation method of hard sheet.
Symbol description
1 non-woven fabrics
1a superfine fibres
1b fibre bundles
2 macromolecular elastomers
3 first top layers
4 intermediate layers
5 second top layers
Specific embodiment
Hereinafter, an implementation method to hard sheet of the invention is described in detail.Fig. 1 is the hard of present embodiment
The constructed profile of matter sheet material 10.In Fig. 1, part thereof of enlarged diagram is shown in the lump in the region surrounded with circle.
As shown in figure 1, hard of the hard sheet 10 comprising non-woven fabrics 1 and the macromolecular elastomer 2 being imparted in non-woven fabrics 1
Sheet material, the non-woven fabrics 1 is the pseudoconjugant of superfine fibre 1a.For hard sheet 10, its JIS-D hardness is more than 45,
Equably carry out 3 deciles in thickness direction, and from face side by 3 deciles after each layer successively the first top layer 3, intermediate layer 4 and
During the second top layer 5, each any 3 points JIS-D hardness for amounting at 6 points is determined in the first top layer 3 and intermediate layer 4, using amounting at 6 points
D hardness, the R% calculated by following formula is 0~20%,
The D hardness average value of R (%)=(the D hardness minimum value in the point of D maximum hardness -6 in 6 points)/6 points ×
100。
Additionally, it is preferred that the respective any 3 points JIS-D hardness for amounting at 6 points in determining the second top layer 5 and intermediate layer 4, using total
6 points of D hardness is counted, the R% calculated by above formula is also 0~20%.And, make what the pH of water changed in the hard sheet
The total content of ion is 400 μ g/cm3Below.
In hard sheet 10, the superfine fibre 1a for forming non-woven fabrics 1 forms fibre bundle 1b, and the fibre bundle 1b is many
Obtained from root superfine fibre 1a bunchys.In addition, multiple fibre bundle 1b is bonded by macromolecular elastomer 2 to each other.It is preferred that many
More than half of individual fibre bundle 1b is bonded by macromolecular elastomer 2.And then, form the superfine fibre 1a of fibre bundle 1b to each other
Bonded also by macromolecular elastomer 2.It is preferred that more than half of superfine fibre 1a is bonded by macromolecular elastomer 2.It is such
The complex of the non-woven fabrics containing non-woven fabrics 1 and macromolecular elastomer 2 and macromolecular elastomer is that space is few, hardness is high and densification
Hard sheet 10.Stiffening effect and the high fill-ratio of hard sheet that such hard sheet 10 is caused due to fibre bundle 1b
(i.e. low porosity), therefore with high rigidity.
Hard sheet 10 contains the non-woven fabrics 1 of the superfine fibre for being formed with fibre bundle.It is present in the non-woven fabrics on surface
Fibre bundle fibrillation or fibrillation in polishing.As a result, exposing the superfine fibre of high microsteping density in burnishing surface.The pole exposed
Fine fibre is contacted with area wide with base material is polished, furthermore it is possible to keep substantial amounts of slurries.And then, due to the superfine fibre for exposing
Dimension makes the surface of polishing pad soften, therefore, load is optionally applied to the condensation product of abrasive grains and is suppressed.As a result,
The generation of cut can be suppressed.
In addition, the JIS-D hardness of hard sheet 10 is more than 45, hardness is adjusted to uniform in thickness direction so that survey
The respective any 3 points JIS-D hardness for amounting at 6 points in fixed first top layer 3 and intermediate layer 2, and using 6 points of D hardness is amounted to, under
The R% that formula is calculated is 0~20%,
R (%)=(D maximum hardness-D hardness minimum value)/D hardness average value × 100.
Additionally, it is preferred that hardness is adjusted into uniform in thickness direction so that in the second top layer 5 of measure and intermediate layer 2 each
Any 3 points JIS-D hardness for amounting at 6 points, and the R% calculated using the D hardness for amounting at 6 points is also 0~20%.So,
By being adjusted so that hardness reaches uniformly, the polishing of homogeneous can be carried out.
And, the total content that hard sheet 10 is adjusted to the ion for making the pH of water change is 400 μ g/cm3Below.
In order to equably assign macromolecular elastomer in thickness direction as described above, in general, gelating agent can be used.Hard piece
Contained ion can change the pH of slurries in polishing sometimes in material.In the case where the pH of slurries there occurs change, easily
Polishing velocity is reduced, or easily condenses abrasive grains.In this case, by wash etc. make it is contained in hard sheet
Ionic compound reduction, it is possible thereby to suppress the reduction of polishing velocity produced because the pH of slurries changes.Need explanation
, the ion for making the pH of water change refers to all ions for changing pH when water is dissolved in.
As described in detail below, the hard sheet of present embodiment is by the fine and close non-woven fabrics in superfine fibre
Thickness direction it is uniform and with containing ratio high impregnation assign macromolecular elastomer and manufacture.In addition, in such hard sheet
In manufacture, in order to be assigned in non-woven fabrics macromolecular elastomer impregnation with containing ratio high, preferably use and contain gelating agent
The emulsion of macromolecular elastomer.And, in the manufacturing process of hard sheet, can be by carrying out washing so that in gelating agent
The contained ion total content for making the pH of water change is 400 μ g/cm3Hereinafter manufacture.
Hereinafter, each key element to the hard sheet of present embodiment is illustrated in further detail.
Non-woven fabrics in present embodiment is formed by superfine fibre, and superfine fibre is preferably formed as fibre bundle.
Superfine fibre has the fiber number of 0.0001~0.5dtex, the preferably fiber number with 0.001~0.01dtex.In pole
Less than in the case of 0.0001dtex, in polishing, the superfine fibre of near surface is difficult to fully fibrillation to the fiber number of fine fibre,
As a result, the reduction of slurries maintenance dose.In the case where the fiber number of superfine fibre is more than 0.5dtex, speed is polished because surface is excessively thick
Degree is reduced, and abrasive grains easily condense upon the surface of superfine fibre.
Superfine fibre is long fibre (long filament), and specifically, preferably average fiber length is more than 100mm, further excellent
Elect more than 200mm as.The upper limit of average fiber length is not particularly limited, as long as being not switched off in obvolvent operation described later,
Several meters, hundreds of meters, the fiber of a few kms or its above length can also for example be included.The long fibre of superfine fibre is by making fiber
Density improves to improve the rigidity of hard sheet.In addition, long fibre is difficult for drop-off in polishing.It should be noted that superfine fibre
The chopped fiber of dimension is difficult to improve fibre density, it is impossible to obtain rigidity hard sheet high.In addition, chopped fiber easily takes off in polishing
Fall.
Form the superfine fibre preferably many superfine fibre bunchys of non-woven fabrics and form fibre bundle.As being present in thickness side
To section fibre bundle average cross-section, especially from from the aspect of can obtain rigidity hard sheet high, preferably 80 μ
m2More than, more preferably 100 μm2More than, particularly preferably 120 μm2More than.
In addition, for being present in the fibre bundle in thickness direction section, relative to the fibre in the section of given thickness direction
Total beam number of beam is tieed up, preferably with 40 μm2The fibre bundle of above sectional area is more than 25%.Particularly it is used to require flatness high
Silicon wafer purposes, semiconductor wafer purposes, the polishing pad of semiconductor equipment purposes in the case of, with 40 μm2With upper section
Long-pending fibre bundle is preferably more than 40%, more preferably more than 50%, particularly preferably 100%.40μm2Fiber above
In the case that the ratio of beam is too low, there is the tendency of polishing velocity reduction or planarization performance step-down.
In addition, in the hard sheet of present embodiment, the Shu Mi of the fibre bundle of the unit area in the section of thickness direction
Degree is preferably 600 beams/mm2Above, more preferably 1000 beams/mm2More than, and preferably 4000 beams/mm2Below, further
Preferably 3000 beams/mm2Below.In the case of such Shu Midu, in polishing, the fibre bundle fibrillation or fibrillation on surface
Change and form many superfine fibres, improve the maintenance dose of slurries.In addition, by fibre bundle fibrillation or fibrillation, burnishing surface
Surface soften and suppress the generation of cut.In the case where Shu Midu is too low, there is the fibre of the superfine fibre for being formed in surface
The tendency of dimension density step-down, polishing velocity reduction or planarization performance reduction.In addition, in the too high situation of the density of fibre bundle
Under, there is the tendency of maintenance dose or the polishing velocity reduction of slurries because of surface excessively densification.It should be noted that in this implementation
In the hard sheet of mode, from from the aspect of improving polishing stable, preferably in thickness direction and the density of face direction fibre bundle
It is uneven small.
Superfine fibre is more than 50 DEG C preferably by glass transition temperature (Tg), further preferred by glass transition temperature
(Tg) it is that more than 60 DEG C of thermoplastic resin is formed.In the case where the Tg of thermoplastic resin is too low, in polishing, rigidity is not
Foot, planarization performance reduction, in addition, rigidity through when reduce and exist polishing stable or polishing uniformity reduction tendency.Tg
The upper limit be not particularly limited, but industry manufacture on be preferably 300 DEG C, more preferably 150 DEG C.It should be noted that
Due to turning into water suction state in polishing process, therefore, further preferably after treatment in 50 DEG C of warm water, in the shape of moistening
It is more than 50 DEG C that the Tg for obtaining is determined under state.In addition, the water absorption rate of thermoplastic resin is preferably below 4 mass %, it is further excellent
Elect as below 2 mass %.In the case where water absorption rate is more than 4 mass %, in polishing, because lentamente absorbing the moisture in slurries
And make rigidity through when reduce.In this case, planarization performance easily through when reduce polishing velocity or polishing it is equal
Even property easily changes.Water absorption rate is preferably 0~2 mass %.
