CN111373509A - Support sheet and composite sheet for forming protective film - Google Patents
Support sheet and composite sheet for forming protective film Download PDFInfo
- Publication number
- CN111373509A CN111373509A CN201880075847.2A CN201880075847A CN111373509A CN 111373509 A CN111373509 A CN 111373509A CN 201880075847 A CN201880075847 A CN 201880075847A CN 111373509 A CN111373509 A CN 111373509A
- Authority
- CN
- China
- Prior art keywords
- protective film
- forming
- film
- meth
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001681 protective effect Effects 0.000 title claims abstract description 577
- 239000002131 composite material Substances 0.000 title claims abstract description 184
- 239000012790 adhesive layer Substances 0.000 claims abstract description 197
- 239000000463 material Substances 0.000 claims abstract description 95
- 238000012360 testing method Methods 0.000 claims abstract description 79
- 239000000853 adhesive Substances 0.000 claims description 276
- 239000010410 layer Substances 0.000 claims description 205
- 239000000758 substrate Substances 0.000 claims description 119
- 239000000203 mixture Substances 0.000 description 280
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 248
- 230000001070 adhesive effect Effects 0.000 description 174
- 229920001187 thermosetting polymer Polymers 0.000 description 112
- 150000001875 compounds Chemical class 0.000 description 110
- 239000002904 solvent Substances 0.000 description 90
- 239000000178 monomer Substances 0.000 description 86
- 239000003431 cross linking reagent Substances 0.000 description 85
- -1 polyethylene Polymers 0.000 description 84
- 239000002585 base Substances 0.000 description 79
- 229920000642 polymer Polymers 0.000 description 69
- 125000000524 functional group Chemical group 0.000 description 62
- 238000000034 method Methods 0.000 description 61
- 239000004065 semiconductor Substances 0.000 description 58
- 229920000058 polyacrylate Polymers 0.000 description 57
- 239000000654 additive Substances 0.000 description 56
- 229920005989 resin Polymers 0.000 description 56
- 239000011347 resin Substances 0.000 description 56
- 239000004840 adhesive resin Substances 0.000 description 51
- 229920006223 adhesive resin Polymers 0.000 description 51
- 239000000049 pigment Substances 0.000 description 46
- 238000001723 curing Methods 0.000 description 45
- 238000004519 manufacturing process Methods 0.000 description 42
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- 239000004925 Acrylic resin Substances 0.000 description 39
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 37
- 239000003086 colorant Substances 0.000 description 33
- 239000003999 initiator Substances 0.000 description 33
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- 238000003860 storage Methods 0.000 description 31
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 29
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
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- 238000004804 winding Methods 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 12
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 12
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 11
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- 238000003825 pressing Methods 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 230000002093 peripheral effect Effects 0.000 description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 238000013007 heat curing Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 235000000126 Styrax benzoin Nutrition 0.000 description 5
- 244000028419 Styrax benzoin Species 0.000 description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 235000019382 gum benzoic Nutrition 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 5
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Abstract
The present invention provides a support sheet which comprises a base material and an adhesive layer on the base material, wherein the surface of the base material on the adhesive layer side is an uneven surface, a test piece is cut from 5 positions of the support sheet, and when the cross section of the adhesive layer in the 5 test pieces is observed, the average value (R value) of the ratio of (the sum of the linear distances between adjacent sharp peaks)/(the linear distance in the direction horizontal to the adhesive layer) is 1.5 or more and less than 5.0. The invention provides a composite sheet for forming a protective film, which is provided with a film for forming a protective film on an adhesive layer in the support sheet.
Description
Technical Field
The present invention relates to a support sheet and a composite sheet for forming a protective film.
Background
In recent years, semiconductor devices have been manufactured using a mounting method called a flip-chip (face down) method. In the flip chip system, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.
A resin film containing an organic material as a protective film is formed on the back surface of the exposed semiconductor chip, and the resin film may be incorporated into a semiconductor device as a semiconductor chip with a protective film. The protective film is used to prevent cracks from being generated on the semiconductor chip after the dicing process or the packaging.
Such a protective film can be formed by curing a curable protective film-forming film, for example. In addition, a non-curable film for forming a protective film, the physical properties of which have been adjusted, may be used as the protective film as it is. Then, a film for forming a protective film is used by being attached to the back surface of the semiconductor wafer. The protective film-forming film may be attached to the back surface of the semiconductor wafer in a state of, for example, a composite sheet for forming a protective film integrated with a support sheet used in processing the semiconductor wafer, or may be attached to the back surface of the semiconductor wafer in a state of not being integrated with the support sheet.
After the composite sheet for forming a protective film is attached to the back surface of the semiconductor chip via the film for forming a protective film, it is appropriate to: forming a protective film by curing the protective film-forming film, cutting the protective film-forming film or the protective film, dividing (dicing) the semiconductor wafer into semiconductor chips, picking up the semiconductor chips (semiconductor chips with protective film-forming film or semiconductor chips with protective film) having the cut protective film-forming film or protective film on the back surface from the support sheet, and the like. When the semiconductor chip with the film for forming a protective film is picked up, the semiconductor chip with the protective film is produced by curing the film for forming a protective film, and finally the semiconductor device is manufactured using the semiconductor chip with the protective film. In this manner, the support sheet in the composite sheet for forming a protective film can be used as a dicing sheet. In the case where the protective film-forming film is non-curable, the protective film-forming film is regarded as a protective film in each of the above steps.
On the other hand, after the protective film forming film is attached to the back surface of the semiconductor wafer in a state not integrated with the support sheet, the support sheet is attached to an exposed surface of the protective film forming film on the opposite side to the attachment surface of the semiconductor wafer. Then, a semiconductor chip with a protective film or a semiconductor chip with a film for forming a protective film is obtained in the same manner as in the case of using the composite sheet for forming a protective film, and a semiconductor device is manufactured. In this case, the protective film-forming film is attached to the back surface of the semiconductor wafer in a state of not being integrated with the support sheet, but the protective film-forming composite sheet is constituted by integrating with the support sheet after the attachment.
As such a composite sheet for forming a protective film, for example, a dicing tape-integrated film for protecting a semiconductor back surface (composite sheet for forming a protective film) is disclosed, which comprises a dicing tape (support sheet) having a base material having a rough processed surface and an adhesive layer laminated on the rough processed surface side of the base material, and a film for protecting a semiconductor back surface (protective film-forming film) laminated on the adhesive layer of the dicing tape, and which has a haze of 45% or less (see patent document 1).
However, in the composite sheet for forming a protective film (dicing tape-integrated semiconductor back surface protection film) disclosed in patent document 1, since the adhesive layer is laminated on the uneven work surface side of the substrate, the adhesive does not sufficiently follow the unevenness of the substrate, and a region where the substrate and the adhesive are not bonded (non-bonded region) may be generated between the substrate and the adhesive. In addition, although printing may be performed on the surface of the protective film or the protective film-forming film on the adhesive layer side by laser irradiation, the visibility of the printing through the substrate and the adhesive layer may be reduced due to the uneven shape of the adhesive layer.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5432853
Disclosure of Invention
Technical problem to be solved by the invention
The present invention aims to provide a support sheet and a composite sheet for forming a protective film provided with the support sheet, wherein the support sheet is configured by providing an adhesive layer on the uneven surface side of a base material, and in the composite sheet for forming a protective film provided with the film for forming a protective film on the adhesive layer of the support sheet, good adhesion between the base material and the adhesive and good printing visibility of the protective film or the film for forming a protective film through the support sheet can be realized.
Means for solving the problems
The present invention provides a support sheet comprising a base material and an adhesive agent layer on the base material, wherein the surface of the base material on the adhesive agent layer side is a concave-convex surface, a test piece is cut from 5 positions of the support sheet, and when the cross section of the adhesive agent layer in the 5 test pieces is observed, the average value of the ratio of (the sum of linear distances between adjacent sharp vertexes)/(the linear distance in the direction horizontal to the adhesive agent layer) is 1.5 or more and less than 5.0.
In the support sheet of the present invention, the adhesive layer may be in direct contact with the uneven surface of the base material.
The present invention also provides a composite sheet for forming a protective film, which comprises a film for forming a protective film on the adhesive layer in the support sheet.
Effects of the invention
By forming the protective film-forming composite sheet using the support sheet of the present invention, it is possible to achieve good adhesion between the substrate and the adhesive and good printing visibility of the protective film or the protective film-forming film through the support sheet.
Drawings
Fig. 1 is a cross-sectional view schematically showing a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film and a support sheet according to an embodiment of the present invention.
Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film and a support sheet according to an embodiment of the present invention.
Fig. 4 is an enlarged cross-sectional view of the support sheet and the composite sheet for forming a protective film shown in fig. 1.
Fig. 5 is an enlarged cross-sectional view of the support sheet and the composite sheet for forming a protective film shown in fig. 1.
Detailed Description
◇ supporting sheet and composite sheet for forming protective film
A support sheet according to one embodiment of the present invention includes a base material, and an adhesive agent layer is provided on the base material, a surface of the base material on the adhesive agent layer side is an uneven surface, a test piece is cut from 5 positions of the support sheet, and when a cross section of the adhesive agent layer in the 5 test pieces is observed, an average value (in the present specification, sometimes referred to as an "R value") of a ratio of (a total of linear distances between adjacent sharp vertices)/(a linear distance in a direction horizontal to the adhesive agent layer) is 1.5 or more and less than 5.0.
In the present specification, when a cross section of the adhesive agent layer is observed, if a step difference between a top of a convex portion of the adhesive agent layer on the substrate side, which changes from a descending state to an ascending state, and a deepest portion of a concave portion of the adhesive agent layer on the substrate side, which changes from an ascending state to a descending state, is 1 μm or more, the step is regarded as being conspicuous, the top portion having the conspicuous step is set as a conspicuous apex of the convex portion, the deepest portion having the conspicuous step is set as a conspicuous apex of the concave portion, the distance between adjacent sharp vertices of the convex portions and the concave portions connected by a straight line is defined as "the straight line distance between adjacent sharp vertices", and the total of the straight line distances between adjacent sharp vertices of the observation target is defined as "the total of the straight line distances between adjacent sharp vertices". In addition, the apparent apex of the observation target is projected onto a plane in the direction horizontal to the adhesive agent layer, and the distance from the start point to the end point of the projected point is defined as "the straight-line distance in the direction horizontal to the adhesive agent layer".
When the cross section of the adhesive agent layer is observed, the average value (R value) of the ratio of (the sum of the linear distances between adjacent sharp vertices)/(the linear distance in the direction horizontal to the adhesive agent layer) is 1.5 or more, whereby the adhesion between the substrate and the adhesive agent is improved. When the R value is less than 5.0, diffraction of the transmitted light at the adhesive-substrate interface can be suppressed, and good printing visibility of the protective film or the protective film-forming film via the support sheet can be achieved.
In a case where a test piece is cut from 5 of the support sheet and the minimum value and the maximum value of the thickness of the adhesive agent layer in the 5 test pieces are respectively obtained, it is preferable that the average value of the minimum values (in this specification, sometimes referred to as "S value") is 1.5 μm or more and the average value of the maximum values (in this specification, sometimes referred to as "L value") is 9 μm or less.
In addition, the composite sheet for forming a protective film according to one embodiment of the present invention includes a film for forming a protective film on the adhesive layer in the support sheet.
Further, by setting the S value of the adhesive agent layer to 1.5 μm or more, the laminating property of the adhesive agent layer and the film for forming a protective film is easily improved. In this specification, unless otherwise specified, "stackability" refers to the degree of normality of the stacking state of two layers as objects. "good lamination properties" means, for example, that there is no non-bonded region (void) between two adjacent layers to be subjected to lamination, or that the number of non-bonded regions is small and the interlayer distance of the non-bonded regions is small.
On the other hand, when the L value of the adhesive agent layer is 9 μm or less, the protective film or the protective film-forming film is likely to have good printing visibility through the support sheet.
The test piece was obtained by cutting the support sheet at the position 5 and cutting the entire area in the thickness direction of the support sheet. The test piece is a thin piece having all layers constituting the support sheet.
The size of the test piece is not particularly limited, and the length of one side of the laminated surface or exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece is preferably 2mm or more. By using a test piece having such a size, the R value, S value, and L value of the adhesive agent layer can be obtained with higher accuracy.
The maximum value of the length of the one side is not particularly limited. For example, the length of the side is preferably 10mm or less in order to facilitate the production of a test piece.
The planar shape of the test piece, that is, the shape of the laminated surface or exposed surface of each layer (substrate, adhesive agent layer, etc.) constituting the test piece is preferably polygonal, and more preferably rectangular in view of easier cutting of the test piece.
Examples of preferred test pieces include rectangular test pieces having a laminated surface or an exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece of 3mm × 3mm in size.
The position of the 5-point position where the test piece is cut from the support sheet is not particularly limited, but may be selected in consideration of the position to be laminated of the protective film-forming film described later in order to obtain the R value, S value, and L value of the adhesive agent layer with higher accuracy.
For example, the following 5 points may be listed: a position 1 where a center (center of gravity) portion of the protective film forming film is to be arranged, among positions of the support sheet where 1 protective film forming film is to be laminated; and 4 positions which are predetermined to be arranged at positions close to the peripheral edge part of the protective film forming film and are point-symmetric with respect to the center (center of gravity) part.
In the support sheet, the distance between the centers (centers of gravity) of the cut positions of the test pieces is preferably 50 to 200 mm. By setting in this manner, the R value, S value, and L value of the adhesive agent layer can be obtained with higher accuracy.
In order to determine the R value of the adhesive layer from the test piece, a new cross section was formed in the test piece, and in the formed cross section, the total of the linear distances between adjacent sharp vertices of each test piece and the linear distance in the direction horizontal to the adhesive layer were measured.
The newly formed cross section of 1 test piece may be only 1 plane, or 2 or more planes, and usually only 1 plane is sufficient.
The R value may be calculated from the sum of the linear distances between at least 5 adjacent distinct vertices and the linear distance in the direction horizontal to the adhesive agent layer.
In order to obtain the S value and L value of the adhesive layer from the test piece, a new cross section was formed in the test piece, and the minimum value and the maximum value of the thickness of the adhesive layer of each test piece were measured in the formed cross section.
The newly formed cross section of 1 test piece may be only 1 plane, or 2 or more planes, and usually only 1 plane is sufficient.
Then, the S value and the L value may be calculated from the at least 5 minimum values and maximum values.
