CN103173149A - Bonding sheet - Google Patents
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- CN103173149A CN103173149A CN2012105589973A CN201210558997A CN103173149A CN 103173149 A CN103173149 A CN 103173149A CN 2012105589973 A CN2012105589973 A CN 2012105589973A CN 201210558997 A CN201210558997 A CN 201210558997A CN 103173149 A CN103173149 A CN 103173149A
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Abstract
The invention provides a bonding sheet, which can prevent fragments and cutting shreds during a bonding sheet cutting process. The bonding sheet comprises a bonding agent layer and a substrate layer and is formed by co-extrusion of bonding agent layer forming materials and substrate layer forming materials. The difference between the anchoring force located between the bonding agent layer and the substrate layer of the bonding sheet, and the bonding force of the bonding agent layer is more than 1.0N/20mm.
Description
Technical field
The present invention relates to adhesive sheet.
Background technology
The semiconductor crystal wafer that is formed by silicon, gallium, arsenic etc. is made with the major diameter state, after the surface forms pattern, and the grinding back side, the thickness of wafer is generally by wear down to 100 μ m～600 μ m left and right.Then, be the element small pieces with the semiconductor crystal wafer cutting and separating (dicing) after grinding, and be transferred to installation procedure.In the operation of grinded semiconductor wafer rear (back side grinding process), use adhesive sheet for the pattern plane of protecting semiconductor crystal wafer.This adhesive sheet is stripped from the most at last.For the adhesive sheet that uses for such purpose, the bounding force that the degree that can not peel off in grinding process overleaf must be arranged can easily be peeled off, not damage the low bounding force of the degree of semiconductor crystal wafer when also requiring on the other hand to peel off after grinding process overleaf.
Adhesive sheet as the making that is used for semiconductor crystal wafer, can use the adhesive sheet that is coated with tackiness agent on base material, for example propose at the adhesive sheet (patent documentation 1) that comprises the binder layer that is provided with the coating acrylic adhesive on the base material of polyethylene-based resin and forms.In the adhesive sheet of patent documentation 1, the power that the surface of the layer that joins at binder layer with this binder layer due to blade when cutting off adhesive sheet applies changes, the small fragment of tackiness agent can be attached to blade, adhesive sheet from it, produce so-called fragment.Because these fragments are attached on blade, the cut-out that sticks on the adhesive sheet on semiconductor crystal wafer becomes difficult, and becoming easily produces the cutting chip on adhesive sheet.In addition, can become also that fragment is attached on semiconductor crystal wafer, semiconductor crystal wafer produces the reason of breaking during grinding.And then, owing to using the blade cut-out that is attached with fragment, the pollution that sometimes produces semiconductor crystal wafer because of fragment.In addition, owing to being involved in the cutting chip, sometimes at semiconductor crystal wafer edge section generation Edge crack (edge crack) and edge breakage (edge chipping).
The prior art document
Patent documentation
Patent documentation 1: the international brochure that discloses No. 2007/116856
Summary of the invention
The problem that invention will solve
The present invention makes in order to solve above-mentioned problem in the past, and its purpose is to provide a kind of adhesive sheet that produces fragment and cutting chip when having suppressed to cut off adhesive sheet.
For the scheme of dealing with problems
Adhesive sheet of the present invention possesses binder layer and substrate layer, forms material and substrate layer forms the material co-extrusion modling and obtains by binder layer.The difference of this binder layer of adhesive sheet of the present invention and the bounding force of the anchor force between this substrate layer and this binder layer is more than 1.0N/20mm.
In preferred embodiment, above-mentioned binder layer comprises polyolefin-based resins.
In preferred embodiment, said polyolefins is that resin comprises the amorphous propene that uses metallocene catalyst polymerisation to form-(1-butylene) multipolymer.
In preferred embodiment, above-mentioned substrate layer comprises vinyl-vinyl acetate copolymer.
In preferred embodiment, the thickness of adhesive sheet of the present invention is 5 μ m～1000 μ m.
In preferred embodiment, adhesive sheet of the present invention is used for semiconductor crystal wafer processing.
The effect of invention
According to the present invention, binder layer is formed the anchor force that material and substrate layer form between that the material co-extrusion modling obtains, substrate layer and binder layer be the adhesive sheet more than 1.0N/20mm with the difference of bounding force by using, produce fragment in the time of can suppressing to cut off adhesive sheet and cut chip.Adherend is polluted on adherend because of adhesive residue when preventing that adhesive sheet from peeling off, the substrate layer of adhesive sheet and the anchor force between binder layer are had requirement.Adhesive sheet of the present invention is owing to having excellent anchoring, tackiness agent arranged and adherend is polluted due to residual on adherend in the time of can preventing therefore that adhesive sheet from peeling off.In addition; adhesive sheet in the past before binder layer forms, base material is implemented surface treatment, but the present invention can be guaranteed the anchor force between substrate layer and binder layer and not implement surface treatment in order to ensure anchoring; thereby can reduce manufacturing process, suppress the cost of manufacture of adhesive sheet.And then adhesive sheet of the present invention is due to the formation operation that does not comprise the binder layer that utilizes coating, therefore can also eliminate the problem of the environmental pressure that in the drying process of binder solution of coating, the organic solvent volatilization produces.