As the specific example of thermoplastic resin, can enumerate for example:(PET, Tg are 77 to polyethylene terephthalate
DEG C, the mass % of water absorption rate 1), isophthalate modified polyethylene terephthalate (Tg be 67~77 DEG C, the matter of water absorption rate 1
Amount %), the modified polyethylene terephthalate of sulfoisophthalic acid (Tg is 67~77 DEG C, the mass % of water absorption rate 1~4),
(Tg is 124 DEG C, water suction for PBN (Tg is 85 DEG C, the mass % of water absorption rate 1), PEN
The mass % of rate 1) etc. aromatic polyester-based resin;Terephthalic acid (TPA) and nonanediol and methyl ethohexadiol copolymer nylon (Tg is 125~
140 DEG C, the mass % of water absorption rate 1~4) etc. semiaromatic polyamide composition resinoid etc..These materials can be used individually, also may be used
To be applied in combination two or more.Wherein, from from the aspect of can also fully keep rigidity, water resistance and wear resistance, preferably gather
Ethylene glycol terephthalate (PET), isophthalate modified polyethylene terephthalate, poly- naphthalenedicarboxylic acid butanediol
Ester, PEN.The modified PET such as particularly PET and isophthalate modified PET, by fabric of island-in-sea type described later
The netted obvolvent sheet material of composite fibre is significantly crispaturaed in forming the humid heat treatment operation of superfine fibre, therefore, from can be with shape
Into fine and close and highdensity fiber pseudoconjugant, easily improve the rigidity of hard sheet and be not likely to produce moisture and cause in polishing
Rheological parameters' change with time etc. from the aspect of be preferred.
In addition, not damaging in the range of effect of the present invention, can contain formed by other thermoplastic resins as needed
Superfine fibre.As such thermoplastic resin, PLA, polybutylene terephthalate (PBT) can be applied in combination, gather right
It is phthalic acid hexylene glycol ester, polydiethylene glycol succinate, polybutylene succinate, poly- butanedioic acid tetramethylene adipate, poly-
The aromatic polyesters such as butyric ester-poly- hydroxyl pentanoate copolymer or aliphatic polyester and its copolymer;Nylon 6, nylon66 fiber,
Amorphous nylon and its copolymers such as nylon 10, nylon 11, nylon 12;The TPOs such as polyethylene, polypropylene;Contain 25~70
The modified polyvinylalcohol of mole % ethylene units;The elastomers such as polyurethane elastomer, nylon-type elastomer, polyester elastomer
Deng.
Hard sheet includes the macromolecular elastomer being imparted in the non-woven fabrics of superfine fibre.
As the specific example of macromolecular elastomer, can enumerate for example:Polyurethane, polyamide-based elastomer, (methyl) third
Olefin(e) acid esters elastomer, (methyl) Acrylate-styrene bipolymer class elastomer, (methyl) acrylic ester-acrylonitrile class elastomer,
(methyl) acrylate-olefin class elastomer, (methyl) acrylate-(hydrogenation) isoprenoid elastomer, (methyl) propylene
Acid esters-butadiene type elastomer, styrene-butadiene class elastomer, styrene-hydrogenated isoprene class elastomer, acrylonitrile-
Butadiene type elastomer, acrylonitrile-butadiene-styrene (ABS) class elastomer, vinyl acetate esters elastomer, (methyl) acrylic acid
Ester-vinyl acetate esters elastomer, ethane-acetic acid ethyenyl ester class elastomer, ethylene-olefin class elastomer, polysiloxane-based bullet
Gonosome, fluoroelastomer and polyester elastomer etc..
Macromolecular elastomer is preferably non-porous state.It should be noted that non-porous state refers to substantially without porous
Shape or spongy macromolecular elastomer have as space (closed pore).For example, referring to not such as to make solvent polyurethane
Such macromolecular elastomer with many closed pores obtained from solidification.
In the case where macromolecular elastomer is non-porous state, polishing stable high is can obtain, it is not easy to wear, in addition, slurry
Liquid residue or polishing pad chip are difficult to remain in space.Therefore, it can keep polishing velocity high for a long time.Further, since right
It is high in the cementability of superfine fibre, therefore, it is difficult to cause coming off for fiber.Further, since high rigidity is can obtain, therefore planarization
Excellent performance.
The water absorption rate of macromolecular elastomer is preferably 0.5~8 mass %, more preferably 1~6 mass %.Macromolecule
In the case that the water absorption rate of elastomer is too low, for the wettability reduction of slurries.As a result, there is polishing velocity, polishing uniformly
Property, polishing stable reduction or abrasive grains easily cohesion tendency.In the situation that the water absorption rate of macromolecular elastomer is too high
Under, polishing when hard sheet rigidity through when reduce, planarization performance reduction.In addition, polishing velocity or polishing uniformity
It is susceptible to change.It should be noted that the water absorption rate of macromolecular elastomer refers to by the macromolecular elastomer after dried process
Water absorption rate of film immersion when making its saturation swelling in the water of room temperature.It should be noted that containing two or more macromolecule
In the case of elastomer, managed in the form of the value sum obtained by mass fraction is multiplied by the water absorption rate of each macromolecular elastomer
By calculating.
The water absorption rate of macromolecular elastomer can be adjusted by importing hydrophilic functional group or the adjustment degree of cross linking
It is whole.As hydrophilic functional group, can enumerate for example:The PAG base of carboxyl, sulfonic group and carbon number below 3
Deng.Hydrophilic radical can be imported by the way that the monomer with hydrophilic radical is carried out into copolymerization.As with hydrophilic radical
Monomeric unit copolymerization ratios, preferably 0.1~20 mass %, more preferably 0.5~10 mass %.
Storage modulus [E ' (150 DEG C, dry (dry))] of the macromolecular elastomer at 150 DEG C be preferably 0.1~
100MPa, more preferably 1~80MPa.The storage modulus of macromolecular elastomer can be adjusted by adjusting the degree of cross linking
It is whole.It should be noted that in the case of containing two or more macromolecular elastomer, each high polymer elastic is multiplied by with mass fraction
The form of the value sum obtained by [E ' (150 DEG C, dry (dry))] of body carries out theoretical calculation.
Macromolecular elastomer may be used singly or in combination of two or more.Wherein, glued to superfine fibre
From the aspect of knot property is excellent, preferred polyurethane.
The superfine fibre of fibre bundle is preferably formed as by macromolecular elastomer boundling, the half of further preferred superfine fibre
Radical above passes through macromolecular elastomer boundling.
Additionally, it is preferred that multiple fibre bundles are bonded by being present in the macromolecular elastomer on the outside of fibre bundle to each other, enter one
The beam for walking more than half of preferred fibre bundle is bonded by macromolecular elastomer and existed with bulk.Glued to each other by fibre bundle
Tie and improve the morphological stability of hard sheet, so as to improve polishing stable.By with macromolecular elastomer by superfine fibre
Boundling or fibre bundle is bonded to one another, can obtain the uniform and high hard sheet of hardness.
In the case where there is no boundling in the superfine fibre for forming fibre bundle, because superfine fibre carries flexibility, therefore
It is difficult to obtain planarization performance high.In addition, superfine fibre easily comes off in polishing, abrasive grains are condensed in the fiber for coming off
Above easily produce cut.Superfine fibre refers to by macromolecular elastomer boundling:It is present in the superfine fibre inside fibre bundle
It is present in the bonding of the macromolecular elastomer inside fibre bundle and is bound.
The ratio (non-woven fabrics/macromolecular elastomer) of non-woven fabrics and macromolecular elastomer in hard sheet is by quality ratio
Preferably 90/10~55/45, more preferably 85/15~65/35.It is upper in the ratio of non-woven fabrics and macromolecular elastomer
In the case of stating scope, the rigidity of hard sheet is easily improved.Furthermore it is possible to fully improve be exposed to hard sheet surface
The density of superfine fibre.As a result, polishing stable, polishing velocity and planarization performance can be improved fully.
From from the aspect of keeping rigidity high, the apparent density of hard sheet is preferably 0.5~1.2g/cm3, it is further excellent
Elect 0.6~1.2g/cm as3。
The JIS-D hardness of the hard sheet of present embodiment is more than 45, and 3 are equably carried out in the section of thickness direction
Decile, and from any one face side by 3 deciles after each layer be set to the first top layer, intermediate layer and the second top layer successively when,
The JIS-D hardness of respective any 3 points of 6 points of totals in the first top layer and intermediate layer is determined, using the D hardness for amounting at 6 points, by following formula
The R% for calculating is 0~20%,
Average value × 100 of the D hardness of R (%)=(D maximum hardness-D hardness minimum value)/6 points.
Additionally, it is preferred that the respective any 3 points JIS-D hardness for amounting at 6 points in determining the second top layer and intermediate layer, uses total
6 points of D hardness, the R% calculated by above formula is also 0~20%.