The cross section can be formed in the test piece by a known method. For example, by using a known Cross-Section sample preparation apparatus (Cross Section Polisher), it is possible to form a Cross Section in a test piece with high reproducibility while suppressing variations.
The total linear distance between adjacent sharp vertices of the adhesive agent layer and the linear distance in the direction horizontal to the adhesive agent layer can be measured, for example, by image processing of the cross section of the test piece using a Scanning Electron Microscope (SEM).
The minimum value and the maximum value of the thickness of the adhesive layer can be measured by observing the cross section of the test piece using a Scanning Electron Microscope (SEM), for example.
In the cross section of each test piece, the region for measuring the total linear distance between adjacent sharp vertices and the linear distance in the direction horizontal to the adhesive layer is preferably a region of 50 to 1500 μm in the direction orthogonal to the lamination direction of each layer (substrate, adhesive layer, etc.) constituting the test piece (direction substantially parallel to the lamination surface or exposed surface of each layer). In the case of cutting a test piece from the elongated support sheet and protective film-forming composite sheet, the cross section is preferably cut in the width direction of the elongated support sheet and protective film-forming composite sheet. By setting in this manner, the total of the linear distances between adjacent sharp peaks and the linear distance in the direction horizontal to the adhesive agent layer can be measured efficiently and with high accuracy. The measurement of the minimum value and the maximum value of the thickness of the adhesive layer is also the same.
In the calculation of the R value, it is not always the case that there are several groups of distinct vertices in the observation region of the cross section of the test piece as "the sum of the linear distances between adjacent distinct vertices". For example, when the observation area of the cross section of the test piece is set to be an area of 1mm, the apparent vertices may be 50 to 500 groups, 75 to 250 groups, or 100 to 200 groups.
When a test piece is cut out from the support sheet at a stage where the composite sheet for forming a protective film is not formed and the support sheet for forming a protective film is formed, and the average value (R value) of the ratio of (the total of the linear distances between adjacent sharp vertices)/(the linear distance in the direction horizontal to the adhesive layer) of the surface on the substrate side of the adhesive layer is compared, these R values are the same as each other, or the R value of the support sheet for forming a protective film is slightly smaller, and even when this is smaller, the difference is negligible.
When the minimum values of the thicknesses of the adhesive layer of the support sheet at the stage where the composite sheet for forming a protective film is not formed and the support sheet for forming a protective film are compared, these minimum values are the same, or the minimum value of the support sheet for forming a protective film is slightly smaller, and even when this is smaller, the difference is negligible.
The same applies to the maximum thickness of the adhesive layer. That is, when the maximum values of the thicknesses of the adhesive layer of the support sheet at the stage where the composite sheet for forming a protective film is not formed and the support sheet for forming a protective film are compared, these maximum values are the same or the maximum value of the thickness of the adhesive layer of the support sheet for forming a protective film is slightly smaller, and even when this is smaller, the difference is negligible.
Therefore, the R value may be obtained by the same method as when the test piece cut from the support sheet is used, and the S value and the L value of the adhesive layer may be obtained by using the test piece cut from the protective film-forming composite sheet instead of the test piece cut from the support sheet. When a test piece cut out from the composite sheet for forming a protective film is used in this manner, the composite sheet for forming a protective film exhibits the above-described effects of the present invention when the R value is 1.5 or more and less than 5.0.
That is, the composite sheet for forming a protective film according to one embodiment of the present invention includes a film for forming a protective film on an adhesive layer in the support sheet, and when a test piece is cut from 5 positions of the composite sheet for forming a protective film and a cross section of the adhesive layer in the 5 test pieces is observed, an average value (R value) of a ratio of (a total of linear distances between adjacent distinct vertices)/(a linear distance in a direction horizontal to the adhesive layer) is 1.5 or more and less than 5.0.
Similarly, the S value and the L value of the adhesive agent layer may be determined by the same method as when the test piece cut from the support sheet is used, using a test piece cut from the protective film forming composite sheet, not a test piece cut from the support sheet at a stage where the protective film forming composite sheet is not constituted. When a test piece cut out from the composite sheet for forming a protective film is used in this manner, the composite sheet for forming a protective film easily exhibits the above-described effects of the present invention when the S value of the adhesive agent layer is 1.5 μm or more and the L value of the adhesive agent layer is 9 μm or less.
That is, when the composite sheet for forming a protective film according to one embodiment of the present invention is provided with a film for forming a protective film on an adhesive layer in the support sheet, and a test piece is cut from 5 positions of the composite sheet for forming a protective film, and the minimum value and the maximum value of the thickness of the adhesive layer in the 5 test pieces are obtained, it is preferable that the average value (S value) of the minimum values is 1.5 μm or more and the average value (L value) of the maximum values is 9 μm or less.
The test piece cut out from the composite sheet for forming a protective film is obtained by cutting the composite sheet for forming a protective film over the entire region in the thickness direction thereof, and is a thin piece having all the layers constituting the composite sheet for forming a protective film.
The overall structure of the composite sheet for forming a protective film of the present invention will be described below with reference to the drawings. For the sake of easy understanding of the features of the present invention, important parts of the drawings used in the following description may be enlarged for convenience, and the dimensional ratios of the respective components are not necessarily the same as those in the actual case.
Fig. 1 is a cross-sectional view schematically showing a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention.
The composite sheet 1A for forming a protective film shown here includes a substrate 11, an adhesive layer 12 on the substrate 11, and a film 13 for forming a protective film on the adhesive layer 12. The support sheet 10 is a laminate of a base material 11 and an adhesive layer 12, in other words, the composite sheet 1A for forming a protective film has a structure in which a protective film forming film 13 is laminated on one surface (in this specification, sometimes referred to as "first surface") 10a of the support sheet 10. The protective film forming composite sheet 1A further includes a release film 15 on the protective film forming film 13.
In the composite sheet 1A for forming a protective film, the adhesive layer 12 is laminated on one surface (in this specification, sometimes referred to as "first surface") 11A of the substrate 11, the film 13 for forming a protective film is laminated on the entire surface of a surface (in this specification, sometimes referred to as "first surface") 12a of the adhesive layer 12 opposite to the substrate 11 side, the adhesive layer 16 for a jig is laminated on a part of the surface (in this specification, sometimes referred to as "first surface") 13a of the film 13 for forming a protective film opposite to the adhesive layer 12 side, that is, a region near the peripheral edge, and the release film 15 is laminated on a surface (upper surface and side surfaces) of the first surface 13a of the film 13 for forming a protective film, on which the adhesive layer 16 for a jig is not laminated, and on a surface 16a (upper surface and side surfaces) of the adhesive layer 16 for a jig, which is not in contact with the film 13 for forming a protective film.
In fig. 1, reference numeral 13b denotes a surface (in this specification, may be referred to as a "second surface") of the protective film forming film 13 on the adhesive agent layer 12 side.
The pressure-sensitive adhesive layer 16 for a jig may have a single-layer structure containing a pressure-sensitive adhesive component, for example, or may have a multilayer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet serving as a core material.
In the composite sheet 1A for forming a protective film, the first surface 11A of the base material 11 is an uneven surface.
The adhesive layer 12 is provided on the first surface (uneven surface) 11a of the substrate 11 so as to be in direct contact therewith. Therefore, the surface 12b of the adhesive layer 12 on the substrate 11 side (in this specification, may be referred to as "second surface") is an uneven surface.
In the composite sheet 1A for forming a protective film, the surface (in this specification, sometimes referred to as "second surface") 11b of the base material 11 on the side opposite to the adhesive layer 12 may be any of an uneven surface and a smooth surface (non-uneven surface, bright surface), but is preferably a smooth surface. The second surface 11b of the base material 11 may be referred to as a surface (in this specification, may be referred to as "second surface") 10b of the support sheet 10 opposite to the protective film forming film 13.
The "uneven surface" and the "smooth surface" will be described in detail later.
The composite sheet 1A for forming a protective film shown in fig. 1 is used in the following manner: in the state where the release film 15 is removed, the back surface of the semiconductor wafer (not shown) is attached to the first surface 13a of the protective film forming film 13, and further, the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.
Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film and a support sheet according to another embodiment of the present invention.
In the drawings subsequent to fig. 2, the same reference numerals as those in the already-described drawings are assigned to the same components as those shown in the already-described drawings, and detailed description thereof is omitted.
The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in fig. 1, except that it does not include the pressure-sensitive adhesive layer 16 for a jig. That is, in the protective film forming composite sheet 1B, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, the protective film forming film 13 is laminated on the entire first surface 12a of the adhesive layer 12, and the release film 15 is laminated on the entire first surface 13a of the protective film forming film 13.
In the composite sheet 1B for forming a protective film, the first surface 11a of the base material 11 is also an uneven surface.
The adhesive layer 12 is provided on the first surface (uneven surface) 11a of the substrate 11 so as to be in direct contact therewith. Therefore, the surface (second surface) 12b of the adhesive layer 12 on the substrate 11 side is an uneven surface.
In the composite sheet 1B for forming a protective film, the second surface 11B of the base material 11 (in other words, the second surface 10B of the support sheet 10) may be either a rough surface or a smooth surface (non-rough surface), but is preferably a smooth surface.
The composite sheet 1B for forming a protective film shown in fig. 2 is used in the following manner: in the state where the release film 15 is removed, the back surface of the semiconductor wafer (not shown) is attached to a partial region on the center side of the first surface 13a of the protective film forming film 13, and further, a region near the peripheral edge portion is attached to a jig such as a ring frame.
Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film and a support sheet according to still another embodiment of the present invention.
The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1B for forming a protective film shown in fig. 2, except that the shape of the film for forming a protective film is different. That is, the composite sheet 1C for forming a protective film includes a substrate 11, an adhesive layer 12 on the substrate 11, and a film 23 for forming a protective film on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, in other words, the composite sheet for forming a protective film 1C has a structure in which the protective film 23 is laminated on the first surface (surface on the protective film 23 side) 10a of the support sheet 10. The composite sheet for forming a protective film 1C further includes a release film 15 on the film for forming a protective film 23.
In the protective film forming composite sheet 1C, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film forming film 23 is laminated on a central region, which is a part of the first surface 12a of the adhesive layer 12. The release film 15 is laminated on the first surface 12a of the adhesive agent layer 12 on the surface 23a (upper surface and side surface) of the protective film forming film 23 not in contact with the adhesive agent layer 12, in the region where the protective film forming film 23 is not laminated.
In fig. 3, reference numeral 23b denotes a surface (in this specification, may be referred to as a "second surface") of the protective film forming film 23 on the adhesive agent layer 12 side.
When the composite sheet for forming a protective film 1C is viewed from above in a downward direction, the surface area of the film for forming a protective film 23 is smaller than that of the adhesive agent layer 12, and has a shape such as a circle.
In the composite sheet 1C for forming a protective film, the first surface 11a of the base material 11 is also an uneven surface.
The adhesive layer 12 is provided on the first surface (uneven surface) 11a of the substrate 11 so as to be in direct contact therewith. Therefore, the surface (second surface) 12b of the adhesive layer 12 on the substrate 11 side is an uneven surface.
In the composite sheet 1C for forming a protective film, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be either a rough surface or a smooth surface (non-rough surface), but is preferably a smooth surface.
The composite sheet 1C for forming a protective film shown in fig. 3 is used in the following manner: in the state where the release film 15 is removed, the back surface of the semiconductor wafer (not shown) is attached to the surface 23a of the protective film forming film 23, and further, the region of the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated is attached to a jig such as a ring frame.
In the composite sheet 1C for forming a protective film shown in fig. 3, a pressure-sensitive adhesive layer for a jig (not shown) may be laminated on a region where the film 23 for forming a protective film is not laminated in the first surface 12a of the pressure-sensitive adhesive layer 12 in the same manner as in the composite sheet 1A for forming a protective film shown in fig. 1. The composite sheet 1C for forming a protective film having such a binder layer for a jig is used by attaching the upper surface of the binder layer for a jig to a jig such as a ring frame, as in the composite sheet for forming a protective film shown in fig. 1.
In this way, the composite sheet for forming a protective film can be provided with the pressure-sensitive adhesive layer for a jig regardless of the form of the support sheet and the film for forming a protective film. However, as shown in fig. 1, a protective film-forming composite sheet having a jig adhesive layer on a protective film-forming film is generally preferred.
The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to the composite sheet shown in fig. 1 to 3, and a composite sheet having a part of the composite sheet for forming a protective film shown in fig. 1 to 3 may be modified or deleted, or a composite sheet having another configuration may be added to the composite sheet for forming a protective film described above, within a range not to impair the effects of the present invention.
For example, in the composite sheet for forming a protective film shown in fig. 1 to 3, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet can be configured by sequentially laminating the base material, the intermediate layer, and the adhesive layer in the thickness direction thereof. As the intermediate layer, any intermediate layer can be selected according to the purpose.
The composite sheet for forming a protective film shown in fig. 1 to 3 may be provided with a layer other than the intermediate layer at an arbitrary position.
In addition, in the composite sheet for forming a protective film, a part of a gap may be generated between the release film and a layer directly contacting the release film.
In the composite sheet for forming a protective film, the size and shape of each layer can be arbitrarily adjusted according to the purpose.
As shown in fig. 1 to 3, in the composite sheet for forming a protective film, the adhesive layer is preferably in direct contact with the uneven surface (first surface) of the substrate, in other words, preferably, an intermediate layer is not provided between the substrate and the adhesive layer, and the adhesive layer is preferably laminated on the substrate in direct contact with the substrate.
In the protective film-forming composite sheet, the protective film-forming film is preferably in direct contact with the first surface of the adhesive agent layer, in other words, the protective film-forming film is preferably laminated on the adhesive agent layer in direct contact with the adhesive agent layer without providing another layer between the adhesive agent layer and the protective film-forming film.
Further, the composite sheet for forming a protective film is more preferably constituted by: the base material, the adhesive layer, and the protective film forming film, which satisfy the above conditions at the same time, are stacked in this order in the thickness direction thereof so as to be in direct contact with each other.
Preferably, the support sheet is transparent.
The support sheet may be colored according to the purpose, or may be vapor-deposited with another layer.
For example, when the protective film-forming film is energy ray-curable, the support sheet preferably transmits energy rays.
In the present specification, the "energy ray" refers to an energy ray having an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation, an electron beam, and the like. The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp (fusion lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.
The transmittance of light having a wavelength of 375nm in the support sheet is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the curing degree of the protective film-forming film is further improved when the protective film-forming film is irradiated with an energy ray (ultraviolet ray) through the support sheet.