Description of drawings
Fig. 1 is the schematic cross sectional view of the adhesive sheet of the preferred embodiment of the present invention.
Description of reference numerals
10 binder layers
20 substrate layers
100 adhesive sheets
Embodiment
A. the one-piece construction of adhesive sheet
Fig. 1 is the schematic cross sectional view of adhesive sheet preferred embodiment of the present invention.Adhesive sheet 100 of the present invention possesses binder layer 10 and substrate layer 20.The difference of the anchor force that the binder layer 10 of adhesive sheet of the present invention and substrate layer are 20 and the bounding force of binder layer 10 is more than 1.0N/20mm.Adhesive sheet of the present invention is by having above-mentioned characteristic, the generation of fragment and cutting chip in the time of can suppressing to cut off adhesive sheet.And then therefore adhesive sheet of the present invention can prevent having tackiness agent that adherend is polluted because of residual on adherend when adhesive sheet from peeling off owing to having excellent anchoring.
Adhesive sheet of the present invention can also further possess other suitable arbitrarily layers.As other layers, for example can list be arranged on substrate layer with binder layer be in opposition side a side, can give adhesive sheet stable on heating upper layer.
The thickness of adhesive sheet 100 is preferably 5 μ m～1000 μ m, more preferably 90 μ m～300 μ m, more preferably 100 μ m～250 μ m.
The thickness of binder layer 10 is preferably 5 μ m～100 μ m, more preferably 10 μ m～100 μ m, more preferably 15 μ m～65 μ m.
The thickness of substrate layer 20 is preferably 30 μ m～300 μ m, more preferably 50 μ m～250 μ m.
As mentioned above, poor (bounding force of the anchor force-binder layer between binder layer and substrate layer) of the bounding force of the binder layer of adhesive sheet of the present invention and the anchor force between substrate layer and binder layer is more than 1.0N/20mm.Be more than 1.0N/20mm by making anchor force between binder layer and substrate layer (below, be called anchor force) and the difference of bounding force, produce fragment and cutting chip in the time of can suppressing to cut off adhesive sheet.And, can prevent having tackiness agent that adherend is polluted because of residual on adherend when adhesive sheet from peeling off.More than the difference of the bounding force of this anchor force and binder layer is preferably 2.0N/20mm, more preferably more than 3.0N/20mm.The higher limit of the difference of this anchor force and bounding force is preferably the value that does not cause fastening destruction in anchor force is measured, for example 10.0N/20mm.Need to prove, will narrate in the back about the measuring method of anchor force and the measuring method of bounding force.
About the anchor force of adhesive sheet of the present invention, so long as being the above value of 1.0N/20mm, the difference of above-mentioned anchor force and bounding force gets final product, can be set as suitable value arbitrarily.The anchor force of adhesive sheet of the present invention is preferably anchor force and fastening destruction greatly, does not occur can't measures the value of anchor force, for example more than 5.0N/20mm.If the anchor force of adhesive sheet in above-mentioned scope, can fully guarantee the adaptation between substrate layer and binder layer, even the power that applies on blade when therefore cutting off adhesive sheet changes, also can suppress the generation of fragment on the interface between substrate layer and binder layer.The pollution to adherend of the generation of the cutting chip in the time of thus, can preventing the adhesive sheet cut-out and fragment.And then, if residual on adherend when the anchor force of adhesive sheet in above-mentioned scope, can prevent that adhesive sheet from peeling off tackiness agent is arranged, pollute adherend.In this specification sheets, " anchor force of adhesive sheet " is the following value that obtains: the adhesive sheet of gained is made the wide test film of 20mm, with the binder layer of this test film and commercially available peeling off with adhesive tape (Nitto Denko Co., Ltd. make, BT-315) binder layer is 23 ℃ of applyings, measures and the value that obtains with T-shaped stripping test (peeling rate 300mm/ minute).
About the bounding force of adhesive sheet of the present invention, so long as being the above value of 1.0N/20mm, the difference of above-mentioned anchor force and bounding force gets final product, can be set as suitable value arbitrarily.The bounding force of adhesive sheet of the present invention is preferably 0.3N/20mm～3.0N/20mm, more preferably 0.4N/20mm～2.5N/20mm.Bounding force by making adhesive sheet can be taken into account bounding force and separability in above-mentioned scope, for example can be formed in the ground finish in the back side grinding process of semiconductor crystal wafer the adhesive sheet of not peeling off, can easily peeling off after ground finish.In present disclosure, " bounding force of adhesive sheet " is the following value that obtains: after being crimped on the binder layer of the adhesive sheet that obtains on Silicon Wafer with the roller round trip of 2kg, placed 30 minutes, and measured by 180 ° of stripping tests (peeling rate 300mm/ minute) value that obtains.
Adhesive sheet of the present invention can provide under the state by the barrier film protection.Adhesive sheet of the present invention can batch as tubular take the state with the barrier film protection.Barrier film has as the protection adhesive sheet until in the function of the protecting materials of reality.As barrier film, for example can list by silicon is to shell from agent ﹑ fluorine series stripping agent, and the strippers such as chain alkyl acrylate series stripping agent have carried out plastics (such as polyethylene terephthalate (PET), polyethylene, polypropylene) film, non-woven fabrics or the paper etc. of surface coated.