The JIS-D hardness of hard sheet is more than 45, preferably 45~75, more preferably 50~70.By by
The hardness on one top layer is adjusted to JIS-D hardness and is calculated as more than 45, can obtain planarization performance high.In JIS-D excessive high hardness
In the case of, easily produce cut.It should be noted that due to making the superfine fibre of high microsteping density be exposed to surface, therefore,
Although the hard sheet of present embodiment is hard, surface is soft.Therefore, it is not likely to produce cut.
The JIS-D hardness of respective any 3 points of 6 points of totals in the first top layer and intermediate layer is determined, it is hard using the D for amounting at 6 points
Degree, the R% calculated by above-mentioned formula is 0~20%, preferably 0~15%.R% in the first top layer and intermediate layer is above-mentioned
In the case of scope, in the case of as polishing pad, the change of the polishing velocity in the first top layer and intermediate layer diminishes, and can obtain
The polishing performance of stabilization.In the case where R% is more than 20%, the change increase of polishing velocity in polishing, it is impossible to obtain stabilization
Polishing performance.It should be noted that the arbitrary point for determining JIS-D hardness refers to:Which point measure in its layer is to appoint
Meaning, no matter it is measured at which point, R% is 0~20%.In this case, due to not only in thickness direction and
And will not also make hardness uneven in width, therefore, polishing velocity is also uniform in the in-plane direction, thus, can obtain stabilization
Polishing performance.Similarly, the JIS-D hardness of respective any 3 points of 6 points of totals in the second top layer and intermediate layer is determined, using total
6 points of D hardness is counted, the R% calculated by above-mentioned formula is 0~20%, more preferably 0~15%.
For the hard sheet of present embodiment, the total content for making the ion that the pH of water changes is 400 μ g/
cm3Below.As described later, the hard sheet of present embodiment is manufactured as follows:For example it is impregnated in the emulsion of macromolecular elastomer
In non-woven fabrics, then macromolecular elastomer is thermally dried and it is solidified, macromolecular elastomer is thus imparted to nothing
In spinning cloth.In such operation, it is dried from surface containing the moisture in the emulsion being immersed in non-woven fabrics.Therefore, with water
The carrying out of point evaporation, the migration for causing emulsion in non-woven fabrics to be moved to top layer.In the case where migration is caused, macromolecular elastomer
Unevenly it is primarily present near the top layer of non-woven fabrics, the macromolecular elastomer near intermediate layer tails off, and space easily remains
Near intermediate layer.Be matched with gelating agent in emulsion by such migrating across, and makes emulsion gel before it is dried and quilt
Suppress.The present inventor etc. has found:In the gelating agent for obtaining it is contained make the ion that the pH of water changes with specified rate with
On residue in hard sheet in the case of, can reduce polishing velocity in polishing.
The total content of the contained ion for making the pH of water change is 400 μ g/cm in hard sheet3Hereinafter, preferably
It is 350 μ g/cm3, more preferably 100 μ g/cm3Below.In addition, the total content of ion is preferably 0 μ g/cm3, from industrial
Washing efficiency from the aspect of, preferably 1~100 μ g/cm3, more preferably 10~50 μ g/cm3Left and right.In hard sheet
The total content of the contained ion for making the pH of water change is more than 400 μ g/cm3In the case of, slurries cause pH to change, and throw
Ray velocity reduction, further condenses easily abrasive grains.
It should be noted that the ion for making the pH of water change is all ions for changing pH when water is dissolved in,
Specifically, sulfate ion contained in for example common gelating agent, nitrate ion, carbanion, ammonium can be enumerated
Ion, sodium ion, calcium ion, potassium ion etc..
[manufacture method of polishing pad]
Below, to the manufacture method of hard sheet is described in detail.Hard sheet for example can be by following
Operation is manufactured.
(1) operation that superfine fibre occurs the long stapled fiber obvolvent piece of fiber type is prepared
In this operation, prepare the long stapled fiber obvolvent piece that superfine fibre occurs fiber type.Superfine fibre generation type
The long stapled fiber obvolvent piece of fiber can for example be manufactured as follows.
First, the long fibre net formed by islands-in-sea bicomponent fibre is manufactured, the islands-in-sea bicomponent fibre is with water-soluble warm
Plastic resin is as sea component, using water-insoluble thermoplastic resin as island component.Islands-in-sea bicomponent fibre is by dissolving sea
Composition and produce the superfine fibre formed by the resin of island component superfine fibre occur fiber type.It should be noted that at this
In implementation method, to being illustrated using islands-in-sea bicomponent fibre as the example that superfine fibre occurs fiber type, but it is also possible to
There is fiber type to replace islands-in-sea bicomponent fibre using the known superfine fibre such as multi-laminate stratotype cross-section fibers.
It is that can dissolve to remove or divide by water, alkaline aqueous solution, acidic aqueous solution etc. as water insoluble thermoplastic resin
The thermoplastic resin for removing is solved, the resin for being capable of melt spinning is used.As the specific example of water insoluble thermoplastic resin, can arrange
Citing is such as:The PVA resinoids such as polyvinyl alcohol (PVA), PVA copolymers;Containing polyethylene glycol and/or sulfonic acid alkali metal salts as altogether
The modified poly ester being polymerized to point;PEO etc..Wherein, PVA resinoids are preferably used.
During by dissolving PVA resinoids as the islands-in-sea bicomponent fibre of sea component containing PVA resinoids, as island component
Superfine fibre significantly crispatura.As a result, can obtain fibre density non-woven fabrics high.In addition, by the island containing PVA resinoids
When type composite fibre dissolves PVA resinoids, will not decompose or dissolve as the superfine fibre or macromolecular elastomer of island component,
Therefore, being difficult to cause the physical property of superfine fibre or macromolecular elastomer reduces.
As PVA resinoids, from from the aspect of the physical property for improving islands-in-sea bicomponent fibre, preferably use and rubbed containing 4~15
The ethylene modified PVA of your % ethylene unit, further preferably 6~13 moles % ethylene units.
The viscometric degree of polymerization of PVA resinoids is preferably 200~500, more preferably 230~470, particularly preferably
250~450 scope.In addition, as the fusing point of PVA resinoids, in terms of mechanical property and excellent heat stability and melting is spun
From the aspect of silk property is excellent, preferably 160~250 DEG C, particularly preferably more preferably 175~224 DEG C, 180~220 DEG C
Scope.
Used as the water-insoluble thermoplastic resin for forming island component, being will not be by water, alkaline aqueous solution, acidic aqueous solution etc.
Dissolving removes or decomposes the thermoplastic resin for removing, it is possible to use be capable of the resin of melt spinning.As water-insoluble thermoplasticity
The specific example of resin, can be used that the various resins of above-mentioned formation superfine fibre, preferably Tg are more than 50 DEG C and water absorption rate is
The thermoplastic resin of below 4 mass %.
In addition, water-insoluble thermoplastic resin can for example contain catalyst, coloring preventing agent, heat-resistant agent, fire retardant, profit
Lubrication prescription, anti-fouling agent, fluorescent whitening agent, delustering agent, colouring agent, gloss improvers, antistatic additive, aromatic, deodorant, antibacterial
The additives such as agent, mite-proof agent, inorganic particles.
Islands-in-sea bicomponent fibre can be manufactured using composite spinning method, and the composite spinning method is by water insoluble thermoplastic
The low water-insoluble thermoplastic resin of the compatibility of resin and water insoluble thermoplastic resin is carried out after melt spinning respectively, is made
Its Composite.And, islands-in-sea bicomponent fibre preferably forms net with long stapled state.
The long stapled net of islands-in-sea bicomponent fibre can be obtained as below:For example, by spun-bond process by water insoluble thermoplastic resin
With water-insoluble thermoplastic resin melt spinning, Composite is then carried out, further after stretching, pile up it.Need explanation
It is that long fibre is the continuous fiber manufactured without cut off operation when manufacturing chopped fiber.Hereinafter, to the compound fibre of fabric of island-in-sea type
One of the manufacture method of the long stapled net of dimension is described in detail.
First, water insoluble thermoplastic resin and water-insoluble thermoplastic resin are utilized respectively into respective extruder to be melted
Melt mixing, the tow for making molten resin from different spinning-nozzles respectively sprays simultaneously.And, the tow being ejected is used compound
After nozzle is compound, it is sprayed from the nozzle bore of spinneret, be consequently formed islands-in-sea bicomponent fibre.
The mass ratio of water insoluble thermoplastic resin and water-insoluble thermoplastic resin in islands-in-sea bicomponent fibre is without spy
Do not limit, preferably 5/95~50/50, more preferably 10/90~40/60.In water insoluble thermoplastic resin and non-aqueous
Property thermoplastic resin mass ratio in the case of above range, from the formation that can obtain highdensity non-woven fabrics, superfine fibre
It is preferred from the aspect of property is also excellent.In addition, in melt composite spinning, the island number in islands-in-sea bicomponent fibre is preferably 4
~4000 islands/fiber, more preferably 10~1000 islands/fiber.In addition, the fiber number of islands-in-sea bicomponent fibre is not limited especially
It is fixed, but from from the viewpoint of industrialness, preferably 0.5~3dtex or so.