The upper limit of the transmittance of light having a wavelength of 375nm in the support sheet is not particularly limited. For example, the transmittance of the light may be 95% or less.
The transmittance of light having a wavelength of 532nm in the support sheet is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of light is in such a range, the protective film-forming film or the protective film can be printed more clearly when the film or the protective film is irradiated with laser light through the support sheet.
The upper limit of the transmittance of light having a wavelength of 532nm in the support sheet is not particularly limited. For example, the transmittance of the light may be 95% or less.
The transmittance of light having a wavelength of 1064nm in the support sheet is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of light is in such a range, the protective film-forming film or the protective film can be printed more clearly when the film or the protective film is irradiated with laser light through the support sheet.
The upper limit of the transmittance of light having a wavelength of 1064nm in the support sheet is not particularly limited. For example, the transmittance of the light may be 95% or less.
The transmissive clarity of the support sheet is preferably 30 or more, more preferably 100 or more, and particularly preferably 200 or more. When the transmission resolution is in such a range, peeling of the protective film forming film due to lifting, defects in printing, and the like can be more easily checked through the support sheet.
The transmissive clarity of the support sheet is not particularly limited. For example, the transmission definition may be 430 or less.
The transmission clarity of the support sheet can be measured in accordance with JIS K7374-2007.
Next, the respective layers constituting the support sheet and the composite sheet for forming a protective film will be described in detail.
○ base material
The base material is sheet-shaped or film-shaped and has a concave-convex surface.
In the present specification, the term "uneven surface" means a surface having a maximum height roughness Rz of 0.01 μm or more as defined in JIS B0601: 2013.
The "smooth surface" is a surface having high smoothness, which is not an uneven surface, and may be referred to as an "uneven surface" or a "bright surface". For example, the smooth surface includes a surface having an extremely small unevenness, which does not correspond to the uneven surface.
In the substrate, only one surface may be an uneven surface or both surfaces may be uneven surfaces, but only one surface is preferably uneven surface. In other words, in the base material, only one side is preferably a smooth surface. In the support sheet, the uneven surface of the base material is a surface having the adhesive layer.
The substrate may be composed of one layer (single layer) or a plurality of layers of two or more layers, and when composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
When the substrate is composed of a plurality of layers, the surface of the outermost layer (the surface closest to the adhesive agent layer, or both surfaces closest to and farthest from the adhesive agent layer) among the plurality of layers is the above-mentioned uneven surface.
In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all the layers may be the same or all the layers may be different from each other, or only a part of the layers may be the same" and "a plurality of layers are different from each other" means "at least one of the constituent material and the thickness of each layer is different from each other" in the case of not being limited to the substrate.
In the uneven surface (first surface) on the side of the substrate provided with the adhesive layer, the R value of the substrate is preferably 1.3 or more and less than 4.8. Preferably 1.5 or more, more preferably 1.7 or more, and may be, for example, any one of 2.1 or more, 2.5 or more, 2.8 or more, and 3.3 or more. By setting the R value of the base material to be not less than the lower limit value, the R value of the adhesive can be adjusted well. Here, the R value of the base material is an average value of a ratio of (total of linear distances between adjacent distinct vertices)/(linear distance in a direction horizontal to the base material) when a test piece is cut from 5 of the base material and the cross section of the base material in the 5 test pieces is observed.
In addition, in the uneven surface (first surface) on the side of the base material provided with the adhesive layer, the maximum height roughness (Rz) measured in accordance with JIS B0601:2013 is preferably 0.01 to 8 μm, more preferably 0.1 to 7 μm, and particularly preferably 0.5 to 6 μm. When Rz of the base material is not less than the lower limit value, it is possible to suppress the occurrence of troubles when the base material is wound into a roll shape alone and unwound. Further, in the production process of the support sheet or the composite sheet for forming a protective film, similarly, the occurrence of defects in winding and unwinding of the laminate including the base material can be suppressed. On the other hand, when Rz of the base material is not more than the upper limit value, the lamination property of the adhesive layer and the protective film-forming film and the printing visibility of the protective film or the protective film-forming film via the support sheet are both good.
When both surfaces of the substrate are concave-convex surfaces, the concave-convex degrees of the two surfaces may be the same as each other or different from each other.
Examples of the material constituting the substrate include various resins.
Examples of the resin include polyethylene such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, and ethylene-norbornene copolymers; vinyl chloride-based resins (resins obtained using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; polystyrene; a polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters having an aromatic ring group in all the structural units; copolymers of two or more of said polyesters; poly (meth) acrylates; a polyurethane; a urethane acrylate; a polyimide; a polyamide; a polycarbonate; a fluororesin; a polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfones; polyether ketones, and the like.
Examples of the resin include a polymer blend such as a mixture of the polyester and a resin other than the polyester. Preferably the amount of resin other than polyester in the polymeric blend of the polyester with resin other than polyester is a minor amount.
Examples of the resin include crosslinked resins obtained by crosslinking one or two or more of the above-exemplified resins; one or two or more kinds of modified resins such as ionomers of the above-exemplified resins are used.
In the present specification, "(meth) acrylic acid" is a concept including "acrylic acid" and "methacrylic acid". Similar terms to (meth) acrylic acid are also the same, and for example, "(meth) acryl" is a concept including "acryl" and "methacryl", and "(meth) acrylate" is a concept including "acrylate" and "methacrylate".
The resin constituting the base material may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The thickness of the base material is preferably in the range of 50 to 300. mu.m, and more preferably in the range of 60 to 150. mu.m. By setting the thickness of the base material within such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or a semiconductor chip can be further improved.
As described above, since the substrate has the uneven surface, the thickness of the substrate varies depending on the portion of the substrate. Therefore, the minimum value of the thickness of the base material may be equal to or greater than the lower limit value, and the maximum value of the thickness of the base material may be equal to or less than the upper limit value.
The "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of a substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.
The thickness of the substrate is measured by observing the side surface or the cross section of the substrate using, for example, a Scanning Electron Microscope (SEM).
The cross section of the base material can be formed, for example, in the same manner as in the case of forming the cross section in the test piece of the support sheet and the composite sheet for forming a protective film.
For example, in the same manner as in the above-described method, a test piece is cut from a plurality of places (for example, 5 places) of the support sheet or the composite sheet for forming a protective film, the minimum value and the maximum value of the thickness of the base material are determined in the test piece, and the average value of the minimum value and the average value of the maximum value are further determined from these values.
The base material may contain various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin.
Preferably, the substrate is transparent.
The substrate may be colored according to the purpose, or may be deposited with another layer.
For example, when the protective film-forming film is energy ray-curable, the substrate preferably transmits energy rays.
In order to improve the adhesion between the substrate and a layer directly contacting the substrate, such as an adhesive layer provided thereon, the substrate may be one having a surface subjected to oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, or the like.
Further, the substrate may be one having a surface subjected to primer treatment.
When the composite sheet for forming an antistatic coating or a protective film is stacked and stored, the base material may have a layer for preventing adhesion of the base material to another sheet or adhesion of the base material to a suction pad.
The substrate can be produced by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
When a substrate having no uneven surface (in other words, a substrate having smooth surfaces on both sides) is used, the uneven surface of the substrate may be treated.
The embossing treatment can be performed by a known method. For example, the uneven surface of the substrate can be formed by pressing a metal roll or a metal plate having an uneven surface against a smooth surface of the substrate. In this case, it is preferable that the metal roll or the metal plate in a heated state is pressed against the smooth surface of the base material.
For example, in addition to the substrate having a desired uneven surface, which can be produced by using metal rolls having different unevenness, even if metal rolls having the same unevenness are used, the substrate having a desired uneven surface can be produced by changing the temperature of the metal rolls or changing the gap interval between the metal rolls and changing the pressing pressure. In addition, the smooth surface of the base material may be subjected to a roughening treatment by sandblasting, solvent treatment, or the like. The effect of the invention is not affected no matter what method is used for manufacturing the concave-convex base material.
○ adhesive layer
The adhesive layer is in a sheet or film shape.
In the adhesive agent layer, usually, at least the surface on the substrate side becomes an uneven surface by the influence of the uneven surface of the substrate, regardless of the presence or absence of an intermediate layer between the substrate and the adhesive agent layer.
The adhesive layer may be composed of one layer (single layer) or a plurality of layers of two or more layers, and in the case of being composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
When the adhesive layer is composed of a plurality of layers, the outermost surface (the surface closest to the base material) among these plurality of layers is the above-mentioned uneven surface.
Here, the base material and the adhesive agent layer will be described in further detail with reference to the drawings.
Fig. 4 is an enlarged cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Here, a composite sheet 1A for forming a protective film shown in fig. 1 will be described as an example. In fig. 4, the release film is not shown.
As described above, the first surface 11a of the substrate 11 is an uneven surface. The adhesive layer 12 is provided on the first surface (uneven surface) 11a of the substrate 11 so as to be in direct contact therewith, and the second surface 12b of the adhesive layer 12 easily follows the first surface 11a of the substrate 11. Therefore, the second surface 12b of the adhesive layer 12 is also an uneven surface.
The linear distance between adjacent distinct apexes is not constant, and varies depending on the position of the adhesive layer 12. Here, the symbol L is useda1、Lb1、La2、Lb2.., the straight line distance between adjacent distinct vertices. Furthermore, with L1Denotes a symbol La1、Lb1、La2、Lb2.., symbol L in the line segment showna1And Lb1A line segment obtained by projecting the line segment on a plane in the direction horizontal to the adhesive layer is represented by L2Denotes a symbol La1、Lb1、La2、Lb2.., symbol L in the line segment showna2And Lb2The line segment is a line segment projected on a plane in the direction horizontal to the adhesive layer.
Test pieces were cut from 5 of the composite sheet 1A for forming a protective film, a cross section was formed on the 5 test pieces, and the linear distances (the above-mentioned symbol L) between all adjacent sharp peaks of the adhesive agent layers were respectively obtained on the newly formed cross sectiona1、Lb1、La2、Lb2...), and the straight-line distance of adjacent distinct apexes in a direction horizontal to the adhesive layer. Then, the straight-line distance (the above symbol L) between all adjacent significant vertices is calculateda1、Lb1、La2、Lb2...)/(linear distance in the direction horizontal to the adhesive agent layer (the above symbol L)1、L2.., the sum of the lengths of the line segments) and an average value (the R value) obtained from at least 5 ratios is 1.5 or more and less than 5.0.
Fig. 5 is an enlarged cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Here, a composite sheet 1A for forming a protective film shown in fig. 1 will be described as an example. In fig. 5, the release film is not shown.
Thickness T of the adhesive layer 12aNot necessarily, it is based on viscosityThe position of the colorant layer 12 fluctuates. Here, the symbol T is useda1The minimum value of the thickness of the adhesive layer 12 is represented by the symbol Ta2The maximum value of the thickness of the adhesive layer 12 is shown.
A test piece was cut from 5 of the composite sheet 1A for forming a protective film, a cross section was formed on the 5 test pieces, and the minimum value T of the thickness of the adhesive layer was determined on the newly formed cross sectiona1And maximum value Ta2. And, according to at least 5Ta1When the average value (the S value) of the above values is determined, the average value is preferably 1.5 μm or more based on at least 5Ta2When the average value (L value) of the above values is determined, the average value is preferably 9 μm or less.
As described above, in the same manner as in the case of cutting a test piece from a support sheet not constituting the composite sheet for forming a protective film, the test piece can be cut from the composite sheet 1A for forming a protective film, the cross section in the test piece can be formed, the R value of the adhesive agent layer in the cross section can be measured, and the minimum value T of the thickness of the adhesive agent layer can be measureda1And maximum value Ta2。
The enlarged cross-sectional view of the support sheet not constituting the composite sheet for forming a protective film is the same as the one in which the protective film forming film 13 is not shown in fig. 4 and 5.
Here, the composite sheet for forming a protective film 1A is illustrated in which a region 91 where the substrate 11 and the adhesive agent layer 12 are not bonded (in this specification, may be referred to as a "non-bonded region") is present between the substrate 11 and the adhesive agent layer 12. However, even if the composite sheet 1A for forming a protective film has such a non-bonded region 91, the composite sheet 1A for forming a protective film in which the size of the non-bonded region 91 in the thickness direction of the composite sheet 1A for forming a protective film is, for example, 0.5 μm or less has good lamination properties of the substrate 11 and the adhesive layer 12, and thus has good characteristics.
In the present specification, the "size of the non-bonded region in the thickness direction of the composite sheet for forming a protective film" means "an interlayer distance between two adjacent layers in the composite sheet for forming a protective film in the thickness direction of the sheet", and may be simply referred to as "interlayer distance". For example, the "size of the non-bonded region 91 in the thickness direction of the protective film forming composite sheet 1A" means "the interlayer distance between the substrate 11 and the adhesive layer 12 in the thickness direction of the sheet 1A".
When the size (interlayer distance) of the non-bonded region varied at 1 point, the maximum value thereof was adopted as the size (interlayer distance) of the non-bonded region.
The size (interlayer distance) of the non-bonded region can be measured by the same method as that for measuring the R value of the adhesive agent layer. That is, in the same manner as when the R value of the adhesive layer is determined, a cross section can be formed in the test piece of the composite sheet for forming a protective film, and the size of the non-bonded region can be determined in the cross section. Alternatively, a cross section may be formed on the composite sheet for forming a protective film itself without fabricating a test piece, and the size of the non-bonded region may be determined on the cross section.
The size of the non-bonded region 91 (the interlayer distance) may be, for example, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less.
In the protective film forming composite sheet 1A, the non-bonded region 91 may not be present at all. In the present specification, when the non-bonded region 91 is not present at all, the size (interlayer distance) of the non-bonded region 91 may be 0 μm.
Here, the description will be given of the substrate and the adhesive layer by taking the composite sheet for forming a protective film 1A as an example, but when the composite sheet for forming a protective film is a composite sheet for forming a protective film of another embodiment such as the composite sheet for forming a protective film 1B or the composite sheet for forming a protective film 1C, the substrate and the adhesive layer are also the same as in the case of the composite sheet for forming a protective film 1A.
The R value of the adhesive agent layer is not particularly limited as long as it is 1.5 or more and less than 5.0, but is preferably 1.7 or more, more preferably 1.9 or more, and may be, for example, any one of 2.3 or more, 2.7 or more, 3.1 or more, and 3.5 or more. When the R value is not less than the lower limit, the adhesion between the substrate and the adhesive is further improved.