Adhesive sheet of the present invention is for example in the situation that without barrier film protection, also can carry out the back side to the outermost layer that is in a side of opposition side with binder layer and process.The back side is processed and is carried out such as strippers such as can using silicon series stripping agent, chain alkyl acrylate series stripping agent.Adhesive sheet of the present invention is processed by carrying out the back side, can batch to be tubular.
B. binder layer
Above layer gets final product above-mentioned binder layer so long as the difference of the anchor force of the adhesive sheet that obtains and bounding force is 1.0N/20mm, can be made of suitable arbitrarily tackiness agent.This binder layer preferably comprises polyolefin-based resins.As the concrete example of polyolefin-based resins, can list ethylene copolymer, the polyolefin modified polymkeric substance etc. such as Low Density Polyethylene, ultra-low density polyethylene, low crystalline polypropylene, amorphous propene-(1-butylene) multipolymer, ionomer resin, vinyl-vinyl acetate copolymer, ethene-(methyl) acrylic copolymer, ethene-(methyl) Acrylic Ester-Maleic Anhydride, ethylene-methyl methacrylate glycidyl ester copolymer.This binder layer more preferably comprises amorphous propene-(1-butylene) multipolymer.If such binder layer can be by making adhesive sheet with the co-extrusion modling of substrate layer, process number is few and with an organic solvent can not obtain adhesive sheet.Need to prove, in this specification sheets, " amorphous " refers to not have the character of the clear and definite fusing point as xln.
Above-mentioned amorphous propene-(1-butylene) multipolymer preferably can be by using metallocene catalyst, obtained by propylene and 1-butylene polymerization.More specifically, amorphous propene-(1-butylene) multipolymer for example can followingly obtain: use metallocene catalyst to make the polymerization process of propylene and 1-butylene polymerization, after this polymerization process, carry out the postprocessing working procedures such as catalyzer removing step, foreign matter removing step.Amorphous propene-(1-butylene) multipolymer is through after such operation, to obtain such as shapes such as Powdered, particulate state.As metallocene catalyst, such as can list the even mixed catalyst of the metallocene that comprises metallocene compound and aikyiaiurnirsoxan beta, load has the metallocene loaded catalyst of metallocene compound etc. on microparticle support.
The amorphous propene that use metallocene catalyst polymerisation as above forms-(1-butylene) multipolymer demonstrates narrow molecular weight distribution.The molecular weight distribution (Mw/Mn) of above-mentioned amorphous propene-(1-butylene) multipolymer is preferably below 3, more preferably below 2, and more preferably 1.1～2, be particularly preferably 1.2～1.9.The low molecular weight compositions of the narrow amorphous propene of molecular weight distribution-(1-butylene) multipolymer is few, if therefore use such amorphous propene-(1-butylene) multipolymer, can obtain to prevent oozing out because of low molecular weight compositions the adhesive sheet that adherend is polluted.
In above-mentioned amorphous propene-(1-butylene) multipolymer, the ratio that contains of the structural unit that propylene is originated is preferably 80mol%～99mol%, more preferably 85mol%～99mol%, more preferably 90mol%～99mol%.
In above-mentioned amorphous propene-(1-butylene) multipolymer, the ratio that contains of the structural unit that 1-butylene is originated is preferably 1mol%～20mol%, more preferably 1mol%～15mol%, more preferably 1mol%～10mol%.If in such scope, can obtain the adhesive sheet of the balance excellence of toughness and flexibility.
Above-mentioned amorphous propene-(1-butylene) multipolymer can be segmented copolymer, also can be random copolymers.
The weight-average molecular weight (Mw) of above-mentioned amorphous propene-(1-butylene) multipolymer is preferably more than 200000, and more preferably 200000～500000, more preferably 200000～300000.The weight-average molecular weight (Mw) of amorphous propene-(1-butylene) multipolymer is if in such scope, compare with common polystyrene thermoplastic resin, acrylic acid series thermoplastic resin (Mw is below 100000), can obtain the adhesive sheet that low molecular weight compositions is few, can prevent the pollution of adherend.In addition, during co-extrusion modling, can form without the bad binder layer of processing, and, suitable bounding force can be obtained.
Above-mentioned amorphous propene-(1-butylene) multipolymer is preferably 1g/10min～50g/10min at 230 ℃, melt flow rate (MFR) during 2.16kgf, more preferably 5g/10min～30g/10min, more preferably 5g/10min～20g/10min.Amorphous propene-(1-butylene) is if the melt flow rate (MFR) of multipolymer in such scope, can form by co-extrusion modling the binder layer of and even thickness bad without processing.Melt flow rate (MFR) can be measured according to the method according to JIS K7210.
In the scope of not damaging effect of the present invention, above-mentioned amorphous propene-(1-butylene) multipolymer can also further comprise the structural unit that other monomers are originated.As other monomers, such as listing the alpha-olefins such as ethene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-Methyl-1-pentene etc.