Islands-in-sea bicomponent fibre after being cooled down by cooling device, using aspirators such as jet nozzles equivalent to leading
The high velocity air for drawing 1000~6000m/ of speed points of speed is stretched, and reaches target fiber number.Then, by that will stretch
Composite fibre afterwards is piled up in the collection face of movable type and forms long stapled net.At this point it is possible to will be piled up as needed
Long fibre net part pressure viscosity.
Then, net is overlapped multiple and make its obvolvent.The obvolvent treatment of net can be processed using needle point method or High-Pressure Water
Etc. carrying out.As representative examples, the obvolvent treatment using needle point method is described in detail.
First, polysiloxane-based finish or the ore deposits such as finish, antistatic finish, the finish of raising obvolvent of pin bending will be prevented
Thing oils finish is imparted in net.Then, net obvolvent is made by needle point method.From operability it is excellent from the aspect of, the net after obvolvent
Weight per unit area is preferably 100~1500g/m2Scope.
Secondly, by making, the long stapled net of obvolvent shrinks and improves fibre density.With make chopped fiber net shrink
Situation is compared, and is shunk by making long stapled net, can significantly be shunk.Shrink process preferably carries out the damp and hot contraction such as steam heating
Treatment.As steam heating condition, can enumerate for example ambient temperature be 60~130 DEG C in the range of, relative humidity more than 75%,
Further preferred relative humidity more than 90%, the condition for heating 60~600 seconds.
Damp and hot shrink process preferably makes institute in the way of percentage reduction of area is more than 35%, more preferably more than 40%
The long stapled net of obvolvent shrinks.So, shrink it by with high shrinkage, fibre density becomes high.From the limit shunk
From the aspect of degree and treatment effeciency, the upper limit of percentage reduction of area is preferably less than 80% Zuo You.It should be noted that area contraction
Rate (%) is calculated using following formula.
Obvolvent before (area of the obvolvent net after the area-shrink process of the obvolvent net before shrink process)/shrink process
Area × 100 of net
The obvolvent net for having carried out damp and hot shrink process in this wise further can be carried further by heating roller or hot pressing
High microsteping density.As the change of the obvolvent net weight per unit area before and after damp and hot shrink process, with the unit before shrink process
Area weight is compared, and the weight per unit area after shrink process is preferably more than 1.2 times (mass ratioes), and more preferably 1.5
Times more than and less than 4 times, more preferably less than 3 times.So, can obtain the long stapled net of islands-in-sea bicomponent fibre
(hereinafter referred to as fiber obvolvent piece).
Such fiber obvolvent piece is converted to apparent density and is by the superfine fibre of islands-in-sea bicomponent fibre below
0.35~0.90g/cm3Non-woven fabrics.
It is significantly damp and hot by superfine fibre containing long stapled obvolvent net compared with the obvolvent net containing chopped fiber
Shrink.Therefore, the fibre density of superfine fibre becomes finer and close.And, by optionally removing islands-in-sea bicomponent fibre
Water insoluble thermoplastic resin, can form the non-woven fabrics of the fibre bundle containing superfine fibre.Now, in water insoluble thermoplastic resin quilt
The part that dissolving is extracted forms space.Macromolecular elastomer is assigned with containing ratio high by the space, fiber will be constituted
The superfine fibre boundling of beam, while fibre bundle is bonded to one another.So, can obtain that fibre density is high, voidage is low, rigidity is high
Hard sheet.
(2) make to contain gelating agent (gelating agent contain make the pH of water change ion) and macromolecular elastomer
First emulsion be impregnated in fiber obvolvent piece, then make first emulsion gelation, then be thermally dried, thus make macromolecule
The operation of elastomer solidification
In this operation, macromolecular elastomer is filled uniformly with fiber obvolvent piece in thickness direction.Due to high score
The emulsion of bullet gonosome be high concentration, low viscosity and impregnation impregnability it is also excellent, therefore, easily height is filled out in fiber obvolvent piece
Fill.In addition, by making to contain gelating agent in the emulsion of macromolecular elastomer, emulsion can be suppressed when drying in thickness direction
Uneven migration.
Situation from the solution using macromolecular elastomer usually used at present is different, is using macromolecular elastomer
In the case of emulsion, the macromolecular elastomer of non-porous state can be formed.
As macromolecular elastomer, from the cementability to fiber it is high from the aspect of, the preferred macromolecular elastomer of hydrogen bond.
The macromolecular elastomer of hydrogen bond be such as polyurethane, polyamide-based elastomer, polyvinyl alcohol elastomer etc. it is such by
The elastomer that the macromolecule for being crystallized by hydrogen bond or being condensed is formed.
It is described in detail as representative examples when hereinafter, for using polyurethane as macromolecular elastomer.
As polyurethane, macromolecule polyol, the organic polyisocyanic acid by making mean molecule quantity 200~6000 can be enumerated
Ester and chain extender are with various polyurethane obtained from given molar ratio reaction.
As the specific example of macromolecule polyol, can enumerate for example:Polyethylene glycol, polypropylene glycol, polytetramethylene two
Polyether alcohol and its copolymer such as alcohol, poly- (methyltetramethylene glycol);Polybutylene glyool adipate, poly- decanedioic acid
Butyl glycol ester diol, polyhexamethylene adipate glycol, poly- (adipic acid 3- methyl isophthalic acids, 5- pentadiol esters) glycol, poly- (decanedioic acid
3- methyl isophthalic acids, 5- pentadiol esters) polyester polyol and its copolymer such as glycol, polycaprolactone glycol;Polyhexamethylene carbonic acid
Esterdiol, poly- (3- methyl isophthalic acids, 5- pentylidene carbonic ester) glycol, poly-5-methylene carbonate glycol, polytetramethylene carbonic ester
The polycarbonate-based polyalcohol such as glycol and its copolymer;Polyestercarbonate polyalcohol etc..In addition, can also combine making as needed
With the polyfunctional alcohols such as 4 functional alcohols such as the functional alcohol of trimethylolpropane etc. 3, pentaerythrite or ethylene glycol, propane diols, 1,4- fourths two
The short chain alcohols such as alcohol, 1,6-HD.These materials may be used singly or in combination of two or more.Particularly from can obtain
To from the aspect of the hard sheet of the excellent in te pins of durability such as hydrolytic resistance, oxidative resistance, preferably use non-crystalline polycarbonate-based
The polycarbonate-based polyalcohol of polyalcohol, ester ring type, the polycarbonate-based polyalcohol of straight-chain and above-mentioned polycarbonate-based polyalcohol with
The mixture of polyether alcohol or polyester polyol.In addition, from the wettability to water it is especially good from the aspect of, preferably contain
There is carbon number below 5, be particularly the polyurethane of PAG base of the carbon number below 3.
As the specific example of organic multiple isocyanate, can enumerate for example:Hexamethylene diisocyanate, isophorone two
The aliphatic such as isocyanates, ENB diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate or alicyclic two isocyanide
Acid esters etc. is without xanthochromia type diisocyanate;2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 4,4 '-diphenylmethyl
Aromatic diisocyanates such as alkane diisocyanate, xylylene diisocyanate polyurethane etc..In addition, as needed can be with
It is applied in combination the polyfunctional isocyanates such as 3 functional isocyanates, 4 functional isocyanates.These materials can be used alone, and also may be used
To be applied in combination two or more.It is wherein, high and from the aspect of can obtain hardness hard sheet high from the cementability to fiber,
It is preferred that 4,4 '-dicyclohexyl methyl hydride diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 4,4 '-two
Methylenebis phenyl isocyanate, xylylene diisocyanate.
As the specific example of chain extender, can enumerate for example:Hydrazine, ethylenediamine, propane diamine, hexamethylene diamine, nine methylenes
Base diamines, xylylene diamine, IPD, piperazine and its derivative, adipic dihydrazide, isophthalic dihydrazide
Deng Diamines;The amine of diethylenetriamine etc. three;The tetraamines such as triethylene tetramine;Ethylene glycol, propane diols, BDO, 1,6-
The glycols such as hexylene glycol, 1,4- double (beta-hydroxy ethyoxyl) benzene, 1,4- cyclohexanediols;The alcohols of trimethylolpropane etc. three;Season penta
The alcohols of tetrol etc. four;Alkamines such as ethylaminoethanol, aminopropanol etc..These materials can be used alone, it is also possible to which combination makes
Use two or more.Wherein, from from the aspect of completing curing reaction in a short time, preferred compositions use hydrazine, piperazine, hexa-methylene
Two or more in the triamine such as diamines, IPD and its derivative, ethene triamine.In addition, in chain extending reaction, can be with
Chain extender is applied in combination with following substances, the material is:The monoamines such as ethamine, propylamine, butylamine;4-Aminobutanoicacid, 6- ammonia
The carboxylic monoamine compound such as base caproic acid;The single methanol class such as methyl alcohol, ethanol, propyl alcohol, butanol.
In addition, by being applied in combination double (hydroxymethyl) propionic acid of 2,2-, double (hydroxymethyl) butyric acid of 2,2-, the double (hydroxyls of 2,2-
Ylmethyl) imported into carboxyl isoiony group in the skeleton of polyurethane, can make to water by the carboxylic glycol such as valeric acid etc.