On the other hand, the R value of the adhesive agent layer may be, for example, 4.5 or less, or may be 4.0 or less. The protective film or the protective film-forming film of such an adhesive layer has good printing visibility through the support sheet.
The R value of the adhesive agent layer can be appropriately adjusted within a range set by arbitrarily combining the above preferable lower limit value and upper limit value. For example, the R value of the adhesive agent layer is preferably 1.5 to 4, more preferably 1.7 to 4, further preferably 1.9 to 4, and may be any of 2.3 to 4, 2.7 to 4, 3.1 to 4, and 3.5 to 4, for example. However, these ranges are only one example of the R value of the adhesive layer.
The S value of the adhesive agent layer is not particularly limited as long as the effects of the present invention are not impaired, and is preferably 1.5 μm or more and less than 9 μm. More preferably 1.7 μm or more, particularly preferably 1.9 μm or more, and may be, for example, 2.3 μm or more, 2.7 μm or more, 3.1 μm or more, or 3.5 μm or more. When the S value is not less than the lower limit, the adhesive layer and the protective film-forming film have better lamination properties.
On the other hand, the S value of the adhesive agent layer may be 8 μm or less, for example. Such an adhesive layer can be formed more easily.
The S value of the adhesive agent layer can be appropriately adjusted within a range set by arbitrarily combining the above preferable lower limit value and upper limit value. For example, the adhesive agent layer preferably has an S value of 1.5 to 8 μm, more preferably 1.7 to 8 μm, and still more preferably 1.9 to 8 μm, and may have any one of the ranges of 2.3 to 8 μm, 2.7 to 8 μm, 3.1 to 8 μm, and 3.5 to 8 μm. However, these ranges are only one example of the S value of the adhesive layer.
The L value of the adhesive agent layer is not particularly limited as long as the effects of the present invention are not impaired, and is preferably 9 μm or less and more than 1.5. mu.m. More preferably 8.6 μm or less, particularly preferably 8.3 μm or less, and may be, for example, 7.7 μm or less, 7.3 μm or less, 6.9 μm or less, or 6.5 μm or less. When the L value is not more than the upper limit value, the protective film or the protective film forming film has better printing visibility through the support sheet.
On the other hand, the L value of the adhesive agent layer may be, for example, 2.5 μm or more. Such an adhesive layer can be formed more easily.
The L value of the adhesive agent layer can be appropriately adjusted within a range set by arbitrarily combining the above preferable lower limit value and upper limit value. For example, the adhesive agent layer preferably has an L value of 2.5 to 9 μm, more preferably 2.5 to 8.6 μm, and still more preferably 2.5 to 8.3 μm, and may have any one of the ranges of 2.5 to 7.7 μm, 2.5 to 7.3 μm, 2.5 to 6.9 μm, and 2.5 to 6.5 μm.
The thickness of the adhesive layer (e.g., T) is not particularly limited as long as the effects of the present invention are not impaireda) The above conditions for the S value and the L value are preferably satisfied, although not particularly limited.
For example, the thickness of the adhesive layer may be 1.5 to 9 μm.
The "thickness of the adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive agent layer. From such a viewpoint, the minimum value and the maximum value of the thickness of the adhesive agent layer are defined.
The adhesive layer contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferred.
In the present specification, the "adhesive resin" is a concept including a resin having adhesiveness and a resin having adhesiveness, and includes, for example, not only a resin having adhesiveness of the resin itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive, a resin exhibiting adhesiveness due to the presence of an inducer (trigger) such as heat or water, and the like.
Preferably, the adhesive layer is transparent.
The adhesive layer may be colored according to the purpose.
For example, when the protective film-forming film is energy ray-curable, the adhesive layer preferably transmits energy rays.
The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. An adhesive layer formed using an energy ray-curable adhesive can be easily adjusted in physical properties before and after curing.
Adhesive composition
The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive layer can be formed at a target site by applying an adhesive composition to a surface to be formed of the adhesive layer and drying the adhesive composition as necessary. More specific methods for forming the adhesive layer will be described in detail later together with methods for forming other layers. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is generally the same as the content ratio of the components in the adhesive layer.
In the present specification, "normal temperature" means a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and includes, for example, a temperature of 15 to 25 ℃.
The adhesive composition may be applied by a known method, and examples thereof include a method using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferably dried by heating. The adhesive composition containing a solvent is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
When the adhesive layer is energy ray-curable, examples of the adhesive composition containing an energy ray-curable adhesive, that is, an energy ray-curable adhesive composition, include: an adhesive composition (I-1) comprising an adhesive resin (I-1a) which is not curable with energy rays (hereinafter, may be abbreviated as "adhesive resin (I-1 a)") and an energy ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)") having an unsaturated group introduced into a side chain of a non-energy ray-curable adhesive resin (I-1 a); and an adhesive composition (I-3) comprising the adhesive resin (I-2a) and an energy ray-curable compound.
< adhesive composition (I-1) >
As described above, the adhesive composition (I-1) contains the non-energy ray-curable adhesive resin (I-1a) and the energy ray-curable compound.
[ adhesive resin (I-1a) ]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
The acrylic resin may have only one kind of structural unit, or two or more kinds of structural units, and when two or more kinds of structural units are present, the combination and ratio of the two or more kinds of structural units can be arbitrarily selected.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched.
More specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearate (meth) acrylate), nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.
Preferably, the acrylic polymer has a structural unit derived from an alkyl (meth) acrylate having 4 or more carbon atoms in the alkyl group, from the viewpoint of improving the adhesive force of the adhesive agent layer. Further, the number of carbon atoms of the alkyl group is preferably 4 to 12, more preferably 4 to 8, from the point of further improving the adhesive force of the adhesive agent layer. The alkyl (meth) acrylate having an alkyl group with 4 or more carbon atoms is preferably an alkyl acrylate.
Preferably, the acrylic polymer further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate.
Examples of the functional group-containing monomer include a functional group-containing monomer in which the functional group reacts with a crosslinking agent described later to form a crosslinking starting point, or in which the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later to introduce an unsaturated group into a side chain of an acrylic polymer.
Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols (unsaturated alcohols having no (meth) acryloyl skeleton) such as vinyl alcohol and allyl alcohol.
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
The functional group-containing monomer constituting the acrylic polymer may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 27% by mass, relative to the total amount of the structural units.
The acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the alkyl (meth) acrylate and the structural unit derived from the functional group-containing monomer.
The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth) acrylate or the like.
Examples of the other monomer include styrene, α -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
The other monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
The acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1 a).
On the other hand, a product obtained by reacting an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) with a functional group in the acrylic polymer can be used as the energy ray-curable adhesive resin (I-2 a).
The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
The content of the adhesive resin (I-1a) in the adhesive composition (I-1) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include a monomer or oligomer having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.
Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.
Examples of the oligomer in the energy ray-curable compound include oligomers obtained by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably urethane (meth) acrylate or urethane (meth) acrylate oligomer in terms of a large molecular weight and a low tendency to decrease the storage modulus of the adhesive agent layer.
The energy ray-curable compound contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), it is preferable that the adhesive composition (I-1) further contains a crosslinking agent.
The crosslinking agent crosslinks the adhesive resins (I-1a) to each other, for example, by reacting with the functional groups.
Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group) such as Hexa [1- (2-methyl) -azidinyl ] triphosphazine ] Hexa [1- (2-methyl) aziridinyl ] triazine triphosphate; metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; an isocyanurate-based crosslinking agent (a crosslinking agent having an isocyanurate skeleton), and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent, because of the point of increasing the cohesive force of the adhesive agent to increase the adhesive force of the adhesive agent layer, the point of easy availability, and the like.
The crosslinking agent contained in the adhesive composition (I-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The content of the crosslinking agent in the adhesive composition (I-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the adhesive resin (I-1 a).
[ photopolymerization initiator ]
The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator is sufficiently cured even when irradiated with relatively low-energy radiation such as ultraviolet light.
Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate and benzoin dimethyl ketal, acylphosphine oxide compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2, 2-dimethoxy-1, 2-diphenylethane-1-one, acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide, α -ketol compounds such as 1-hydroxycyclohexylphenyl ketone, azo compounds such as azobisisobutyronitrile, titanocene compounds such as titanocene, thioxanthone compounds such as thioxanthone, peroxide compounds, diketone compounds such as butanedione, benzoin, 2, 4-diethylthioxanthone, 2-diethylthioxanthone, 2- [1- (2-methyl) methyl ] methyl-1- (2-chloro) acetone, and the like.
Further, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like.
The photopolymerization initiator contained in the adhesive composition (I-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable compound.
[ other additives ]
The adhesive composition (I-1) may further contain other additives not included in any of the above components within a range not impairing the effects of the present invention.
Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).
The reaction retarder is an additive that suppresses the unintended crosslinking reaction of the adhesive composition (I-1) during storage due to the action of the catalyst mixed in the adhesive composition (I-1), for example. Examples of the reaction retarder include a reaction retarder which forms a chelate complex (chelate complex) by using a chelate of a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.
The adhesive composition (I-1) may contain only one other additive, or may contain two or more other additives, and when two or more other additives are contained, the combination and ratio of these additives may be arbitrarily selected.
The content of the other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive composition (I-1) may contain a solvent. By adding the solvent to the adhesive composition (I-1), the coating suitability to the surface to be coated is improved.
The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
The solvent may be used as it is in the adhesive composition (I-1) without removing the solvent used in the production of the adhesive resin (I-1a) from the adhesive resin (I-1a), or a solvent which is the same as or different from the solvent used in the production of the adhesive resin (I-1a) may be added separately in the production of the adhesive composition (I-1).
The adhesive composition (I-1) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio of the two or more solvents can be arbitrarily selected.
The content of the solvent in the adhesive composition (I-1) is not particularly limited as long as it is appropriately adjusted.
< adhesive composition (I-2) >
As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1 a).
[ adhesive resin (I-2a) ]
The adhesive resin (I-2a) is obtained, for example, by reacting an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group with a functional group in the adhesive resin (I-1 a).
The unsaturated group-containing compound is a compound having, in addition to the energy ray-polymerizable unsaturated group, a group that can be bonded to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1 a).
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (also referred to as an ethylene group), an allyl group (also referred to as a 2-propenyl group), and the like, and a (meth) acryloyl group is preferable.
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxyl group or an epoxy group.
Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.
The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass, based on the total mass of the adhesive composition (I-2).
[ crosslinking agent ]
For example, when the acrylic polymer having a structural unit derived from a functional group-containing monomer, which is the same as that in the adhesive resin (I-1a), is used as the adhesive resin (I-2a), the adhesive composition (I-2) may further contain a crosslinking agent.
The crosslinking agent in the adhesive composition (I-2) may be the same crosslinking agent as that in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-2) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator is sufficiently cured even when irradiated with relatively low-energy radiation such as ultraviolet light.
The photopolymerization initiator in the adhesive composition (I-2) may be the same photopolymerization initiator as that in the adhesive composition (I-1).
The photopolymerization initiator contained in the adhesive composition (I-2) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The content of the photopolymerization initiator in the adhesive composition (I-2) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the adhesive resin (I-2 a).
[ other additives ]
The adhesive composition (I-2) may further contain other additives not included in any of the above components within a range not impairing the effects of the present invention.
Examples of the other additives in the adhesive composition (I-2) include the same other additives as those in the adhesive composition (I-1).
The adhesive composition (I-2) may contain only one other additive, or may contain two or more other additives, and when two or more other additives are contained, the combination and ratio of these additives may be arbitrarily selected.
The content of the other additives in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
The solvent in the adhesive composition (I-2) may be the same solvent as that in the adhesive composition (I-1).
The adhesive composition (I-2) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio of the solvents can be arbitrarily selected.
In the adhesive composition (I-2), the content of the solvent is not particularly limited as long as it is appropriately adjusted.
< adhesive composition (I-3) >
As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable compound.
In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-3).
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray, and examples of the energy ray-curable compound include the same energy ray-curable compounds as those contained in the adhesive composition (I-1).
The energy ray-curable compound contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the energy ray-curable compound in the adhesive composition (I-3) is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator is sufficiently cured even when irradiated with relatively low-energy radiation such as ultraviolet light.
The photopolymerization initiator in the adhesive composition (I-3) may be the same photopolymerization initiator as that in the adhesive composition (I-1).
The photopolymerization initiator contained in the adhesive composition (I-3) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.
[ other additives ]
The adhesive composition (I-3) may further contain other additives not included in any of the above components within a range not impairing the effects of the present invention.
Examples of the other additives include the same other additives as those in the adhesive composition (I-1).
The adhesive composition (I-3) may contain only one other additive, or may contain two or more other additives, and when two or more other additives are contained, the combination and ratio of these additives may be arbitrarily selected.
The content of the other additives in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-3) include the same solvents as those in the adhesive composition (I-1).
The adhesive composition (I-3) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio of the solvents can be arbitrarily selected.
In the adhesive composition (I-3), the content of the solvent is not particularly limited as long as it is appropriately adjusted.
< adhesive compositions other than the adhesive compositions (I-1) to (I-3) >
Although the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) have been mainly described so far, the components described as the components contained therein can be similarly used in all adhesive compositions other than the three adhesive compositions (in the present specification, referred to as "adhesive compositions other than the adhesive compositions (I-1) to (I-3)").
Examples of the adhesive compositions other than the adhesive compositions (I-1) to (I-3) include energy ray-curable adhesive compositions and non-energy ray-curable adhesive compositions.
Examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, or an ester resin, and a non-energy ray-curable adhesive composition containing an acrylic resin is preferable.
The adhesive compositions other than the adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents, and the content thereof may be set to the same level as in the case of the adhesive composition (I-1) or the like.
< adhesive composition (I-4) >
A preferable adhesive composition (I-4) includes, for example, an adhesive composition containing the adhesive resin (I-1a) and a crosslinking agent.
[ adhesive resin (I-1a) ]
The adhesive resin (I-1a) in the adhesive composition (I-4) may be the same adhesive resin (I-1a) as the adhesive resin (I-1a) in the adhesive composition (I-1).
The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-4).
In the adhesive composition (I-4), the proportion of the content of the adhesive resin (I-1a) to the total content of all components except the solvent (i.e., the content of the adhesive resin (I-1a) in the adhesive layer) is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and particularly preferably 50 to 80% by mass.
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), it is preferable that the adhesive composition (I-4) further contains a crosslinking agent.