Preferably, above-mentioned binder layer essence does not comprise F
-, Cl
-, Br
-, NO
2 -, NO
3 -, SO
4 2-, Li
+, Na
+, K
+, Mg
2+, Ca
2+, NH
4 +This is because can prevent that adherend is by this ionic soil.The adhesive sheet that possesses such binder layer for example is being used for the semiconductor crystal wafer processing used time, can not produce the broken string of circuit or short circuit etc.The binder layer that does not comprise above-mentioned ion for example can be by using as mentioned above metallocene catalyst to make to comprise in this binder layer amorphous propene-(1-butylene) multipolymer carry out solution polymerization and obtain.This uses in the solution polymerization of metallocene catalyst, amorphous propene-(1-butylene) multipolymer can use the poor solvent different from polymer solvent to repeat to separate out to separate (reprecipitation method) and purifying, therefore can obtain not containing the binder layer of above-mentioned ion.Need to prove, in this specification sheets, " essence does not comprise F
-, Cl
-, Br
-, NO
2 -, NO
3 -, SO
4 2-, Li
+, Na
+, K
+, Mg
2+, Ca
2+, NH
4 +" refer in the ion chromatography (for example, use Dionex company to make, commodity are called the ion chromatography of " DX-320 ", " DX-500 ") in standard lower than detectability.Particularly, refer to the binder layer with respect to 1g, F
-, Cl
-, Br
-, NO
2 -, NO
3 -, SO
4 2-And K
+Be respectively below 0.49 μ g Li
+And Na
+Be respectively below 0.20 μ g Mg
2+And Ca
2+Be respectively below 0.97 μ g NH
4 +It is the following situation of 0.5 μ g.
The storage modulus of above-mentioned binder layer (G ') be preferably 0.5 * 10
6Pa～1.0 * 10
8Pa, more preferably 0.8 * 10
6Pa～3.0 * 10
7Pa.The storage modulus of above-mentioned binder layer (G ') if in such scope, can obtain the adhesive sheet that the irregular adherend of effects on surface tool can have the separability of sufficient bounding force and appropriateness concurrently.In addition, the adhesive sheet that possesses the above-mentioned binder layer of such storage modulus (G ') is being used for the semiconductor crystal wafer processing used time, and in the time of can helping the back side grinding of wafer, the grinding accuracy of excellence reaches.Need to prove, and the storage modulus in the present invention (G ') can measure by the dynamic viscoelastic spectrometry.
It is resin that above-mentioned binder layer can comprise crystalline polypropylene.Be resin by comprising crystalline polypropylene, can reduce above-mentioned bounding force, increase above-mentioned storage modulus (G ').Crystalline polypropylene is containing ratio and can being set as suitable ratio arbitrarily according to bounding force and the storage modulus (G ') of expectation of resin.Be the gross weight of resin with respect to above-mentioned amorphous propene-(1-butylene) multipolymer and this crystalline polypropylene, crystalline polypropylene is that the ratio that contains of resin is preferably 0 % by weight～50 % by weight, more preferably 0 % by weight～40 % by weight.
Above-mentioned crystalline polypropylene is that resin can be homopolymer polypropylene, can be also by propylene and the multipolymer that can obtain with the monomer of copolymerization of propylene.As can with the monomer of copolymerization of propylene, such as listing the alpha-olefins such as ethene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-Methyl-1-pentene etc.Above-mentioned crystalline polypropylene is that resin is in situation by propylene and the multipolymer that can obtain with the monomer of copolymerization of propylene, can be random copolymers, also can be segmented copolymer.
Above-mentioned crystalline polypropylene be resin preferably, with above-mentioned amorphous propene-(1-butylene) multipolymer in the same manner, can obtain by using metallocene catalyst carry out polymerization.If using the crystalline polypropylene that obtains like this is resin, can prevent from because of oozing out of low molecular weight compositions, adherend being polluted.
Above-mentioned crystalline polypropylene is that the degree of crystallinity of resin is preferably more than 10%, more preferably more than 20%.Degree of crystallinity is representational is to utilize differential scanning calorimetric analysis (DSC) or X-ray diffraction to try to achieve.
In the scope of not damaging effect of the present invention, above-mentioned binder layer can further comprise other compositions.As this composition, such as listing antioxidant, UV light absorber, photostabilizer, heat-resisting stabilizing agent, static inhibitor etc.The kind of other compositions and usage quantity can suitably be selected according to purpose.
C. substrate layer
Above layer gets final product above-mentioned substrate layer so long as the difference of the anchor force of the adhesive sheet that obtains and bounding force is 1.0N/20mm, can use suitable resin arbitrarily.Above-mentioned substrate layer preferably comprises vinyl-vinyl acetate copolymer.
The weight-average molecular weight of above-mentioned vinyl-vinyl acetate copolymer (Mw) is preferably 10000～200000, and more preferably 30000～190000.If the weight-average molecular weight of vinyl-vinyl acetate copolymer (Mw) in such scope, can form when co-extrusion modling without the bad substrate layer of processing.
Above-mentioned vinyl-vinyl acetate copolymer is preferably 2g/10min～20g/10min at 190 ℃, melt flow rate (MFR) during 2.16kgf, more preferably 5g/10min～15g/10min, more preferably 7g/10min～12g/10min.If the melt flow rate (MFR) of vinyl-vinyl acetate copolymer in such scope, during co-extrusion modling, can form without the bad substrate layer of processing.