Wettability further improve.
In addition, water absorption rate, storage modulus in order to control polyurethane, preferably contain more than 2 energy by adding intramolecular
The crosslinking agent or polyisocyanates of enough functional groups with for forming the functional group reactionses that the monomeric unit of polyurethane has
The self-crosslinking compound such as compound, multifunctional blocked isocyanate class compound and form cross-linked structure.
As the combination of the functional group of the functional group and crosslinking agent of monomeric unit, can enumerate:Carboxyl andOxazoline base, carboxylic
Base and carbodiimide-based, carboxyl and epoxy radicals, carboxyl and cyclocarbonate radical, carboxyl and '-aziridino, carbonyl and hydrazine derivate,
Hydrazide derivatives etc..Wherein, it is especially excellent from from the aspect of easily forming crosslinking, the rigidity of hard sheet or excellent in wear resistance
Choosing has the monomeric unit of carboxyl and hasThe combination of the crosslinking agent of oxazoline base, carbodiimide-based or epoxy radicals, with hydroxyl
The combination of the monomeric unit and the crosslinking agent with blocked isocyanate base of base or amino and the monomeric unit with carbonyl and
The combination of hydrazine derivate or hydrazide derivatives.It should be noted that from the emulsion intercalation method that can keep macromolecular elastomer
From the aspect of, preferably form cross-linked structure in the heat treatment step after polyurethane is imparted in fiber obvolvent piece.Wherein,
The useful life of particularly preferred cross-linking properties and emulsion is excellent and carbodiimide-based that also had no problem in secure context
And/orOxazoline base.As the crosslinking agent with carbodiimide-based, such as Misshin Spinning Co., Ltd's manufacture can be enumerated
The moisture such as " CARBODILITE E-01 ", " CARBODILITE E-02 ", " CARBODILITE V-02 " dissipates Carbodiimides
Compound.In addition, conduct hasThe crosslinking agent of oxazoline base, can enumerate such as Nippon Shokubai Co., Ltd's manufacture
The moisture such as " Epocros K-2010E ", " Epocros K-2020E ", " EpocrosWS-500 " dissipatesOxazoline compound.Make
It is the use level of crosslinking agent, relative to polyurethane, the active ingredient of crosslinking agent is preferably 1~20 mass %, more preferably 1.5~
1 mass %, more preferably 2~10 mass %.
In addition, from improving to the cementability of superfine fibre so as to from the aspect of the rigidity for improving fibre bundle, as polyurethane
The containing ratio of the composition of middle macromolecule polyol, preferably below 65 mass %, more preferably below 60 mass %.Separately
Outward, from can be by assigning the elasticity of appropriateness come from the aspect of the generation for suppressing cut, preferably more than 40 mass %, further
Preferably more than 45 mass %.
The method for preparing the emulsion of polyurethane is not particularly limited, it is possible to use known method.Specifically, can enumerate
For example polyurethane is assigned as copolymer composition by using the monomer with hydrophilic radicals such as carboxyl, sulfonic group, hydroxyls
Self emulsifiable method to water or add surfactant in polyurethane and make the method that it emulsifies.Due to containing tool
There is the monomeric unit of hydrophilic radical excellent to the wettability of water as the macromolecular elastomer of copolymer composition, therefore, it can protect
Hold substantial amounts of slurries.
As the specific example of the surfactant that can be used to emulsify, can enumerate for example:Lauryl sodium sulfate, dodecane
It is base ammonium sulfate, polyoxyethylene tridecyl ether sodium acetate, neopelex, alkyl diphenyl base ether sodium disulfonate, two pungent
The anionic surfactant such as base sodium sulfosuccinate;Ethylene nonyl phenyl ether, NONIN HS 240, polyoxy
The non-ionic surfaces such as ethene lauryl ether, polyoxyethylene stearyl base ether, polyox-yethylene-polyoxypropylene block copolymer are lived
Property agent etc..Further, it is possible to use the so-called reactive surfactant with reactivity.In addition, being lived by appropriate selection surface
Property agent cloud point, can to emulsion assign heat-sensitive gel.
As the solid component concentration of emulsion, from macromolecular elastomer being filled in into fibre thickness direction is equably high
From the viewpoint of in dimension obvolvent piece, preferably 15~40 mass %, more preferably 25~35 mass %.In addition, as breast
The particle diameter of liquid, more preferably preferably 0.01~1 μm, 0.03~0.5 μm.
First emulsion includes the gelating agent containing the ion for making the pH of water change.Gelating agent is by making emulsion
PH changes and is used to make emulsion particle gelation by heating.Done from surface containing the moisture in the emulsion being immersed in non-woven fabrics
It is dry.Therefore, the carrying out of the evaporation of adjoint moisture, the migration for easily causing the emulsion in non-woven fabrics to be moved to top layer.In non-woven fabrics
In emulsion there occurs migration in the case of, macromolecular elastomer is unevenly largely present near the top layer of non-woven fabrics, in
Macromolecular elastomer near interbed tails off, the easy residual clearance near intermediate layer.In voids left near intermediate layer
In the case of, the hardness reduction in intermediate layer, in addition, hardness becomes uneven.Such migration can be matched with by by gelating agent
Make in emulsion and before it is dried emulsion gel and be suppressed.
As gelating agent, as long as the pH of emulsion is changed and is reached can make the journey of emulsion particle gelation by heating
The water miscible salt of degree, it is possible to use with being not particularly limited.As its specific example, can enumerate as monovalence or divalence
Inorganic salts such as sodium sulphate, ammonium sulfate, sodium carbonate, calcium chloride, calcium sulfate, calcium nitrate, zinc oxide, zinc chloride, chlorination
Magnesium, potassium chloride, potassium carbonate, sodium nitrate, plumbi nitras etc..
It is excellent from from the aspect of can moderately assign gelation as the content ratio of the gelating agent in first emulsion
Phase selection is 0.5~5 mass parts, more preferably 0.6~4 mass parts for the mass parts of macromolecular elastomer 100.
First emulsion can further contain penetrant, defoamer, lubricant, waterproofing agent, oil-proofing agent, tackifier, increment
Agent, curing accelerator, antioxidant, ultra-violet absorber, fluorescer, mould inhibitor, foaming agent, polyvinyl alcohol and carboxymethylcellulose calcium
Deng water-soluble high-molecular compound, dyestuff, pigment, inorganic particles etc..
The method for making first emulsion be impregnated in fiber obvolvent piece is not particularly limited, for example, dip/squeeze can be used
(nip), the method such as cutter painting, rod painting or roller coat.
And, after first emulsion is impregnated in fiber obvolvent piece, heated, thus, first emulsion is embraced in fiber
Close gelation in piece.As the heating condition for such gelation, preferably use for example 40~90 DEG C, further preferably
The condition of 0.5~5 minute or so is kept at 50~80 DEG C.In addition, suppressing to cause because moisture drastically evaporates from top layer from one side
Emulsion migration, while can also be uniformly heated up from the aspect of internal layer, heated preferably by steam.
And, make after first emulsion gelation, it is thermally dried, thus solidify macromolecular elastomer.
As heat drying, the method that is thermally dried in the drying devices such as air drier can be set forth in or red
Method being thermally dried in drying machine after outside line heating etc..As the condition of heat drying, can enumerate for example with most
The mode that high-temperature is 130~160 DEG C, further preferred maximum temperature is 135~150 DEG C heats the condition of 2~10 minutes.It is logical
Heat drying is crossed, is made the moisture evaporation in first emulsion and macromolecular elastomer is equably condensed, it is possible thereby to by macromolecule
Elastomer is also equably imparted in fiber obvolvent piece in thickness direction.
(3) superfine fibre treatment is carried out by there is fiber type to superfine fibre, is formed and containing non-woven fabrics and macromolecule
The operation of the first complex of elastomer
There is the contained islands-in-sea bicomponent fibre in the fiber obvolvent piece of macromolecular elastomer to carry out pole by that will be impregnated with to assign
Fibrillating treatment, forms the first complex of the non-woven fabrics containing superfine fibre and macromolecular elastomer.
This operation is by from containing as the water insoluble thermoplastic resin of island component and as the water-insoluble of sea component
The superfine fibreization treatment of water insoluble thermoplastic resin is removed in the islands-in-sea bicomponent fibre of thermoplastic resin and superfine fibre is formed
The operation of dimension.
Superfine fibreization treatment be by by the fiber obvolvent piece containing islands-in-sea bicomponent fibre water, alkaline aqueous solution,
The water insoluble thermoplastic resin dissolving that hot water heating treatment is carried out in acidic aqueous solution etc. and sea component will be formed is removed or decomposed
The treatment of removing.
As the specific example that hot water heating is processed, for example following method is preferably used:Fiber obvolvent piece impregnated in 65
In~90 DEG C of hot water 5~300 seconds as the first stage, then further in 85~100 DEG C of hot water treatment 100~
600 seconds used as second stage.In addition, in order to improve dissolved efficiency, can carry out as needed using extrusion process, the height of roller
Pressure current treatment, ultrasonication, flushing treatment, stir process, rub and process etc..