The crosslinking agent in the adhesive composition (I-4) may be the same crosslinking agent as that in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-4) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The content of the crosslinking agent in the adhesive composition (I-4) is preferably 0.01 to 50 parts by mass, more preferably 0.3 to 50 parts by mass, still more preferably 1 to 50 parts by mass, and may be, for example, any one of 10 to 50 parts by mass, 15 to 50 parts by mass, and 20 to 50 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1 a).
[ other additives ]
The adhesive composition (I-4) may further contain other additives not included in any of the above components within a range not impairing the effects of the present invention.
Examples of the other additives include the same other additives as those in the adhesive composition (I-1).
The adhesive composition (I-4) may contain only one other additive, or may contain two or more other additives, and when two or more other additives are contained, the combination and ratio of these additives may be arbitrarily selected.
The content of the other additives in the adhesive composition (I-4) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
The solvent in the adhesive composition (I-4) may be the same solvent as that in the adhesive composition (I-1).
The adhesive composition (I-4) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio of the solvents can be arbitrarily selected.
In the adhesive composition (I-4), the content of the solvent is not particularly limited as long as it is appropriately adjusted.
In the composite sheet for forming a protective film, the adhesive layer is preferably non-energy ray-curable. This is because, if the adhesive layer is energy ray-curable, the adhesive layer may not be inhibited from being simultaneously cured when the protective film-forming film is cured by irradiation with an energy ray. If the adhesive layer and the protective film-forming film are cured simultaneously, the cured protective film-forming film (i.e., protective film) and the adhesive layer may stick to each other at their interface to such an extent that they cannot be peeled off. In this case, it is difficult to peel the semiconductor chip (semiconductor chip with protective film) having the protective film as the film for forming the protective film after curing on the back surface from the support sheet having the cured adhesive layer, and the semiconductor chip with the protective film cannot be picked up normally. In the support sheet, by making the adhesive agent layer non-energy ray-curable, such a problem can be avoided reliably, and the semiconductor chip with the protective film can be picked up more easily.
Here, although the effect when the adhesive agent layer is non-energy ray-curable is described, the same effect is exhibited even if the layer of the support sheet that is in direct contact with the film for forming a protective film is a layer other than the adhesive agent layer, as long as the layer is non-energy ray-curable.
Preparation method of adhesive composition
The adhesive compositions other than the adhesive compositions (I-1) to (I-3), such as the adhesive compositions (I-1) to (I-3) and the adhesive composition (I-4), can be obtained by blending the components for constituting the adhesive compositions, that is, the adhesive and, if necessary, the components other than the adhesive.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any of the components other than the solvent to preliminarily dilute the components, or the solvent may be mixed with the components without preliminarily diluting any of the components other than the solvent to use the mixture.
The method for mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer (mixer); a method of mixing by applying ultrasonic waves, and the like.
The temperature and time when the components are added and mixed are not particularly limited as long as the components are not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
◎ film for forming protective film
The protective film-forming film may be a protective film by curing or may be a protective film in its own state without curing. The protective film is used to protect the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer or the semiconductor chip. The protective film-forming film is soft and can be easily attached to an object to be attached.
The protective film-forming film may be curable or non-curable.
The curable protective film-forming film may be either thermosetting or energy ray-curable, and may have both thermosetting and energy ray-curable properties.
The protective film-forming film can be formed using a protective film-forming composition containing the constituent material thereof.
In the present specification, "non-curable" refers to a property that curing does not proceed even by any means such as heating or irradiation with energy rays.
In the present invention, as long as the laminated structure of the cured product of the support sheet and the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, even after the film for forming a protective film is cured, the laminated body is referred to as a "composite sheet for forming a protective film".
The protective film may be formed of one layer (single layer) or a plurality of layers of two or more layers, regardless of the type of the protective film-forming film. When the protective film-forming film is composed of a plurality of layers, these plurality of layers may be the same as each other or different from each other.
Here, the adhesive layer and the protective film-forming film will be described in further detail with reference to fig. 4 again.
As described above, the first surface 11a of the substrate 11 is an uneven surface. In particular, when the R value of the adhesive agent layer 12 is less than 5.0, the influence of the uneven surface can be suppressed, and the unevenness of the first surface 12a of the adhesive agent layer 12 can be easily reduced. Therefore, the adhesive layer 12 and the protective film-forming film 13 are easily laminated well. Further, by setting the S value to 1.5 μm or more, the influence of the uneven surface can be suppressed, and the unevenness of the first surface 12a of the adhesive layer 12 can be reduced. For example, even if there are regions (non-bonded regions) 92 where the adhesive layer 12 and the protective film-forming film 13 are not bonded between the adhesive layer 12 and the protective film-forming film 13, the number thereof is extremely small, and 3 or less positions are present over the entire region of the protective film-forming film 13-forming region in the protective film-forming composite sheet 1A. The non-bonded region 92 can be easily confirmed by, for example, observing the composite sheet for forming a protective film 1A from the substrate 11 side.
Further, even if the composite sheet for forming a protective film 1A has such a non-bonded region 92, the composite sheet for forming a protective film 1A in which the size (interlayer distance) of the non-bonded region 92 in the thickness direction of the composite sheet for forming a protective film 1A is, for example, 0.5 μm or less has more favorable lamination properties of the adhesive layer 12 and the film for forming a protective film 13. Here, the "size (interlayer distance) of the non-bonded region 92" means "the interlayer distance between the adhesive layer 12 and the protective film-forming film 13 in the thickness direction of the protective film-forming composite sheet 1A".
The size of the non-bonded region 92 (the interlayer distance) is preferably 0.5 μm or less, and may be, for example, any one of 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, and 0.1 μm or less, as in the interlayer distance (size) of the non-bonded region 91.
For example, the size (interlayer distance) of the non-bonded region 92 can be determined by the same method as the case of determining the size (interlayer distance) of the non-bonded region 91, except that the combination of the two target layers is different.
In the protective film forming composite sheet 1A, the non-bonded region 92 may not be present at all. In the present specification, when the non-bonded region 92 is not present at all, the size (interlayer distance) of the non-bonded region 92 may be 0 μm.
On the other hand, as described above, the first surface 12a of the adhesive layer 12 has the unevennessIt is easy to be small. Therefore, the thickness T of the protective film forming film 13pThe thickness is not always constant, but varies depending on the portion of the protective film-forming film 13 (adhesive agent layer 12), but the variation width is extremely small.
Further, as described above, since the unevenness of the first surface 12a of the adhesive layer 12 is likely to be small, the surface (second surface) 13b of the protective film forming film 13 on the adhesive layer 12 side is smooth or the unevenness is likely to be small. Therefore, the appearance of the protective film forming film 13 is not easily impaired.
In the protective film formed from the protective film forming film 13, the surface (second surface) on the adhesive agent layer 12 side is also smooth or has a small degree of unevenness, and the appearance of the protective film is not easily impaired.
In this way, in the composite sheet 1A for forming a protective film, both the film 13 for forming a protective film and the protective film can be made excellent in design.
In the second surface 13b of the protective film forming film 13, the maximum height difference between the highest portion of the convex portion and the deepest portion of the concave portion is preferably 2 μm or less, and may be, for example, 1.5 μm or less and 1 μm or less. The protective film-forming film 13 and the protective film are particularly excellent in design.
The maximum height difference of the second surface 13b of the protective film-forming film 13 can be determined, for example, by forming a cross section in a test piece of the protective film-forming composite sheet or the protective film-forming composite sheet itself by the method described above and observing the cross section using a Scanning Electron Microscope (SEM).
Here, the adhesive layer and the film for forming the protective film are described by taking the composite sheet 1A for forming the protective film as an example, but when the composite sheet for forming the protective film is a composite sheet for forming the protective film of another embodiment such as the composite sheet 1B for forming the protective film, the composite sheet 1C for forming the protective film, and the like, the adhesive layer and the film for forming the protective film are also the same as in the case of the composite sheet 1A for forming the protective film.
In the composite sheet for forming a protective film of the present invention, the thickness (e.g., T) of the film for forming a protective filmp) Preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably5 to 50 μm. When the thickness of the protective film forming film is not less than the lower limit value, a protective film having higher protective performance can be formed. When the thickness of the protective film forming film is not more than the upper limit, the thickness can be suppressed from becoming too thick.
When the thickness of the protective film-forming film varies depending on the position of the protective film-forming film, the minimum value of the thickness of the protective film-forming film may be equal to or greater than the lower limit value, and the maximum value of the thickness of the protective film-forming film may be equal to or less than the upper limit value.
The "thickness of the protective film-forming film" refers to the thickness of the entire protective film-forming film, and for example, the thickness of the protective film-forming film composed of a plurality of layers refers to the total thickness of all the layers constituting the protective film-forming film.
The thickness of the protective film-forming film can be measured by, for example, observing the side surface or the cross section of the protective film-forming film using a Scanning Electron Microscope (SEM).
The cross section of the protective film-forming film can be formed, for example, by the same method as in the case of forming the cross section in the test piece of the support sheet and the protective film-forming composite sheet.
For example, in the case where a test piece is cut out from a plurality of places (for example, 5 places) of the composite sheet for forming a protective film by the method described above, the minimum value and the maximum value of the thickness of the film for forming a protective film in the test piece are obtained, and the average value of the minimum value and the average value of the maximum value are further obtained from these values, the average value of the minimum values may be equal to or more than the lower limit value of the thickness of the film for forming a protective film, and the average value of the maximum values may be equal to or less than the upper limit value of the thickness of the film for forming a protective film.
The protective film-forming film can be formed using a protective film-forming composition containing the constituent material thereof. For example, a film for forming a protective film can be formed on a target site by applying a composition for forming a protective film on a surface to be formed of the film for forming a protective film and drying the composition as necessary. The content ratio of the components that do not vaporize at normal temperature in the composition for forming a protective film is generally the same as the content ratio of the components of the film for forming a protective film.
The coating of the composition for forming a protective film may be carried out by a known method, and examples thereof include methods using various coating machines such as a knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the protective film-forming composition are not particularly limited, but when the protective film-forming composition contains a solvent described later, it is preferably dried by heating. The solvent-containing composition for forming a protective film is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example. Among them, when the protective film-forming composition is thermosetting, it is preferable to dry the protective film-forming composition so that the formed protective film-forming film is not thermally cured.
Hereinafter, the film for forming a protective film and the composition for forming a protective film will be described in detail.
○ film for forming thermosetting protective film
Examples of a preferable thermosetting protective film-forming film include a thermosetting protective film-forming film containing a polymer component (a) and a thermosetting component (B).
The polymer component (a) can be considered as a component formed by a polymerization reaction of a polymerizable compound.
The thermosetting component (B) is a component that can cause a curing (polymerization) reaction using heat as a trigger of the reaction. The polymerization reaction in the present invention also includes a polycondensation reaction.
The curing conditions for the thermosetting protective film-forming film to be adhered to the back surface of the semiconductor wafer and then thermally cured are not particularly limited as long as the cured product has a degree of curing sufficient to exert its function, and may be appropriately selected depending on the kind of the thermosetting protective film-forming film.
For example, the heating temperature for thermosetting the film for forming a thermosetting protective film is preferably 100 to 200 ℃, more preferably 110 to 180 ℃, and particularly preferably 120 to 170 ℃. The heating time during curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.
< composition for Forming thermosetting protective film (III-1) >
Examples of a preferable thermosetting protective film-forming composition include a thermosetting protective film-forming composition (III-1) (which may be abbreviated as "composition (III-1)" in the present specification) containing a polymer component (A) and a thermosetting component (B).
[ Polymer component (A) ]
The polymer component (a) is a component for imparting film formability, flexibility, and the like to the film for forming a thermosetting protective film.
The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include acrylic resins, polyesters, urethane resins, acrylic urethane resins, silicone resins, rubber resins, phenoxy resins, thermosetting polyimides, and the like, and acrylic resins are preferred.
As the acrylic resin in the polymer component (a), a known acrylic polymer can be mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000. By setting the weight average molecular weight of the acrylic resin to be not less than the lower limit, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. Further, by setting the weight average molecular weight of the acrylic resin to be not more than the upper limit value, the film for forming a thermosetting protective film easily follows the uneven surface of the adherend, and generation of voids (void) and the like between the adherend and the film for forming a thermosetting protective film is further suppressed.
In the present specification, unless otherwise specified, the weight average molecular weight refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
The glass transition temperature (Tg) of the acrylic resin is preferably-60 to 70 ℃, more preferably-30 to 50 ℃. When the Tg of the acrylic resin is not less than the lower limit, for example, the adhesion between the cured product of the protective film-forming film (i.e., the protective film) and the supporting sheet can be suppressed, and the releasability of the supporting sheet can be appropriately improved. Further, by setting Tg of the acrylic resin to the upper limit value or less, the adhesive strength of the thermosetting protective film-forming film and the protective film to the adherend is improved.
The Tg of the resin in the present specification is determined by, for example, not being limited to an acrylic resin: the temperature of the object to be measured was changed between-70 ℃ and 150 ℃ by setting the temperature increase rate or the temperature decrease rate at 10 ℃/min using a Differential Scanning Calorimeter (DSC), and the inflection point was confirmed.
Examples of the acrylic resin include polymers of one or two or more kinds of (meth) acrylic acid esters; and copolymers of two or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
Examples of the (meth) acrylic ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate);
cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylimide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
and substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate. Here, "substituted amino group" refers to a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.
The acrylic resin may be copolymerized with one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide, for example, in addition to the (meth) acrylate.
The acrylic resin may be composed of only one monomer, or two or more monomers, and when two or more monomers are used, the combination and ratio of the monomers can be selected arbitrarily.
The acrylic resin may have a functional group capable of bonding to another compound, such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described later, or may be directly bonded to another compound without the crosslinking agent (F). The acrylic resin is bonded to another compound through the functional group, and thus the reliability of a package obtained using the composite sheet for forming a protective film tends to be improved.
In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter, may be abbreviated as "thermoplastic resin") may be used alone without using an acrylic resin, or an acrylic resin and a thermoplastic resin other than an acrylic resin may be used together. By using the thermoplastic resin, the releasability of the protective film from the support sheet may be improved, or the film for forming a thermosetting protective film may easily follow the uneven surface of the adherend, and generation of a void or the like between the adherend and the film for forming a thermosetting protective film may be further suppressed.
The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, and more preferably 3000 to 80000.
The glass transition temperature (Tg) of the thermoplastic resin is preferably-30 to 150 ℃, and more preferably-20 to 120 ℃.
Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like
The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1), the proportion of the content of the polymer component (a) to the total content of all components except the solvent (i.e., the content of the polymer component (a) of the film for forming a thermosetting protective film) is preferably 5 to 85 mass%, more preferably 5 to 75 mass%, and may be, for example, any one of 5 to 65 mass%, 5 to 50 mass%, 10 to 35 mass%, and the like, regardless of the type of the polymer component (a).
The polymer component (A) may be a thermosetting component (B). In the present invention, when the composition (III-1) contains such a component belonging to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing the polymer component (A) and the thermosetting component (B).
[ thermosetting component (B) ]
The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film.
The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., and epoxy thermosetting resins are preferred.
(epoxy thermosetting resin)
The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio of these may be arbitrarily selected.
Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and epoxy resins having a phenylene skeleton.
As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may also be used. The compatibility of the epoxy resin having an unsaturated hydrocarbon group with the acrylic resin is greater than the compatibility of the epoxy resin having no unsaturated hydrocarbon group with the acrylic resin. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming a protective film is improved.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a part of the epoxy group of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof with an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene group (vinyl group), a 2-propenyl group (allyl group), (meth) acryloyl group, and (meth) acrylamido group, with acryloyl group being preferred.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 300 to 10000, and particularly preferably 300 to 3000, in view of curability of the thermosetting protective film-forming film and strength and heat resistance of the protective film after curing.
In the present specification, unless otherwise specified, the number average molecular weight refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 150 to 950 g/eq.
In the present specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K7236: 2001.
The epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
Heat-curing agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups reactive with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group obtained by anhydrizing an acid group, and the like, and a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group are preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenol curing agent having a phenolic hydroxyl group in the heat curing agent (B2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.
Examples of the amine-based curing agent having an amino group in the thermosetting agent (B2) include dicyandiamide.
The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the unsaturated hydrocarbon group-containing thermosetting agent (B2) include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with an unsaturated hydrocarbon group-containing group, a compound in which an unsaturated hydrocarbon group-containing group is directly bonded to an aromatic ring of a phenol resin, and the like.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-described epoxy resin having an unsaturated hydrocarbon group.
When a phenol curing agent is used as the heat curing agent (B2), the heat curing agent (B2) preferably has a high softening point or glass transition temperature, from the viewpoint of improving the releasability of the protective film from the support sheet.
Among the heat-curing agents (B2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, and is preferably 60 to 500, for example.
The heat-curing agent (B2) may be used alone or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the thermosetting agent (B2) in the composition (III-1) and the film for forming a thermosetting protective film is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, 1 to 10 parts by mass, and the like, relative to 100 parts by mass of the content of the epoxy resin (B1). When the content of the thermosetting agent (B2) is not less than the lower limit value, the film for forming a thermosetting protective film can be more easily cured. Further, when the content of the thermosetting agent (B2) is not more than the upper limit, the moisture absorption rate of the thermosetting protective film-forming film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.
In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, still more preferably 40 to 150 parts by mass, and may be, for example, 45 to 100 parts by mass or 50 to 80 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). When the content of the thermosetting component (B) is in such a range, for example, the adhesion between the cured product of the film for forming a protective film and the supporting sheet can be suppressed, and the releasability of the supporting sheet can be improved.
[ curing Accelerator (C) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the composition (III-1).
Examples of the preferable curing accelerator (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which 1 or more hydrogen atoms are substituted with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organophosphines (phosphines in which 1 or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylboron tetraphenylphosphine and triphenylphosphine tetraphenylborate.
The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the curing accelerator (C) is used, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, per 100 parts by mass of the thermosetting component (B) in the composition (III-1) and the film for forming a thermosetting protective film. By setting the content of the curing accelerator (C) to the lower limit or more, the effect of using the curing accelerator (C) can be more remarkably obtained. Further, by setting the content of the curing accelerator (C) to the upper limit or less, for example, the effect of suppressing the migration and segregation of the highly polar curing accelerator (C) to the side of the adhesive interface with the adherend in the thermosetting protective film-forming film under the conditions of high temperature and high humidity is improved, and the reliability of the semiconductor chip with a protective film obtained by using the protective film-forming composite sheet is further improved.
[ Filler (D) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By containing the filler (D) in the thermosetting protective film-forming film, the water absorption and the adhesive force variation rate can be more easily adjusted to the target ranges. Further, by making the thermosetting protective film-forming film and the protective film contain the filler (D), the adjustment of the thermal expansion coefficient becomes easier, and by optimizing the thermal expansion coefficient with respect to the object to be formed of the thermosetting protective film-forming film or the protective film, the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming the protective film is further improved. Further, by incorporating the filler (D) into the thermosetting protective film-forming film, the moisture absorption rate of the protective film can be reduced, and the heat dissipation property can be improved.
The filler (D) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler.
Examples of preferable inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic filler materials; glass fibers, and the like.
Among them, the inorganic filler is preferably silica or alumina, and more preferably silica.
The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the filler (D) is used, the content of the filler (D) in the composition (III-1) relative to the total content of all the components except the solvent (i.e., the content of the filler (D) in the film for forming a thermosetting protective film) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and may be, for example, any one of 20 to 65% by mass, 30 to 65% by mass, 40 to 65% by mass, and the like. By setting the content of the filler (D) in such a range, the adjustment of the thermal expansion coefficient becomes easier, and the strength of the protective film-forming film and the protective film is further improved.
[ coupling agent (E) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a substance having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the thermosetting protective film-forming film to an adherend can be improved. Further, by using the coupling agent (E), the water resistance of the cured product (protective film) of the film for forming a thermosetting protective film can be improved without impairing the heat resistance.
The coupling agent (E) is preferably a compound having a functional group reactive with the functional group of the polymer component (a), the thermosetting component (B), or the like, and more preferably a silane coupling agent.
Examples of the preferable silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (E) is used, the content of the coupling agent (E) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B) in the composition (III-1) and the film for forming a thermosetting protective film. By setting the content of the coupling agent (E) to the lower limit or more, effects of using the coupling agent (E) such as improvement of dispersibility of the filler (D) in the resin and improvement of adhesiveness between the thermosetting protective film-forming film and the adherend can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the upper limit value or less, the occurrence of degassing can be further suppressed.
[ crosslinking agent (F) ]
When a substance having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which is capable of bonding to another compound, such as the acrylic resin, is used as the polymer component (a), the composition (III-1) and the film for forming a thermosetting protective film may contain the crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and by crosslinking in this way, the initial adhesive force and cohesive force of the film for forming a thermosetting protective film can be adjusted.
Examples of the crosslinking agent (F) include an organic polyisocyanate (polyisocynate) compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.
Examples of the organic polyisocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively abbreviated as "aromatic polyisocyanate compound, etc.); trimers, isocyanurate bodies and adducts of the aromatic polyisocyanate compounds and the like; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compound and the like with a polyol compound. The "adduct" refers to a reactant of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Examples of the adduct include xylylene diisocyanate adducts of trimethylolpropane described later. Further, the "isocyanate-terminated urethane prepolymer" is the same as described above.
More specific examples of the organic polyisocyanate compound include 2, 4-tolylene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding one or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or a part of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, and the like.
Examples of the organic polyimine compound include N, N ' -diphenylmethane-4, 4 ' -bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate, tetramethylolmethane-tris- β -aziridinylpropionate, and N, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine.
When an organic polyisocyanate compound is used as the crosslinking agent (F), a hydroxyl group-containing polymer is preferably used as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinked structure can be easily introduced into the film for forming a thermosetting protective film by the reaction of the crosslinking agent (F) with the polymer component (a).
The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer component (A). By setting the content of the crosslinking agent (F) to the lower limit or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. Further, by making the content of the crosslinking agent (F) the upper limit value or less, the excessive use of the crosslinking agent (F) can be suppressed.
[ energy ray-curable resin (G) ]
The composition (III-1) may contain an energy ray-curable resin (G). By incorporating the energy ray-curable resin (G) into the film for forming a thermosetting protective film, the properties can be changed by irradiation with an energy ray.
The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylic ester-based compound include (meth) acrylates having a chain-like aliphatic skeleton such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate; a (meth) acrylate having a cyclic aliphatic skeleton such as dicyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; a urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylates; a polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; itaconic acid oligomers, and the like.
The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30000, more preferably 300 to 10000.
The energy ray-curable compound used for the polymerization may be one kind only, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
The energy ray-curable resin (G) contained in the composition (III-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) in the composition (III-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total content of all components except the solvent.
[ photopolymerization initiator (H) ]
When the composition (III-1) contains the energy ray-curable resin (G), a photopolymerization initiator (H) may be contained in order to efficiently advance the polymerization reaction of the energy ray-curable resin (G).
Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2, 2-dimethoxy-1, 2-diphenylethane-1-one, acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide, α -ketol compounds such as 1-hydroxycyclohexylphenyl ketone, azo compounds such as azobisisobutyronitrile, titanocene compounds such as titanocene, thioxanthone compounds such as thioxanthone, peroxide compounds, diketone compounds such as succinyl benzil, benzoin-1, 2-diethylbenzoin-1, 2- [ 2- (2-diethylmethyl) phenyl-ketone ] methyl ketal, and 2- (2-chloro-methyl) acetone.
Further, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like.
The photopolymerization initiator (H) contained in the composition (III-1) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable resin (G).
[ colorant (I) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a colorant (I).
Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.
Examples of the organic pigments and organic dyes include aminium (aminium) pigments, cyanine pigments, merocyanine pigments, croconium (croconium) pigments, squarylium (squarylium) pigments, azulenium (azulenium) pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalimide (naphthaloctamide) pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt pigments), dithiol metal complex pigments, indole pigments, triarylmethane pigments, anthraquinone pigments, biphenol pigments, naphthol pigments, and naphthol pigments, Azomethine pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, and the like.
Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium tin oxide) pigments, ATO (antimony tin oxide) pigments, and the like.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of the colorant (I), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
When the colorant (I) is used, the content of the colorant (I) in the film for forming a thermosetting protective film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the protective film, the printing visibility at the time of laser printing on the protective film can be adjusted. Further, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the design of the protective film can be improved, and the grinding traces on the back surface of the semiconductor wafer can be made less noticeable. In view of these points, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all the components except the solvent (i.e., the content of the colorant (I) in the film for forming a thermosetting protective film) is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and particularly preferably 0.1 to 5% by mass. By setting the content of the colorant (I) to the lower limit value or more, the effect of using the colorant (I) can be more remarkably obtained. Further, by setting the content of the colorant (I) to the upper limit or less, it is possible to suppress an excessive decrease in light transmittance of the thermosetting protective film-forming film.
[ general additive (J) ]
The composition (III-1) and the film for forming a thermosetting protective film may further contain a general-purpose additive (J) within a range not to impair the effects of the present invention.
The general-purpose additive (J) may be any known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, but preferable additives include, for example, a plasticizer, an antistatic agent, an antioxidant, and a gettering agent (gettergent).
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of the general-purpose additive (J), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the general-purpose additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected depending on the purpose.
[ solvent ]
Preferably, the composition (III-1) further contains a solvent. The composition (III-1) containing a solvent was excellent in handling properties.
The solvent is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the composition (III-1) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like, since the components contained in the composition (III-1) can be mixed more uniformly.
Preparation method of composition for Forming thermosetting protective film
The thermosetting protective film-forming composition such as composition (III-1) can be obtained by blending the respective components constituting it.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any of the components other than the solvent to preliminarily dilute the components, or the solvent may be mixed with the components without preliminarily diluting any of the components other than the solvent to use the mixture.
The method for mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time when the components are added and mixed are not particularly limited as long as the components are not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
○ film for forming energy ray-curable protective film
The energy ray-curable protective film-forming film includes an energy ray-curable protective film-forming film containing an energy ray-curable component (a), and preferably an energy ray-curable protective film-forming film containing an energy ray-curable component (a) and a filler.
In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive. Here, "energy ray" and "energy ray curability" are the same as those described above.
When the cured product has a degree of curing to sufficiently exert its function, the curing conditions for curing the energy ray-curable protective film-forming film after it is attached to the back surface of the semiconductor wafer are not particularly limited, and may be appropriately selected depending on the kind of the energy ray-curable protective film-forming film.
For example, when the film for forming the energy ray-curable protective film is cured, the illuminance of the energy ray is preferably 120 to 280mW/cm2. The amount of the energy ray during curing is preferably 100 to 1000mJ/cm2。
< composition for Forming energy ray-curable protective film (IV-1) >
Examples of a preferable energy ray-curable composition for forming a protective film include an energy ray-curable composition for forming a protective film (IV-1) (which may be abbreviated as "composition (IV-1)" in the present specification) containing the energy ray-curable component (a).
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and is also a component for imparting film formability, flexibility, and the like to the energy ray-curable protective film-forming film, and for forming a hard protective film after curing.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000; and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000. At least a portion of the polymer (a1) may or may not be crosslinked by a crosslinking agent.
(a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000.)
Examples of the polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000 include an acrylic resin (a1-1) obtained by reacting an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound with an energy ray-curable compound (a12) having an energy ray-curable group such as a group reactive with the functional group and an energy ray-curable double bond.
Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which 1 or 2 hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxyl group in terms of a point of preventing corrosion of a circuit of a semiconductor wafer, a semiconductor chip, or the like.
Among them, the functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a11)
Examples of the acrylic polymer having a functional group (a11) include a polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group, and a polymer obtained by further copolymerizing a monomer other than the acrylic monomer (a non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method may be used.
Examples of the acrylic monomer having the functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols (unsaturated alcohols having no (meth) acryloyl skeleton) such as vinyl alcohol and allyl alcohol.
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be one type only, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also referred to as lauryl (meth) acrylate), tridecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester has 1 to 18 carbon atoms, such as tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate).
Examples of the acrylic monomer having no functional group include (meth) acrylates containing an alkoxyalkyl group such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and non-crosslinkable (meth) acrylic esters having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one type only, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio in such a range, the content of the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be easily adjusted to a preferable range of the degree of curing of the protective film.
The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (IV-1), the proportion of the content of the acrylic resin (a1-1) to the total content of the components other than the solvent (i.e., the content of the acrylic resin (a1-1) in the energy ray-curable protective film-forming film) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass.
Energy ray-curable compound (a12)
The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with a functional group of the acrylic polymer (a11), and more preferably the energy ray-curable compound (a12) has an isocyanate group as the group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with a hydroxyl group of the acrylic polymer (a11) having the hydroxyl group as the functional group.
The energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably has 1 to 3 energy ray-curable groups.
Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloxymethyl) ethyl isocyanate;
an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
and an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate.
Among them, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is in such a range, the adhesive force of the protective film after curing becomes larger. Further, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the proportion of the content is 100 mol%, but when the energy ray-curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the proportion of the content may exceed 100 mol%.
The weight average molecular weight (M) of the polymer (a1)W) Preferably 100000-2000000, more preferably 300000-1500000.
When at least a part of the polymer (a1) is crosslinked by a crosslinking agent, the polymer (a1) may be a polymer which is polymerized by a monomer having a group which reacts with the crosslinking agent and is not one of the monomers described above as monomers constituting the acrylic polymer (a11) and which is crosslinked at a group which reacts with the crosslinking agent, or may be a polymer which is crosslinked at a group which reacts with the functional group from the energy ray-curable compound (a12)
The polymer (a1) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000.)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and preferable examples thereof include a (meth) acryloyl group, a vinyl group and the like.
The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low molecular weight compounds having an energy ray-curable group, epoxy resins having an energy ray-curable group, and phenol resins having an energy ray-curable group.
Examples of the low molecular weight compound having an energy ray-curable group in the compound (a2) include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloyloxypropyloxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and mixtures thereof, Bifunctional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and 2-hydroxy-1, 3-di (meth) acryloyloxypropane;
polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate;
and polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.
As the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group in the compound (a2), for example, the resins described in paragraph 0043 and the like of jp 2013-a 194102 can be used. Such a resin also belongs to a resin constituting a thermosetting component described later, but it is regarded as the compound (a2) in the present invention.
The weight average molecular weight of the compound (a2) is preferably 100 to 30000, more preferably 300 to 10000.
The compound (a2) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the composition (IV-1) and the energy ray-curable protective film-forming film contain the compound (a2) as the energy ray-curable component (a), it is preferable that the composition further contains a polymer (b) having no energy ray-curable group.
The polymer (b) may be one at least partially crosslinked with a crosslinking agent or one that is not crosslinked.
Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.
Among them, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known acrylic polymer, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers (non-acrylic monomers) other than the acrylic monomers.
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, glycidyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, and substituted amino group-containing (meth) acrylates. Here, the "substituted amino group" is the same as described above.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth, And alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester has 1 to 18 carbon atoms, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).
Examples of the (meth) acrylate having a cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate, and the like.
Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate and the like.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate and the like.
Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
Examples of the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked by a crosslinking agent, include polymers obtained by reacting a reactive functional group in the polymer (b) with a crosslinking agent.
The reactive functional group may be appropriately selected depending on the kind of the crosslinking agent, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among them, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among them, a carboxyl group having high reactivity with an epoxy group is preferable. However, from the viewpoint of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip, it is preferable that the reactive functional group is a group other than a carboxyl group.
Examples of the polymer (b) having the reactive functional group and not having an energy ray-curable group include polymers obtained by polymerizing a monomer having at least the reactive functional group. When the polymer (b) is the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer exemplified as the monomer constituting the acrylic polymer (b-1) may be used as the monomer having the reactive functional group. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and in addition to these, polymers obtained by polymerizing a monomer obtained by substituting one or two or more hydrogen atoms of the above-mentioned acrylic monomer or non-acrylic monomer mentioned above for the reactive functional group.
In the polymer (b) having a reactive functional group, the proportion (content) of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer (b) is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass. By setting the ratio in such a range, the degree of crosslinking in the polymer (b) becomes a more preferable range.
From the viewpoint of further improving the film-forming property of the composition (IV-1), the weight-average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 1500000. Here, "weight average molecular weight" is the same as that explained above.
The composition (IV-1) and the energy ray-curable protective film-forming film may contain only one kind of polymer (b) having no energy ray-curable group, or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
The composition (IV-1) may be a composition containing either one or both of the polymer (a1) and the compound (a 2). When the composition (IV-1) contains the compound (a2), it preferably further contains a polymer (b) having no energy ray-curable group, and in this case, it preferably further contains the compound (a 1). The composition (IV-1) may contain the polymer (a1) and the polymer (b) having no energy ray-curable group, in addition to the compound (a 2).
When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the content of the compound (a2) in the composition (IV-1) is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the energy ray-curable protective film-forming film) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray-curability of the energy ray-curable protective film-forming film becomes more favorable.
The composition (IV-1) may contain one or more selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive, depending on the purpose, in addition to the energy ray-curable component.
For example, by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component, the adhesive force of the formed energy ray-curable protective film-forming film to an adherend is improved by heating, and the strength of the protective film formed from the energy ray-curable protective film-forming film is also improved.
Further, by using the composition (IV-1) containing the energy ray-curable component and the colorant, the formed energy ray-curable protective film-forming film can exhibit the same effects as those when the thermosetting protective film-forming film described above contains the colorant (I).
The thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive in the composition (IV-1) may be the same as those of the thermosetting component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H), the colorant (I) and the general-purpose additive (J) in the composition (III-1), respectively.
In the composition (IV-1), the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant and general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the purpose, and is not particularly limited.
Since the handling properties of the composition (IV-1) are improved by dilution, it is preferable to further contain a solvent.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The composition (IV-1) may contain only one solvent, or may contain two or more solvents.
Method for producing composition for forming energy ray-curable protective film
The energy ray-curable composition for forming a protective film, such as the composition (IV-1), can be obtained by blending the components constituting it.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any of the components other than the solvent to preliminarily dilute the components, or the solvent may be mixed with the components without preliminarily diluting any of the components other than the solvent to use the mixture.
The method for mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time when the components are added and mixed are not particularly limited as long as the components are not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
○ film for forming non-curable protective film
The film for forming a non-curable protective film does not show a change in characteristics due to curing, and in the present invention, it is considered that a protective film is formed at the stage of being bonded to a target portion such as the back surface of a semiconductor wafer.
Examples of a preferable non-curable protective film-forming film include a non-curable protective film-forming film containing a thermoplastic resin.
< composition for Forming non-curable protective film (V-1) >
Examples of the composition for forming a non-curable protective film include the composition (V-1) for forming a non-curable protective film (hereinafter, abbreviated as "composition (V-1)") containing the thermoplastic resin.
[ thermoplastic resin ]
The thermoplastic resin is not particularly limited.
More specifically, the thermoplastic resin may be the same resin as the non-curable resin such as acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene or polystyrene, which is exemplified as the component contained in the composition (III-1).
The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (V-1), the proportion of the content of the thermoplastic resin with respect to the total content of the components other than the solvent (i.e., the content of the thermoplastic resin in the non-curable protective film-forming film) is preferably 5 to 90% by mass, and may be, for example, any one of 10 to 80% by mass and 20 to 70% by mass.
The composition (V-1) may contain, in addition to the thermoplastic resin, one or more selected from the group consisting of a filler, a coupling agent, a crosslinking agent, a colorant and a general-purpose additive, depending on the purpose.
For example, by using the composition (V-1) containing the thermoplastic resin and the colorant, the formed film for forming a non-curable protective film exhibits the same effects as those in the case where the film for forming a thermosetting protective film described above contains the colorant (I).
The filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the composition (V-1) may be the same as the filler (D), coupling agent (E), crosslinking agent (F), colorant (I) and general-purpose additive (J) in the composition (III-1).
In the composition (V-1), the filler, the coupling agent, the crosslinking agent, the colorant and the general-purpose additive may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the filler, the coupling agent, the crosslinking agent, the colorant and the general-purpose additive in the composition (V-1) may be appropriately adjusted according to the purpose, and is not particularly limited.
Since the handling properties of the composition (V-1) are improved by dilution, it is preferable to further contain a solvent.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
The composition (V-1) may contain only one kind of solvent, or may contain two or more kinds of solvents.
Preparation method of composition for Forming non-curable protective film
The composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending the respective components constituting it.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any of the components other than the solvent to preliminarily dilute the components, or the solvent may be mixed with the components without preliminarily diluting any of the components other than the solvent to use the mixture.
The method for mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time when the components are added and mixed are not particularly limited as long as the components are not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
◎ other layers
The support sheet may include other layers such as the intermediate layer in addition to the base material and the adhesive layer, within a range not impairing the effects of the present invention.
In addition, the composite sheet for forming a protective film may include other layers in addition to the base material, the adhesive agent layer, and the film for forming a protective film, within a range not impairing the effects of the present invention, and in this case, the other layers may be the other layers included in the support sheet or may be disposed so as not to be in direct contact with the support sheet.
The other layer may be arbitrarily selected according to the purpose, and the kind thereof is not particularly limited.
Examples of an embodiment of the composite sheet for forming a support sheet and a protective film include: the adhesive layer is non-energy ray-curable, the adhesive layer contains the acrylic polymer and a crosslinking agent, wherein the acrylic polymer at least has a structural unit derived from (methyl) acrylic acid alkyl ester, the content of the crosslinking agent in the adhesive layer is 0.3-50 parts by mass relative to 100 parts by mass of the acrylic polymer, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01-8 mu m.
Examples of an embodiment of the composite sheet for forming a support sheet and a protective film include: the adhesive layer is non-energy ray-curable, the adhesive layer contains the acrylic polymer and a crosslinking agent, wherein the acrylic polymer at least comprises a structural unit derived from alkyl (meth) acrylate, the content of the crosslinking agent in the adhesive layer is 0.3-50 parts by mass relative to 100 parts by mass of the acrylic polymer, the acrylic polymer comprises a structural unit derived from alkyl (meth) acrylate with 4 or more carbon atoms of alkyl and a structural unit derived from a hydroxyl-containing monomer, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01-8 [ mu ] m.
Examples of an embodiment of the composite sheet for forming a support sheet and a protective film include: the adhesive layer is non-energy ray-curable, and the adhesive layer contains the acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate and a crosslinking agent, wherein the content of the crosslinking agent is 0.3 to 50 parts by mass relative to 100 parts by mass of the acrylic polymer, the acrylic polymer has a structural unit derived from an alkyl (meth) acrylate having 4 or more carbon atoms in an alkyl group and a structural unit derived from a hydroxyl group-containing monomer, the content of the structural unit derived from the hydroxyl group-containing monomer in the acrylic polymer is 1 to 35% by mass relative to the total amount of the structural units, and the maximum height roughness (Rz) of the first surface of the base material is 0.01 to 8 [ mu ] m.
Examples of an embodiment of the composite sheet for forming a support sheet and a protective film include: the adhesive agent layer is non-energy ray-curable, the adhesive agent layer contains the acrylic polymer and a cross-linking agent, wherein the acrylic polymer at least contains a structural unit derived from alkyl (methyl) acrylate and the cross-linking agent, the content of the cross-linking agent is 0.3-50 parts by mass relative to 100 parts by mass of the acrylic polymer, the acrylic polymer contains a structural unit derived from alkyl (methyl) acrylate with 4 or more carbon atoms of alkyl and a structural unit derived from a hydroxyl-containing monomer, the content of the structural unit derived from the hydroxyl-containing monomer in the acrylic polymer is 1-35% by mass relative to the total amount of the structural units, the cross-linking agent is isocyanate cross-linking agent, and the supporting sheet and the protective film forming composite sheet have the maximum height roughness (Rz) of the first surface of the base material of 0.01-8 mu m.
◇ method for manufacturing composite sheet for forming protective film
The composite sheet for forming a protective film can be produced, for example, by a production method (in the present specification, sometimes referred to as "production method (S1)") including the steps of: a step of producing a laminated sheet in which a substrate, an adhesive layer, and a film for forming a protective film are laminated in this order in the thickness direction (in this specification, this step may be referred to as "laminated sheet production step (1)"); and a step of storing the laminate sheet while pressing the laminate sheet along the thickness direction thereof (in this specification, the step may be referred to as a "laminate sheet storing step").
The formation method of each layer (substrate, adhesive layer, and protective film-forming film) is as described above.
The above-described production method (S1) will be described in further detail below for each step.
◎ method for manufacturing (S1)
Step (1) of producing laminated sheet
In the laminated sheet production step (1), a laminated sheet is produced in which a base material, an adhesive agent layer, and a protective film-forming film are laminated in this order in the thickness direction thereof.
In this step, for example, the layers (the base material, the adhesive agent layer, the protective film-forming film, and the like) are laminated so as to have a corresponding positional relationship, thereby producing a laminated sheet having the same laminated structure as that of the composite sheet for forming a target protective film.
In the present specification, unless otherwise specified, "laminate sheet" means a laminate sheet having the same laminate structure as that of the composite sheet for forming a protective film of interest as described above and having not been subjected to the above-described laminate sheet storage step.
For example, when the adhesive layer is laminated on a substrate in the production of a support sheet, the adhesive composition may be applied to the substrate and dried as necessary.
On the other hand, for example, when a film for forming a protective film is further laminated on an adhesive layer laminated on a substrate, the film for forming a protective film can be directly formed by applying the composition for forming a protective film on the adhesive layer. In the same manner, a layer other than the film for forming a protective film can be laminated on the adhesive layer using the composition for forming the layer. In this manner, when a laminated structure of two continuous layers is formed using either composition, a new layer can be formed by further applying the composition to a layer formed of the composition. Among them, it is preferable that a post-laminated layer of the two layers is formed in advance on another release film using the composition, and an exposed surface of the formed layer on the opposite side to the side in contact with the release film is bonded to an exposed surface of the formed layer, thereby forming a continuous two-layer laminated structure. In this case, the composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film may be removed as necessary.
For example, when a composite sheet for forming a protective film (a composite sheet for forming a protective film in which a support sheet is a laminate of a substrate and an adhesive layer) is produced by laminating an adhesive layer on a substrate and laminating a film for forming a protective film on the adhesive layer, the adhesive layer is laminated on the substrate by applying an adhesive composition to the substrate and drying it as necessary, and the film for forming a protective film is formed on a release film by applying a composition for forming a protective film to the release film and drying it as necessary. Then, the exposed surface of the film for forming a protective film is laminated on the adhesive layer by bonding the exposed surface of the film for forming a protective film to the exposed surface of the adhesive layer laminated on the base material, thereby obtaining the laminated sheet.
In addition, when the adhesive layer is laminated on the substrate, as described above, the adhesive layer may be formed on the release film by applying the adhesive composition to the release film and drying it as necessary, and the adhesive layer may be laminated on the substrate by bonding the exposed surface of the layer to one surface of the substrate, instead of applying the adhesive composition to the substrate.