In the scope of not damaging effect of the present invention, above-mentioned substrate layer can further comprise other compositions.As these other compositions, for example can use the composition identical with illustrated binder layer other compositions that can comprise in above-mentioned B item.
D. can give stable on heating upper layer
Adhesive sheet of the present invention can further possess can give stable on heating upper layer.What this upper layer can be arranged on above-mentioned substrate layer is in a side of opposition side with binder layer.This upper layer preferably comprises polypropylene-based resin.
Above-mentioned polypropylene-based resin preferably obtains by the polymerization of using metallocene catalyst.More specifically, polypropylene-based resin for example can followingly obtain: use metallocene catalyst to make the polymerization process of the monomer composition polymerization that comprises propylene, after this polymerization process, carry out the postprocessing working procedures such as catalyzer removing step, foreign matter removing step.Polypropylene-based resin is through after such operation, to obtain such as shapes such as Powdered, particulate state.As metallocene catalyst, such as can list the even mixed catalyst of the metallocene that comprises metallocene compound and aikyiaiurnirsoxan beta, load has the metallocene loaded catalyst of metallocene compound etc. on microparticle support.
The polypropylene-based resin that uses as mentioned above metallocene catalyst polymerisation to obtain demonstrates narrow molecular weight distribution.Particularly, the molecular weight distribution of above-mentioned polypropylene-based resin (Mw/Mn) is preferably below 3, and more preferably 1.1～3, more preferably 1.2～2.9.The low molecular weight compositions of the polypropylene-based resin that molecular weight distribution is narrow is few, if therefore use such polypropylene-based resin, can prevent oozing out of low molecular weight compositions, obtains the adhesive sheet of spatter property excellence.Such adhesive sheet for example is suitable as semiconductor crystal wafer processing and uses.
The weight-average molecular weight of above-mentioned polypropylene-based resin (Mw) is preferably more than 50000, and more preferably 50000～500000, more preferably 50000～400000.The weight-average molecular weight of polypropylene-based resin (Mw) can prevent oozing out of low molecular weight compositions if in such scope, obtains the adhesive sheet of spatter property excellence.Such adhesive sheet for example is suitable for semiconductor crystal wafer processing.
The fusing point of above-mentioned polypropylene-based resin is preferably 110 ℃～200 ℃, more preferably 120 ℃～170 ℃.More preferably 125 ℃～160 ℃.If in such scope, just can obtain the adhesive sheet of excellent heat resistance.Adhesive sheet of the present invention possesses in the situation of upper layer of the polypropylene-based resin that comprises the fusing point with such scope, can access and have stable on heating adhesive sheet, even particularly for have bonding after heating, the adhesive sheet surface also is difficult to the adhesive sheet of the character of melting.Such adhesive sheet is particularly useful when Contact Heating.For example, in the situation that adhesive sheet uses as adhesive sheet for semiconductor wafer processing, the adhesive sheet surface is difficult for welding on the warm table of semiconductor-fabricating device, can prevent from processing bad.And then the adhesive sheet of this embodiment is on the basis of excellent heat resistance, and flexibility is also excellent as mentioned above.For the adhesive sheet of such thermotolerance and flexibility balance excellence, be for example useful as adhesive sheet for semiconductor wafer processing.The adhesive sheet for semiconductor wafer processing of the manufacture (that is, 2in1 manufacture) of more specifically, carrying out in online (in-line) mode as the operation that is used for finishing from back side grinding process to cutting action is useful.In such manufacture, provide adhesive sheet to back side grinding process and cutting action serially.If adhesive sheet of the present invention uses as the adhesive sheet for semiconductor wafer processing in the 2in1 manufacture, when pasting cutting film (or diced chip mounts film) with the back side of the semiconductor crystal wafer of adhesive sheet, even adhesive sheet contacts with warm table (for example 100 ℃), can prevent that also adhesive sheet surface welding is on warm table, and, can prevent the damage take the contact of this adhesive sheet as the semiconductor crystal wafer of cause.
The softening temperature of above-mentioned polypropylene-based resin is preferably 100 ℃～170 ℃, and more preferably 110 ℃～160 ℃, more preferably 120 ℃～150 ℃.If in such scope, just can obtain the adhesive sheet of excellent heat resistance.Need to prove, the softening temperature in this specification sheets refers to the value according to ring and ball method (JIS K6863) mensuration.
Above-mentioned polypropylene-based resin is preferably 3g/10min～30g/10min at 230 ℃, melt flow rate (MFR) during 2.16kgf, more preferably 5g/10min～15g/10min, more preferably 5g/10min～10g/10min.If the melt flow rate (MFR) of polypropylene-based resin in such scope, by co-extrusion modling, can form the upper layer without the bad even thickness of processing.Melt flow rate (MFR) can be measured by the method based on JIS K7210.
In the scope of not damaging effect of the present invention, above-mentioned polypropylene-based resin can further comprise the structural unit that other monomers are originated.As other monomer, such as listing the alpha-olefins such as ethene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-Methyl-1-pentene.Comprise in the situation of structural unit in other monomers sources, can be segmented copolymer, also can be random copolymers.
Above-mentioned polypropylene-based resin can use commercially available product.As the concrete example of commercially available polypropylene-based resin, can list Japan Polypropylene Co., the commodity that Ltd. makes " WINTEC " by name, " WELNEX " series etc.