Hot water heating treatment is carried out by fiber obvolvent piece, water insoluble thermoplastic resin is molten from islands-in-sea bicomponent fibre
Solve and form superfine fibre.It should be noted that when superfine fibre is formed, superfine fibre is significantly crispaturaed.The pole because this is crispaturaed
The fibre density of fine fibre becomes fine and close.In addition, by removing water insoluble thermoplastic resin from islands-in-sea bicomponent fibre, in water
Part existing for dissolubility thermoplastic resin forms space.Thereafter in operation, macromolecular elastomer is filled into the space.Separately
Outward, hot water heating treatment is carried out by fiber obvolvent piece, contained gelating agent is also dissolved in hot water in fiber obvolvent piece
And be removed.It is consequently formed the first complex.
(4) second emulsion containing gelating agent and macromolecular elastomer is impregnated in the first complex, then make
Two emulsion gels, then be thermally dried, thus solidify macromolecular elastomer, so as to form the operation of the second complex
As described above, being combined in first formed by removing water insoluble thermoplastic resin from islands-in-sea bicomponent fibre
In body, space is formed in the part existing for water insoluble thermoplastic resin.In order to obtain the homogeneous of present embodiment and with height
The hard sheet of hardness, fills the space in the first complex to fetter superfine fibre using macromolecular elastomer.
By macromolecular elastomer is filled in remove water insoluble thermoplastic resin and in the space that is formed, can will be superfine
The collection of filaments and reduce the voidage of hard sheet.In the case where superfine fibre forms fibre bundle, easily showed using capillary
As impregnation emulsion.
As second emulsion, the emulsion same with first emulsion can be used.It should be noted that second emulsion and the first breast
Liquid can be constituted for identical, or different compositions.
In this operation, preferably assign second emulsion and make its gelation so that the second complex that will be formed is in thickness
Degree direction equably 3 decile, and from any one face side by 3 deciles after each layer be set to the first top layer, intermediate layer successively
And during the second top layer, the difference of the voidage in the first top layer and intermediate layer is less than 5%, is more preferably less than 3%.By so entering
Row adjustment, can obtain homogeneous and hardness hard sheet high.
It should be noted that the difference of the voidage in the first top layer and intermediate layer is calculated by following formula.
Difference (%)=absolute value (top layer of voidage (%)-the first in intermediate layer of the voidage in the first top layer and intermediate layer
Voidage (%))
The voidage of each layer is obtained as follows.Using scanning electron microscope, with 30 times to the second composite thickness direction
Section shot.Then, image analysis software Popimaging (Digital being kids.Co manufactures), use are used
Dynamic thresholding method carries out binaryzation, specific space part to the image of resulting photo.And, describe inscribe in each space part
Circle, using the gross area of its inscribed circle as all layers of pore volume.Then, using its photo, will be from the second composite thickness side
To a surface rise thickness direction be divided into 1/3 part be set to the first top layer, will be from another surface in thickness side
The second top layer being set to the part for being divided into 1/3, remaining layer being set to intermediate layer, total face of inscribed circle is obtained according to each layer
Product, as the pore volume of each layer.Then, the voidage of each layer is obtained using following formula.
Pore volume × 100 (%) of the voidage of each layer=each layer pore volume/all layers
As the method in making second emulsion be impregnated in the first complex, make the method for its gelation and be thermally dried
Method, can be used same with the method, the method that makes the method for its gelation and be thermally dried for making first emulsion impregnation
Method.It is consequently formed the second complex.
(5) the second complex is washed so that the total content for making the ion that pH changes is 400 μ g/cm3Below
Operation
As described above, the hard sheet of present embodiment is when macromolecular elastomer is imparted in non-woven fabrics, in order to press down
Emulsion processed uses the emulsion containing gelating agent to the migration on top layer.The present inventor etc. has found:It is residual in the hard sheet for obtaining
In the case of staying contained ion in many gelating agents, polishing velocity is reduced in polishing.And find:By washing
The residual quantity for making ion is 400 μ g/cm3When following, the reduction of polishing velocity can be suppressed.
The operation washed is that the total content of the contained ion for making the pH of water change with hard sheet is 400
μg/cm3Below, 350 μ g/cm are preferably turned into3, further preferably turn into 100 μ g/cm3The operation that following mode is washed.
As method for washing, consider from washing efficiency this respect high, preferably for example heat washing process.As specific condition, for example
During second complex impregnated in into more than 80 DEG C of hot water.Specifically, can enumerate in the following example such as following conditions:As first
In the stage, impregnated 5~300 seconds in 65~90 DEG C of hot water, then carry out the hot water at 85~100 DEG C as second stage
Middle treatment 100~600 seconds.In addition, in order to improve washing efficiency, can carry out as needed using extrusion process, the height of roller
Pressure current treatment, ultrasonication, flushing treatment, stir process, rub and process etc..
(6) in order that the case hardness of hard sheet is JIS-D hardness more than 45, will be answered selected from the first complex, second
At least one of fit and hard sheet carries out the operation of hot pressing
Being present in the space inside hard sheet reduces the uniformity of hardness and hardness.In this operation, by will be upper
The first complex, the second complex and/or the hard sheet stated carry out hot pressing, reduce space.Subtracted by making space in this wise
Few, the apparent density of hard sheet is improved, and hardness, the uniformity of hardness and rigidity are improved.As autoclaving conditions, using setting
For be heated to temperature that superfine fibre and macromolecular elastomer do not decompose, be for example heated to 160~180 DEG C of metallic roll with
The condition that 30~100kg/cm of line pressure is pressurizeed.
Such operation, can obtain the hard sheet of present embodiment more than.The hard sheet of present embodiment is excellent
It is elected to be as the polishing layer of polishing pad is used.Specifically, desired processing can be implemented as desired by hard sheet
And form polishing layer.For example, implementing the fluffing treatment or the reversely brushing of sealing carried out using sand paper or pin cloth, diamond etc.
Treatment, hot pressurized treatments or Embossing processing etc..Furthermore it is possible to form clathrate, concentric circles, whirlpool on the surface of hard sheet
The grooves such as shape or hole.
In addition, as needed, can using hard sheet as polishing layer with compile thing, fabric, non-woven fabrics, elastic resin film or
The elastomer layer lamination such as elastic sponge body.As elastic membrane and elastic sponge body, except containing being soaked with the current general polyurethane for using
Non-woven fabrics (such as " Suba400 " (Nitta Hass (strain) manufactures)) outside, can enumerate:Natural rubber, nitrile rubber, poly- fourth
The rubber such as diene rubber, silicon rubber;Polyester-type thermoplastic elastomer, polyamide-type thermoplastic elastomer, fluorine-containing thermoplastic elastic
The thermoplastic elastomer (TPE)s such as body;Foamed plastic;Polyurethane etc..So, by laminar flexible body layer, the part of polished surface can be made
Flatness (local flat of chip) is improved.It should be noted that polishing pad is except polishing layer and elastomer layer are by melting
Bonding etc., also will be two-layer bonded using bonding agent or two-sided tape etc. directly obtained from engagement outside polishing pad
Polishing pad or further between the two layers in the presence of other layers polishing pad.
The polishing pad of the hard sheet of present embodiment has been used to can be used for chemically-mechanicapolish polishing (CMP), the chemistry
Mechanical polishing (CMP) is using known CMP devices and makes polished surface and throwing with constant speed under elevated pressure using slurries
Light pad contacts certain hour.Slurries for example contain the liquid-like mediums such as water or oil;Silica, aluminum oxide, cerium oxide, oxidation
The polishing agents such as zirconium, carborundum;The compositions such as alkali, acid, surfactant.In addition, when carrying out CMP, as needed can by slurries with
Lubricating oil, cooling agent etc. are applied in combination.
It is not particularly limited as the article of polishing object, can be enumerated for example:Crystal, silicon, glass, optical substrate, electronics
Circuit substrate, multi-layer wire substrate, hard disk etc..As polishing object, particularly preferably silicon wafer, semiconductor wafer.As half
The specific example of conductor chip, can enumerate for example has the insulation of silica, fluorinated silicon oxide, organic polymer etc. on surface
The semiconductor wafer of the barrier metal films such as the wiring material such as film, copper, aluminium, tungsten metal film, tantalum, titanium, tantalum nitride, titanium nitride etc..
Embodiment
Hereinafter, the present invention is illustrated by embodiment.It should be noted that the present invention is not by any limit of embodiment
It is fixed.
First, the evaluation method that will be used in the present embodiment is summarized as follows and illustrates.
[apparent density of hard sheet]
With the quality (g/cm of unit area hard sheet2) divided by the value obtained by thickness (cm) as apparent density (g/
cm3).Then, to determining apparent density at any the 10 of hard sheet, arithmetic average is carried out, using resulting value as apparent
Density.It should be noted that thickness is in load 240gf/cm according to JISL1096 standards2Lower measure.
[calculating of the measure and R% of the JIS-D hardness on the surface of hard sheet, the first top layer and intermediate layer]
The D hardness on the surface of hard sheet, the first top layer and intermediate layer according to JISK7311 standard tests.It is specific and
Speech, for the D hardness on hard sheet surface, 8 is overlapped by the hard sheet of thickness about 1.25mm, impartial in width
Ground determines 3 points of hardness, is averaged D hardness of the value as hard sheet surface.