In the scope of not damaging effect of the present invention, above-mentioned upper layer can also further comprise other compositions.As these other compositions, for example can use the composition identical with illustrated binder layer other compositions that can comprise in above-mentioned B item.
E. the making method of adhesive sheet
Adhesive sheet of the present invention is made the material co-extrusion modling that forms the material of above-mentioned binder layer and form above-mentioned substrate layer.The difference that can easily obtain anchor force and bounding force by co-extrusion modling is the adhesive sheet more than 1.0N/20mm.By utilizing co-extrusion modling to form adhesive sheet, make binder layer formation material and substrate layer form material and carry out stacked under molten state.Thus, think and to obtain the adhesive sheet that the cementability between binder layer and substrate layer improves, has excellent anchor force.In addition, can be with less process number and do not make the good adhesive sheet of adhesiveness between layers with an organic solvent.
In above-mentioned co-extrusion modling, the formation material of above-mentioned binder layer and above-mentioned substrate layer can use the material that the composition of above-mentioned each layer is mixed with any appropriate means.
Concrete grammar as above-mentioned co-extrusion modling, for example can list: at least 2 forcing machines that connect mould, supply with binder layer to 1 respectively and form material, supply with substrate layer to another 1 and form material, extrude after melting, utilize the touch roll method of forming to take out, be shaped to the method for duplexer.When extruding, each part that forms material interflow is preferably near mould outlet (mould lip).This is that respectively to form the interflow of material bad because be difficult for generation in mould.Therefore, as above-mentioned mould, preferably use the mould of branch manifold form.Need to prove, occur in the bad situation in interflow, the bad orders such as the interflow is inhomogeneous, particularly inhomogeneous for producing wavy outward appearance between the binder layer extruded and substrate layer occur, is not preferred.In addition, collaborate bad be large due to the difference of for example mobility (melt viscosity) of formation material not of the same race in mould, and the difference of the velocity of shear of the formation material of each layer produce greatly, if therefore use the mould of branch manifold form, compared with other forms (for example feed block (feed block) form), for the formation material not of the same race that poor fluidity is arranged, also can enlarge the scope that material is selected.The screw-type that is used for the forcing machine of each melting that forms material can be single shaft or 2 axles.Forcing machine also can be for more than 3.Forcing machine is in situation more than 3, can further supply with the formation material of other layer (for example can give stable on heating upper layer).In addition, in the situation of the adhesive sheet of forcing machine 2 layers of structure of making (substrate layer+binder layer) of use more than 3, supply with same formation material to adjacent forcing machine more than 2 and get final product, for example, when using 3 forcing machines, can supply with same to adjacent 2 forcing machines and form material.
Mold temperature in above-mentioned co-extrusion modling is preferably 160 ℃～220 ℃, more preferably 170 ℃～200 ℃.If in such scope, forming stability is excellent.
Above-mentioned binder layer forms 180 ℃ of temperature, the velocity of shear 100sec of material and above-mentioned substrate layer formation material
-1The time poor (binder layer forms material-substrate layer and forms material) of shear viscosity, be preferably-150Pas～600Pas more preferably-100Pas～550Pas, more preferably-50Pas～500Pas.If in such scope, the mobility in the mould of above-mentioned binder layer formation material and substrate layer formation material is close, can prevent from collaborating bad generation.Need to prove, shear viscosity can use the elongation viscosity instrumentation of double capillary (twin capillary) type fixed.
Embodiment
Below, illustrate the present invention by embodiment, but the present invention is not limited by these embodiment.Need to prove, the test in embodiment etc. and evaluation method are the following stated.In addition, part refers to weight part.
Embodiment 1
Form material as binder layer, the amorphous propene that use forms by metallocene catalyst polymerisation-(1-butylene) multipolymer (sumitomo chemical company manufacturing, commodity are called " TafthrenH5002 ": the structural unit 10mol% that the structural unit 90mol% that propylene is originated/1-butylene is originated, Mw=230,000, Mw/Mn=1.8).
Form material as substrate layer, use ethane-acetic acid ethyenyl ester polymkeric substance (commodity are called " EVAFLEXp-1007 " for Du Pont-Mitsui Co., Ltd. making).
100 parts of above-mentioned binder layers are formed material and 100 parts of substrate layers formation material inputs forcing machine separately, (forcing machine: GMENGINEERING company makes, trade(brand)name " GM30-28 "/T-shaped mould: feed block mode to carry out T-shaped mould melting coextrusion; 180 ℃ of extrusion temperatures), (Mitsubishi Chemical Ind makes with silicon coating PET barrier film to touch roll forming part paper feed with the resin of molten state, commodity are called " DiafoilMRF ": after 38 μ m) stacked, cooling, obtaining binder layer thickness is that 45 μ m, substrate layer thickness are the adhesive sheet of 85 μ m.Need to prove, the thickness of each layer is controlled by the shape of T-shaped mould outlet.
Embodiment 2
Except the thickness of the substrate layer that makes the adhesive sheet that obtains is the mode co-extrusion modling of 160 μ m, operation obtains adhesive sheet similarly to Example 1.