In addition, for the D hardness on the first top layer, by by the hard sheet of thickness about 1.25mm from the second top layer side
It is ground, has obtained the sheet material on first top layer of thickness 0.40mm.Then, the sheet material on the first top layer that will be obtained overlaps 25
, 3 points of hardness is equably determined in width, it is averaged JIS-D hardness of the value as the first top layer.In addition, for
For the D hardness in intermediate layer, equably it is ground from the first top layer side and the second top layer side by by hard sheet, is obtained
The sheet material in the intermediate layer of thickness 0.40mm.Then, the sheet material in the intermediate layer that will be obtained overlaps 25, is equably surveyed in width
Fixed 3 points hardness, is averaged hardness of the value as intermediate layer.And, using 3 points of the first top layer for obtaining of D hardness and
The value of the JIS-D hardness of 6 points of the total of the D hardness of 3 points of intermediate layer has obtained R (%) by following formula.
R (%)=(D maximum hardness-D hardness minimum value)/D hardness average value × 100
[making the total content of the ion that the pH of water changes]
The part and water 10mL that rectangular hard sheet will be cut into are put into screw-cap test tube.Then, block heater is used
Screw-cap test tube is heated 2 hours at 90 DEG C, the water-soluble substances in hard sheet has been carried out into hot water extraction.Then, use
Chromatography of ions (ICS-1600) detects the ion component in its extract solution.Wherein, determine as the pH for making water change from
The sulfate ion of son and the total amount of ammonium ion, are scaled contained ionic weight in unit volume hard sheet.
[polishing velocity]
By the way that hard sheet to be cut into the toroidal of diameter 51cm, and clathrate ground is spaced in surface and is formed with 15.0mm
The groove of width 1.0mm, depth 0.5mm, has thus made polishing pad.And, paste adhesive tape, Ran Houan at the back side of polishing pad
Loaded on CMP planarization device (open country village of Co., Ltd. makes manufactured " PP0-60S ").Then, in platen rotating speed 70 rev/min, turn
69 revs/min of rotating speed of head, polish pressure 40g/cm2Under conditions of, while with 100ml/ points of speed supply slurries (Showa electrician strain
The SHOROX A-31 of formula commercial firm manufacture) while being polished 3 hours to the synthetic quartz of 4 inches of diameter.And, after determining polishing
Any 25 points of thickness in the face of synthetic quartz, average by the thickness polished in each point obtains polishing divided by polishing time
Speed (nm/ points).
It should be noted that measure makes what first top layer and intermediate layer of the hard sheet of thickness about 1.25mm were exposed respectively
The polishing velocity of the hard sheet of thickness 0.70mm.
[embodiment 1]
Using water-solubility PVA as sea component, using 6 moles of isophthalate modified PET of % of modified degree as island into
Point.By water-solubility PVA and isophthalate modified PET at 260 DEG C with 25/75 (mass ratio) from melt composite spinning nozzle
(island number:25 islands/fiber) spray.And, adjustment injector pressure makes spinning speed for 3700m/min, in online trapping fiber number
The long fibre of 3dtex, obtains weight per unit area 35g/m2Net.
By cross layered, overlapping 16 is thrown the net, and has made total weight per unit area 480g/m2Overlay network.And, it is right
Overlay network spraying prevents the finish that pin bends.Then, barb number 1 and the knitting needle and barb number 6 of knitting branch yarn 42 are used
The knitting needle of individual and knitting branch yarn 42, by overlay network with 3150 pin holes/cm2Needling treatment is carried out, obvolvent net is resulting in.
The weight per unit area of obvolvent net is 770g/m2, splitting power is 9.6kg/2.5cm.In addition, obtained by needling treatment
Percentage reduction of area is 25.8%.
Then, by obvolvent net under conditions of 110 DEG C, 23.5%RH steam treatment 70 seconds.Percentage reduction of area now
It is 44%.Then, after drying in 90~110 DEG C of baking box it, hot pressing is carried out at 115 DEG C, thus obtains unit plane
Product weight 1312g/m2, apparent density 0.544g/cm3, thickness 2.41mm fiber obvolvent piece.
Then, make to be impregnated in fiber obvolvent piece as the emulsion of the polyurethane of first emulsion.It should be noted that poly- ammonia
Ester is the PAG by polycarbonate-based polyalcohol and carbon number 2~3 with 99.8:0.2 (mol ratio) is mixed
Mixture as polyol component, and containing the 1.5 carboxylic monomers of mass % without xanthochromia type polyurethane.In addition, poly- ammonia
Ester is the polyurethane of the imporosity that cross-linked structure is formed by being heat-treated.First emulsion is adjusted to:Relative to poly-
The mass parts of urethane 100, containing the mass parts of Carbodiimides crosslinking agent 4.6 and the mass parts of ammonium sulfate 1.8 as gelating agent,
And the solid constituent of polyurethane is 20%.
By will containing be soaked with the fiber obvolvent piece of first emulsion heated under 90 DEG C, 30%RH atmosphere and made first breast
Pension gelation, has further carried out dried process at 150 DEG C.Then, hot pressing is carried out at 140 DEG C, is thus adjusted to single
Position area weight 1403g/m2, apparent density 0.716g/cm3, thickness 1.96mm.
Then, processed by using extrusion process and High-Pressure Water, the fiber obvolvent piece for having polyurethane will be assigned at 95 DEG C
Hot water in dipping 10 minutes and dissolve remove water-solubility PVA, be converted into the superfine fibre of fiber number 0.09dtex, then done
It is dry.Thus, weight per unit area 1009g/m has been obtained2, apparent density 0.538g/cm3, thickness 1.87mm the first complex.
Then, make to be impregnated in the first complex as the emulsion (the mass % of solid constituent 30) of the polyurethane of second emulsion
In.It should be noted that polyurethane is identical with the polyurethane being above impregnated with.Second emulsion is adjusted to:Relative to polyurethane
100 mass parts, containing the mass parts of Carbodiimides crosslinking agent 4.6 and the mass parts of ammonium sulfate 1.0, and polyurethane solid constituent
It is 30%.
By will containing be soaked with the first complex of second emulsion heated under 90 DEG C, 60%RH atmosphere and made second breast
Pension gelation, has carried out dried process at 150 DEG C.Thus, weight per unit area 1245g/m has been obtained2, apparent density
0.748g/cm3, thickness 1.66mm the second complex.The difference of the voidage on first top layer and intermediate layer of the second complex is
1.8%.
Then, the second complex is impregnated 10 points in 95 DEG C of hot water by using extrusion process and High-Pressure Water treatment
Clock is washed.Then, dried at 180 DEG C.And, enter by under the conditions of line pressure 100kg/cm, 160 DEG C
Row hot-pressing processing, has obtained weight per unit area 1212g/m2, apparent density 0.795g/cm3, thickness 1.53mm hard sheet
Intermediate.
Each grinding 0.15mm is distinguished to the two sides top layer of hard sheet intermediate using #100 paper, unit area is finish-machined to
Weight 994g/m2, apparent density 0.788g/cm3, thickness 1.26mm hard sheet.The JIS-D hardness of hard sheet is 52,
The R% of JIS-D hardness is 11.3%.In addition, the sulfate radical as the ion for making pH change contained in hard sheet
The total amount of ion and ammonium ion is 26.9 μ g/cm3。
Evaluation result is shown in table 1.
[embodiment 2]
Except carrying out heat under the conditions of line pressure 100kg/cm, 160 DEG C to the first complex before assigning second emulsion
Outside pressure treatment, operate similarly to Example 1, manufacture hard sheet and evaluated.It should be noted that what is obtained is hard
The weight per unit area of matter sheet material is 996g/m2, apparent density be 0.808g/cm3, thickness be 1.23mm.Show the result in table 1.
[embodiment 3]
In addition to reducing the washing degree of the second complex in embodiment 1, operate similarly to Example 1, manufacture
Hard sheet is simultaneously evaluated.Contained sulfate ion and ammonium as the ion for making pH change in hard sheet
The total amount of ion is 300 μ g/cm3.Show the result in table 1.
[comparative example 1]
Except not washed to the second complex in embodiment 1, thus come replace by by the second complex 95
DEG C hot water in dipping beyond being washed, operate similarly to Example 1 within 10 minutes, manufacture hard sheet is simultaneously commented
Valency.Show the result in table 1.
[comparative example 2]
In embodiment 1, the first complex further hot pressing has been carried out under the conditions of line pressure 100kg/cm, 160 DEG C
Treatment, then, thus the emulsion of same composition of the impregnation without gelating agent is come to replace impregnation containing gelating agent second
Emulsion, in addition, operates similarly to Example 1, manufactures hard sheet and is evaluated.It should be noted that obtaining
Hard sheet weight per unit area be 969g/m2, apparent density be 0.817g/cm3, thickness be 1.19mm.Show the result in
Table 1.
[comparative example 3]
In addition to reducing the washing degree of the second complex in embodiment 1, operate similarly to Example 1, manufacture
Hard sheet is simultaneously evaluated.Contained sulfate ion and ammonium as the ion for making pH change in hard sheet
The total amount of ion is 404 μ g/cm3.Show the result in table 1.
[comparative example 4]
In addition to reducing the washing degree of the second complex in embodiment 1, operate similarly to Example 1, manufacture
Hard sheet is simultaneously evaluated.Contained sulfate ion and ammonium as the ion for making pH change in hard sheet
The total amount of ion is 504 μ g/cm3.Show the result in table 1.