Embodiment 3
Except the thickness of the binder layer that makes the adhesive sheet that obtains is 65 μ m, the thickness of substrate layer is outside the mode co-extrusion modling of 140 μ m, and operation obtains adhesive sheet similarly to Example 1.
Embodiment 4
form material as binder layer, mix and use the 60 parts of amorphous propene that is polymerized by metallocene catalyst-(1-butylene) multipolymer (sumitomo chemical company manufacturings, commodity are called " TafthrenH5002 ": the structural unit 10mol% that the structural unit 90mol% that propylene is originated/1-butylene is originated, Mw=230000, Mw/Mn=1.8) and 40 parts of crystalline polypropylenes that are polymerized by metallocene catalyst are resin (Japan Polypropylene Co., Ltd. make, commodity are called " WINTEC WFX4 "), in addition, operation obtains adhesive sheet similarly to Example 1.
Comparative example 1
Under 25 ℃, drop into 100 parts of n-butyl acrylates, 3 parts of vinylformic acid, 0.1 part 2,2 '-Diisopropyl azodicarboxylate in the 500ml flask.Then, import nitrogen approximately 1 hour while stirring in flask, use the nitrogen replacement inner air.Then, the heating flask makes the flask interior temperature rise to 60 ℃, keeps approximately carrying out polymerization in 6 hours, obtains polymers soln
In 100 parts of polymers solns that obtain, add 2 parts of polyisocyanate compounds (Nippon Polyurethane Industry Co., Ltd. make, commodity are called " CORONATE L "), (Mitsubishi's gas chemistry is made for 0.5 part of multi-functional epoxy compound, commodity are called " tetrad C "), dilute with ethyl acetate on the limit, and the limit is stirred to evenly, obtains binder solution.
The binder solution that obtains is coated on the PET barrier film, and the use drying oven is distinguished dry 3 minutes under 70 ℃ and 130 ℃, and forming thickness is the binder layer of 15 μ m.Then, extrude in the mode that vinyl-vinyl acetate copolymer (commodity are called " EVAFLEXp-1007 " for Du Pont-Mitsui Co., the Ltd. manufacturing) thickness that forms material as substrate layer is 115 μ m, fit with this binder layer, obtain adhesive sheet.
Comparative example 2
Make the compounding composition copolymerization in toluene solution that comprises 0.3mol ethyl propenoate, 0.7mol butyl acrylate, reaches 0.3mol vinylformic acid-2-hydroxyl ethyl ester, obtain acrylic acid series copolymerized polymer solution.
With respect to 100 parts of acrylic acid series copolymerized polymer solution (solids component) that obtain, mixing 1 part of polyisocyanates is linking agent (Nippon Polyurethane Industry Co., Ltd. make, commodity are called " CORONATE L "), the preparation binder solution.
Be coated on the binder solution that obtains on the barrier film that the demoulding processed and after carrying out drying, form binder layer (thickness is 30 μ m).
At base material (Toray Industries, Inc. make, commodity are called " LumirrorS105 " (PET film), and thickness is 50 μ m) on extrude stacked ethylene-ethyl acrylate copolymer (EEA), obtain having the laminate film in EEA middle layer (thickness is 100 μ m).
The middle layer of the laminate film that obtains and above-mentioned binder layer are fitted obtain adhesive sheet.
Comparative example 3
As substrate layer, use the laminate film of propenoic methyl carbamate (AU) film (middle layer, thickness are 100 μ m) and PET film (thickness is 50 μ m), this AU film and binder layer are fitted, in addition operate equally with comparative example 1, obtain adhesive sheet.
Estimate
The adhesive sheet that obtains in embodiment and comparative example is carried out following evaluation.Result is as shown in table 1.
(1) bounding force
The roller round trip that makes 2kg is crimped on the binder layer of the adhesive sheet that obtains on Silicon Wafer, place after 30 minutes, (Tamsui corporation makes to use the peeling strength test machine, tensile testing machine), carry out 180 ° of stripping tests (peeling rate is 300mm/min), measure bounding force.
(2) anchor force
The adhesive sheet of gained is cut to 20mm wide, makes test film.The binder layer crimping of the binder layer of this test film and commercially available peeling off adhesive tape (a day eastern electrician (strain) makes, trade(brand)name " BT-315 ").Use peeling strength test machine (Tamsui corporation makes, tensile testing machine), carry out T-shaped stripping test (peeling rate 300mm/min), measure anchor force.
(3) cutting chip number
Use NITTO SEIKO CO., the adhesive tape sticking device " DR-3000II " that LTD. makes sticks on the adhesive sheet that obtains on Silicon Wafer (thickness is 725 μ m).The quantity of the cutting chip that the periphery of the adhesive sheet after visual instrumentation is pasted is accompanying.Make 10 wafers that are pasted with adhesive sheet, with the mean values of 10 as cutting chip number.
(4) wafer grinding test
With the wafer that is pasted with adhesive sheet of making in above-mentioned (3), use wafer grinding attachment (Disco company make, " DFG8560 ") to be ground to wafer thickness and become 50 μ m.Then, release adhesive sheet from the wafer, Visual Confirmation has or not wafer to break and the edge section crackle.
Table 1
The difference of anchor force and bounding force is not produce the cutting chip in the above embodiment 1～4 of 1.0N/20mm.And then, do not confirm and produce that wafer breaks and the wafer of Edge crack after the wafer grinding.There is no the adhesive bonding agent on wafer after the stickup adhesive sheet and the wafer after the release adhesive sheet, can prevent the pollution of crystal column surface.
On the other hand, in the comparative example 1～3 of the difference of anchor force and bounding force lower than 1.0N/20mm, produce fragment during cutting, can confirm to have on adhesive sheet more cutting chip.In addition, can confirm after the wafer grinding and to produce that wafer breaks and the wafer of Edge crack.The adhesive sheet anchor force of comparative example 1～3 is little, is attached with fragment and/or tackiness agent on the wafer after the stickup adhesive sheet and the wafer after the release adhesive sheet.
Utilizability on industry
Adhesive sheet of the present invention is such as the protection that goes for the workpiece (semiconductor crystal wafer etc.) of semiconductor device when making.
Claims (6)
1. adhesive sheet, it possesses binder layer and substrate layer, binder layer is formed material and substrate layer forms the material co-extrusion modling and obtains,
The difference of the anchor force of this binder layer and this substrate layer and the bounding force of this binder layer is more than 1.0N/20mm.
2. adhesive sheet according to claim 1, wherein, described binder layer comprises polyolefin-based resins.
3. adhesive sheet according to claim 2, wherein, described polyolefin-based resins comprises the amorphous propene that uses metallocene catalyst polymerisation to form-(1-butylene) multipolymer.
4. the described adhesive sheet of any one according to claim 1～3, wherein, described substrate layer comprises vinyl-vinyl acetate copolymer.
5. the described adhesive sheet of any one according to claim 1～4, its thickness is 5 μ m～1000 μ m.
6. the described adhesive sheet of any one according to claim 1～5, it is used for semiconductor crystal wafer processing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011277806A JP2013129686A (en) | 2011-12-20 | 2011-12-20 | Adhesive sheet |
| JP2011-277806 | 2011-12-20 |
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| Publication Number | Publication Date |
|---|---|
| CN103173149A true CN103173149A (en) | 2013-06-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105589973A Pending CN103173149A (en) | 2011-12-20 | 2012-12-20 | Bonding sheet |
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| Country | Link |
|---|---|
| JP (1) | JP2013129686A (en) |
| CN (1) | CN103173149A (en) |
| TW (1) | TWI540196B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289588A (en) * | 2012-03-02 | 2013-09-11 | 日东电工株式会社 | Adhesive sheet |
| CN103305146A (en) * | 2012-03-12 | 2013-09-18 | 日东电工株式会社 | Adhesive sheet |
| CN105622805A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | 1-butylene polymer preparation method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5970191B2 (en) * | 2012-01-13 | 2016-08-17 | 日東電工株式会社 | Adhesive tape |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008087169A (en) * | 2006-09-29 | 2008-04-17 | Sumitomo Chemical Co Ltd | Pressure-sensitive adhesive film and its manufacturing method |
| CN102190974A (en) * | 2010-03-01 | 2011-09-21 | 日东电工株式会社 | Protective sheet and use thereof |
| CN102399504A (en) * | 2010-09-16 | 2012-04-04 | 日东电工株式会社 | Pressure-sensitive adhesive tape |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005068420A (en) * | 2003-08-07 | 2005-03-17 | Mitsui Chemicals Inc | Pressure-sensitive adhesive sheet |
| JP2006143948A (en) * | 2004-11-24 | 2006-06-08 | Sumitomo Chemical Co Ltd | Adhesive, and laminated film or sheet made of adhesive |
| JP2008208173A (en) * | 2007-02-23 | 2008-09-11 | Nitto Denko Corp | Surface protecting sheet |
-
2011
- 2011-12-20 JP JP2011277806A patent/JP2013129686A/en active Pending
-
2012
- 2012-10-12 TW TW101137834A patent/TWI540196B/en not_active IP Right Cessation
- 2012-12-20 CN CN2012105589973A patent/CN103173149A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008087169A (en) * | 2006-09-29 | 2008-04-17 | Sumitomo Chemical Co Ltd | Pressure-sensitive adhesive film and its manufacturing method |
| CN102190974A (en) * | 2010-03-01 | 2011-09-21 | 日东电工株式会社 | Protective sheet and use thereof |
| CN102399504A (en) * | 2010-09-16 | 2012-04-04 | 日东电工株式会社 | Pressure-sensitive adhesive tape |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289588A (en) * | 2012-03-02 | 2013-09-11 | 日东电工株式会社 | Adhesive sheet |
| CN103305146A (en) * | 2012-03-12 | 2013-09-18 | 日东电工株式会社 | Adhesive sheet |
| CN103305146B (en) * | 2012-03-12 | 2016-10-26 | 日东电工株式会社 | Bonding sheet |
| CN105622805A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | 1-butylene polymer preparation method |
| CN105622805B (en) * | 2014-10-30 | 2018-05-15 | 中国石油化工股份有限公司 | A kind of preparation method of 1- butene polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI540196B (en) | 2016-07-01 |
| JP2013129686A (en) | 2013-07-04 |
| TW201333144A (en) | 2013-08-16 |
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Application publication date: 20130626 |