As shown in Table 1, JIS-D hardness has been used to be 0~20%, make water for more than 45, R% for of the invention
The total contents of ion that change of pH be 400 μ g/cm3The polishing pad of the hard sheet that following embodiment 1~3 is obtained and
Speech, the polishing velocity on its first top layer, i.e. initial burnishing speed are 120nm/ point, to 5 hours after average value can keep at the beginning of
More than the 90% of beginning polishing velocity.On the other hand, for using in second emulsion coordinate gelating agent and do not carry out fully
For the polishing pad of the hard sheet of the comparative example 1 of washing, the polishing velocity on its first top layer is significant lower, is 93nm/ points.Separately
Outward, the hard sheet of comparative example 2 is the homogenization that hard sheet is sought by hot pressing, thus replaces matching somebody with somebody in second emulsion
Gelating agent is closed to fill uniformly with the example of macromolecular elastomer.For the polishing pad of comparative example 2, the total content of ion
It is few, but R% is 30.2% and uneven.As a result, being only capable of keeping the 89% of initial burnishing speed to the average value after 5 hours.
In addition, the total content of ion is 404 μ g/cm3The μ g/cm of comparative example 3 and 5043Comparative example 4, to 5 hours after average value it is equal
About the 84% of initial burnishing speed can only be kept.
Claims (16)
1. a kind of hard sheet, non-woven fabrics and be imparted to institute that it includes the superfine fibre with 0.0001~0.5dtex fiber numbers
The macromolecular elastomer in non-woven fabrics is stated,
The JIS-D hardness of the hard sheet is more than 45,
To the section of thickness direction equably 3 decile, and from any one face side by 3 deciles after each layer be set to successively
When one top layer, intermediate layer and the second top layer,
The JIS-D hardness of any 3 points of 6 points of totals of respective width in first top layer and the intermediate layer is determined, is made
With the D hardness for amounting at 6 points, the R% calculated by following formula is 0~20%,
Average value × 100 of R (%)=(D maximum hardness-D hardness minimum value)/D hardness
Also, the total content for making the ion that the pH of water changes is 400 μ g/cm3Below.
2. hard sheet according to claim 1, wherein, the total content of the ion is 1~100 μ g/cm3。
3. hard sheet according to claim 1, wherein, the superfine fibre is long fibre, and forms fibre bundle.
4. hard sheet according to claim 3, wherein, the apparent density of the non-woven fabrics is 0.35~0.90g/cm3。
5. hard sheet according to claim 3, wherein, in the section of thickness direction, form the institute of the fibre bundle
At least a portion for stating superfine fibre passes through the macromolecular elastomer boundling.
6. hard sheet according to claim 5, wherein, in the section of thickness direction, at least the one of the fibre bundle
Part is bonded by the macromolecular elastomer each other.
7. hard sheet according to claim 3, wherein, in the section of thickness direction, form the institute of the fibre bundle
The radical for stating more than half of superfine fibre passes through the macromolecular elastomer boundling.
8. hard sheet according to claim 7, wherein, in the section of thickness direction, the half of the fibre bundle with
On beam bonded by the macromolecular elastomer each other.
9. hard sheet according to claim 1, wherein, the macromolecular elastomer is non-porous macromolecular elastomer.
10. hard sheet according to claim 1, wherein, the mass ratio of the non-woven fabrics and the macromolecular elastomer
(non-woven fabrics/macromolecular elastomer) is 90/10~55/45.
11. hard sheets according to claim 10, its apparent density is 0.50~1.2g/cm3。
12. hard sheets according to claim 1, wherein, the JIS-D hardness on second top layer is more than 45,
Each any 3 points JIS-D hardness for amounting at 6 points is determined in second top layer and the intermediate layer, using amounting at 6 points
D hardness, the R% calculated by following formulas is 0~20%,
R (%)=(D maximum hardness-D hardness minimum value)/D hardness average value × 100.
A kind of 13. polishing pads, it possesses hard sheet any one of claim 1~12 as polishing layer.
A kind of 14. manufacture methods of hard sheet, the method includes following operations:
(1) operation that superfine fibre occurs the long stapled fiber obvolvent piece of fiber type is prepared, the superfine fibre generation type is fine
The long stapled fiber obvolvent piece of dimension can be processed by superfine fibre and form the superfine fibre with below 0.5dtex fiber numbers
The non-woven fabrics of dimension, and the apparent density of the non-woven fabrics is 0.35g/cm3More than;
(2) first emulsion containing gelating agent and macromolecular elastomer is impregnated in the fiber obvolvent piece, then make
One emulsion gel, then be thermally dried, the operation for thus solidifying macromolecular elastomer, the gelating agent contains and makes water
The ions that change of pH;
(3) superfine fibre treatment is carried out by there is fiber type to the superfine fibre, is formed and containing the non-woven fabrics and institute
State the operation of the first complex of macromolecular elastomer;
(4) second emulsion containing the gelating agent and the macromolecular elastomer is made to be impregnated in first complex,
It is thermally dried again, thus solidifies the macromolecular elastomer, so that the operation of the second complex is formed, by described second
Complex equably carries out 3 deciles in thickness direction, and from any one face side by 3 deciles after each layer be set to successively
When one top layer, intermediate layer and the second top layer, the difference of the voidage in first top layer and the intermediate layer is less than 5%;
(5) second complex is washed so that the total content of the ion is 400 μ g/cm3Hereinafter, it is hard so as to obtain
The operation of matter sheet material;And
(6) in order that the case hardness of the hard sheet is JIS-D hardness more than 45, will be selected from first complex, institute
Stating at least one of the second complex and the hard sheet carries out the operation of hot pressing.
The manufacture method of 15. hard sheets according to claim 14, wherein, the total content of the ion is 1~100 μ
g/cm3。
The manufacture method of 16. hard sheets according to claim 14, wherein, it is bag that the superfine fibre occurs fiber type
Island containing the water insoluble thermoplastic polyvinyl alcohol resin as sea component, the water-insoluble thermoplastic resin as island component
Type composite fibre,
The superfine fibreization treatment of the operation (3) be make the water insoluble thermoplastic polyvinyl alcohol resin be dissolved in warm water and
The operation for optionally removing.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-024525 | 2013-02-12 | ||
JP2013024525 | 2013-02-12 | ||
PCT/JP2014/000616 WO2014125797A1 (en) | 2013-02-12 | 2014-02-05 | Rigid sheet and process for manufacturing rigid sheet |
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US (1) | US20160002835A1 (en) |
EP (1) | EP2957672B1 (en) |
JP (1) | JP6220378B2 (en) |
KR (1) | KR102136441B1 (en) |
CN (1) | CN105008614B (en) |
TW (1) | TWI607832B (en) |
WO (1) | WO2014125797A1 (en) |
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CN107431467B (en) * | 2015-04-17 | 2021-02-19 | 株式会社村田制作所 | Resonance circuit, band elimination filter and band pass filter |
DE102016222063A1 (en) * | 2016-11-10 | 2018-05-17 | Siltronic Ag | Method for polishing both sides of a semiconductor wafer |
US20180134918A1 (en) * | 2016-11-11 | 2018-05-17 | Jh Rhodes Company, Inc. | Soft polymer-based material polishing media |
JP6951895B2 (en) * | 2017-07-25 | 2021-10-20 | ニッタ・デュポン株式会社 | Abrasive cloth |
KR102652060B1 (en) * | 2018-08-27 | 2024-03-28 | 주식회사 쿠라레 | Artificial leather base material, manufacturing method thereof, and napped artificial leather |
JP7111609B2 (en) * | 2018-12-27 | 2022-08-02 | 株式会社クラレ | Fiber composite polishing pad and method for polishing glass-based substrate using the same |
KR20220113689A (en) * | 2019-12-20 | 2022-08-16 | 도레이 카부시키가이샤 | Sheet-like article and manufacturing method thereof |
WO2021125029A1 (en) * | 2019-12-20 | 2021-06-24 | 東レ株式会社 | Sheet material and method for producing same |
KR20220113397A (en) * | 2019-12-26 | 2022-08-12 | 주식회사 쿠라레 | Silver leather type seat |
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- 2014-02-05 CN CN201480007963.2A patent/CN105008614B/en active Active
- 2014-02-05 US US14/767,115 patent/US20160002835A1/en not_active Abandoned
- 2014-02-05 EP EP14752242.9A patent/EP2957672B1/en not_active Not-in-force
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Also Published As
Publication number | Publication date |
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CN105008614A (en) | 2015-10-28 |
EP2957672A1 (en) | 2015-12-23 |
KR20150116876A (en) | 2015-10-16 |
WO2014125797A1 (en) | 2014-08-21 |
KR102136441B1 (en) | 2020-07-21 |
EP2957672B1 (en) | 2018-05-02 |
TWI607832B (en) | 2017-12-11 |
JPWO2014125797A1 (en) | 2017-02-02 |
US20160002835A1 (en) | 2016-01-07 |
TW201440956A (en) | 2014-11-01 |
JP6220378B2 (en) | 2017-10-25 |
EP2957672A4 (en) | 2016-07-27 |
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