In either method, the release film may be removed at any timing after the formation of the target laminated structure.
In this manner, since the layers other than the base material constituting the composite sheet for forming a protective film can be formed in advance on the release film and laminated by a method of bonding to the surface of the target layer, the layer to be used in such a step can be appropriately selected as necessary to produce the laminated sheet.
For example, the composite sheet for forming a protective film is generally stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side to the support sheet. Therefore, the laminate sheet can be obtained even when a composition for forming the layer constituting the outermost layer, such as a composition for forming a protective film, is applied to the release film (preferably, on the release-treated surface thereof) and dried as necessary to form the layer constituting the outermost layer on the release film, and other layers are laminated on the exposed surface of the layer on the opposite side to the side in contact with the release film by any of the above-described methods, and the release film is bonded without being removed.
When the composite sheet for forming a protective film includes the other layer, a step of providing the other layer may be added as appropriate at an appropriate timing in the laminate sheet production step (1) so that the other layer is disposed at an appropriate position.
The shape of the laminate sheet produced in the laminate sheet production step (1) is not particularly limited. For example, a long laminated sheet suitable for winding into a roll shape may be produced, or a laminated sheet having a shape other than a long one may be produced.
Storage Process for laminated sheet
In the laminated sheet storage step, the laminated sheet is stored while being pressed in the thickness direction thereof.
In this step, as a method for storing the laminated sheet while pressing it, for example, the following methods can be mentioned: a method of winding a long laminate sheet into a roll shape, holding the wound laminate sheet in this state, and storing the laminate sheet while applying pressure generated by winding to one surface or both surfaces of the laminate sheet; and a method of storing a long laminated sheet while applying pressure to one surface or both surfaces of the laminated sheet in an unfolded state or the laminated sheet not in a long state without winding the laminated sheet in a roll shape.
When the long laminate sheet is wound into a roll shape, it is preferable to wind the laminate sheet in the longitudinal direction thereof.
When the laminate sheet is wound, for example, the winding tension is preferably 150 to 170N/m, the winding speed is preferably 45 to 55 m/min, and the taper ratio (reduction rate) of the winding tension is preferably 85 to 95%. By adopting such winding conditions, the laminated sheet can be stored under pressure with a more appropriate pressure. Such winding conditions are particularly suitable for application to a laminate sheet having a thickness of 100 to 300 μm, a width of 300 to 500mm and a length of 40 to 60m, for example, but the size of the laminate sheet is not limited thereto.
For example, the laminate sheet may be wound at normal temperature or room temperature, or may be wound under the same temperature conditions as those in the case of storing the wound laminate sheet under heating and pressing as described later.
The laminated sheet wound in a roll shape can be stored at normal temperature or room temperature, but is preferably stored while being heated. By performing the heat and pressure storage in this manner, a composite sheet for forming a protective film having excellent lamination properties of the adhesive layer and the film for forming a protective film and excellent printing visibility of the protective film or the film for forming a protective film via the support sheet can be obtained.
The heating temperature for storage when the laminate sheet is wound into a roll is not particularly limited, but is preferably 53 to 75 ℃, more preferably 55 to 70 ℃, and particularly preferably 57 to 65 ℃.
The storage time when the laminate sheet is wound into a roll shape is not particularly limited, but is preferably 24 to 720 hours (1 to 30 days), more preferably 48 to 480 hours (2 to 20 days), and particularly preferably 72 to 240 hours (3 to 10 days).
The laminate sheet wound in a roll shape may be, for example, the following laminate sheet: a laminated sheet is obtained by processing a protective film forming film and a support sheet into a specific shape, attaching the protective film forming film side of a laminate of the support sheet and the protective film formed in this manner to a long release film, and aligning the laminate in the longitudinal direction of the release film. The protective film forming film in this case preferably has the same or almost the same planar shape (usually circular shape) as the semiconductor wafer. Further, it is preferable that the support sheet at this time has the same or almost the same peripheral shape as that of the jig for fixing the support sheet in the cutting device. In this case, it is preferable that a strip-shaped sheet is provided so as not to overlap with the laminate in the vicinity of the peripheral edge portion in the short-side direction of the bonding surface of the laminate of the release film. When the laminated sheet is wound into a roll shape, the sheet is used to suppress the occurrence of a level difference (in this specification, it may be referred to as "lamination mark") on the surface of the laminated article. In the roll of the laminated sheet, the lamination position of the laminate (the laminate of the processed support sheet and the protective film forming film) does not coincide with each other in the radial direction of the roll, and therefore the lamination mark is generated by applying a large pressure to the surface of the laminate. When the sheet is provided in the vicinity of the peripheral edge portion, such a large pressure is not applied to the surface of the laminate, and the occurrence of lamination marks can be suppressed.
When the long laminated sheet is set in an unfolded state without being wound into a roll shape, and when the laminated sheet is not long, it is preferable to further laminate and store a plurality of the laminated sheets. When the laminated sheets are laminated in this manner, it is preferable that the orientation and the position of the peripheral edge of the plurality of laminated sheets are set to be matched with each other.
The shape and size of the laminate sheet that is not long (in other words, a plate-like laminate sheet) are not particularly limited. For example, it is preferable that: using a cutting device, the shape and size of the laminated sheet are adjusted to be suitable for processing 1 semiconductor wafer according to the shape and size of the semiconductor wafer and the shape and size of a fixture for fixing the supporting sheet in the cutting device.
The laminated sheet in a laminated state may be stored at normal temperature or room temperature, but is preferably stored while being heated. By performing the heat and pressure storage in this manner, a composite sheet for forming a protective film having excellent lamination properties of the adhesive layer and the film for forming a protective film and excellent printing visibility of the protective film or the film for forming a protective film via the support sheet can be obtained.
Further, the heating temperature and the storage time when the laminated sheet in the laminated state is stored under pressure can be set to be the same as those when the laminated sheet is wound into a roll shape.
In the manufacturing method (S1), after the laminate storage step is completed, the intended composite sheet for forming the protective film is obtained by pressing the laminate and, if necessary, releasing the heating.
In the laminated sheet production step (1) of the production method (S1), the order of lamination (bonding) of the base material, the adhesive agent layer, and the protective film-forming film is not particularly limited, but when a support sheet is produced in advance (the adhesive agent layer is laminated on the base material in advance), a protective film-forming film is produced in advance, and the protective film-forming film is laminated on the support sheet, either one or both of the support sheet and the protective film-forming film may be stored under pressure separately by the same method as in the case of the above laminated sheet, before the support sheet and the protective film-forming film are laminated. By storing the support sheet before lamination alone under pressure, the occurrence of the non-bonded region between the base material and the adhesive layer can be more effectively suppressed. Further, by separately storing the protective film-forming film before lamination under pressure, the degree of unevenness (smoothness) of the adhesive layer side surface (second surface) of the protective film-forming film and the protective film is reduced (smoothness is increased), and the design properties of the protective film-forming film and the protective film are improved.
That is, the composite sheet for forming a protective film can be produced, for example, by a production method (which may be referred to as "production method (S2)" in the present specification) including: a step of laminating a protective film-forming film on the adhesive layer of a support sheet obtained by laminating a base material and an adhesive layer to prepare a laminated sheet in which the base material, the adhesive layer, and the protective film-forming film are laminated in this order in the thickness direction thereof (in this specification, this step may be referred to as a "laminated sheet-preparing step (2)"); and a step (storage step) of storing the laminate sheet along the thickness direction thereof by pressing the laminate sheet, wherein the production method (S2) further comprises a step of storing either one or both of the support sheet and the protective-film-forming film along the thickness direction thereof by pressing the support sheet and the protective-film-forming film along the thickness direction thereof, before the laminate sheet production step (2) (i.e., before the support sheet and the protective-film-forming film are laminated) (in this specification, the step of storing the support sheet is sometimes referred to as a "support sheet storage step", and the step of storing the protective-film-forming film is sometimes referred to as a "protective-film-forming film storage step").
◎ method for manufacturing (S2)
The manufacturing method (S2) is the same as the manufacturing method (S1) except that the laminate sheet manufacturing step (2) is performed as the laminate sheet manufacturing step (1), and either one or both of the support sheet storage step and the protective film-forming film storage step are further performed.
Step (2) of producing laminated sheet
The laminated sheet production step (2) is the same as the laminated sheet production step (1) in the production method (S1), except for the points that the support sheet is produced in advance, the protective film-forming film is produced in advance, and the lamination order of the layers is defined so that the protective film-forming film is laminated on the support sheet.
Storage Process for supporting sheet and storage Process for film for Forming protective film
The support sheet storage step and the protective film-forming film storage step may be performed in the same manner as the laminate sheet storage step in the manufacturing method (S1), respectively, except that the storage object is not a laminate sheet, but a support sheet or a protective film-forming film.
In this case, for example, the holding time of the support sheet and the protective film-forming film may be in any range of 24 to 720 hours (1 to 30 days), 48 to 480 hours (2 to 20 days), and 72 to 240 hours (3 to 10 days), independently, as in the case of the laminate sheet.
On the other hand, in addition to the point of changing the storage object as described above and further changing the storage time of the storage object (the support sheet or the film for forming the protective film), the support sheet storage step and the film for forming the protective film storage step may be performed in the same manner as the laminate sheet storage step in the manufacturing method (S1), respectively.
In this case, for example, the holding time of the support sheet and the protective film forming film may be set independently in any range of 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours (0.5 to 10 days). However, these ranges are only one example of the retention time.
Examples
The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.
< raw Material for production of composition for Forming protective film >
The raw materials used for preparing the composition for forming a protective film are shown below.
Polymer component (A)
(A) -1: acrylic Polymer (weight-average molecular weight 370000, glass transition temperature 6 ℃ C.) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass)
Thermosetting component (B1)
(B1) -1: bisphenol A epoxy resin ("jER 828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184-194 g/eq)
(B1) -2: bisphenol A type epoxy resin ("jER 1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 800 to 900g/eq)
(B1) -3: dicyclopentadiene type epoxy resin ("EPICLON HP-7200 HH" manufactured by DIC CORPORATION, epoxy equivalent 255-260 g/eq)
Heat-curing agent (B2)
(B2) -1: dicyandiamide ("ADEKA HARDENER EH-3636 AS" manufactured by ADEKACORPORATION, heat-activated latent epoxy resin curing agent, active hydrogen equivalent 21g/eq)
Curing Accelerator (C)
(C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole ("CURZOL 2 PHZ-PW" manufactured by SHIKOKU CHEMICALS CORPORATION)
Filler (D)
(D) -1: silica Filler (SC 2050MA manufactured by Admatechs corporation, silica Filler surface-modified with an epoxy compound, average particle diameter 0.5 μm)
Coupling agent (E)
(E) -1: 3-aminopropyltrimethoxysilane (NUC CO., LTD. "A-1110")
Colorant (I)
(I) -1: black pigment (Dainiciseika Color & Chemicals Mfg. Co., Ltd.; Ltd.)
[ example 1]
< production of supporting sheet >
(preparation of adhesive composition (I-4))
A non-energy ray-curable adhesive composition (I-4) having a solid content of 30 mass% was prepared, which contained 100 parts by mass of an acrylic polymer and 40 parts by mass (solid content) of a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Kogyo chemical Co., Ltd.) and further contained a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate as a solvent. The acrylic polymer was a pre-copolymer having a weight average molecular weight of 800000, copolymerized from 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass).
(production of support sheet)
The adhesive composition (I-4) obtained above was applied to a release-treated surface of a polyethylene terephthalate film using a release film (SP-PET 381031 manufactured by Lintec Corporation, "thickness 38 μm") whose one surface was subjected to release treatment by silicone treatment, and dried by heating at 120 ℃ for 2 minutes, thereby forming a non-energy ray-curable adhesive layer. At this time, the adhesive composition (I-4) was applied under the condition that the thickness of the adhesive layer was set to 4 μm.
A polypropylene film (manufactured by Mitsubishi Plastics, inc., thickness 80 μm) was sandwiched between a metal roll having an uneven surface and a metal roll having a smooth surface, and the uneven surface of the metal roll was pressed against one surface of the polypropylene film while being rotated while being heated to 60 ℃, thereby producing a substrate having an uneven surface on one surface and a smooth surface (bright surface) on the other surface. The uneven surface of the base material was measured for the R value of the base material in the same manner as for the R value of the adhesive agent layer, and the result was 1.8 μm.
Next, the uneven surface of the base material is bonded to the exposed surface of the adhesive layer obtained above, whereby a support sheet is obtained in which the base material, the adhesive layer, and the release film are sequentially laminated in the thickness direction thereof. The width of the resulting support sheet (in other words, the width of the base material and the adhesive layer) was 400mm, and the length was 250 m.
Through the way, the support sheet is obtained.
Immediately thereafter, the support sheet was evaluated for a non-bonded region between the base material and the adhesive layer, which will be described later. The support sheet is used in this state as it is for producing a protective film-forming composite sheet to be described later.
< production of composite sheet for Forming protective film >
(preparation of composition for Forming protective film (III-1))
A thermosetting composition (III-1) for forming a protective film having a solid content of 51 mass% was obtained by dissolving or dispersing the polymer component (a) -1(150 parts by mass), the thermosetting component (B1) -1(60 parts by mass), (B1) -2(10 parts by mass), (B1) -3(30 parts by mass), (B2) -1(2 parts by mass), the curing accelerator (C) -1(2 parts by mass), the filler (D) -1(320 parts by mass), the coupling agent (E) -1(2 parts by mass), and the colorant (I) -1(18 parts by mass) in a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate, and stirring at 23 ℃. The blending amounts shown here are all solid component amounts.
(production of film for Forming protective film)
The above-obtained composition (III-1) for forming a protective film was coated on the release-treated surface of a polyethylene terephthalate film using a release film (second release film, "SP-PET 381031" manufactured by Lintec Corporation, having a thickness of 38 μm) whose one surface was subjected to release treatment by silicone treatment, and a blade coater, and dried at 100 ℃ for 2 minutes, thereby producing a thermosetting film for forming a protective film having a thickness of 25 μm.
Further, a release-treated surface of a release film (first release film, "SP-PET 381031 manufactured by Lintec Corporation," thickness 38 μm ") was bonded to the exposed surface of the obtained protective film-forming film on the side not having the second release film, thereby obtaining a laminated film having the first release film on one surface and the second release film on the other surface of the protective film-forming film. The width of the obtained laminated film (in other words, the width of the protective film-forming film, the first release film, and the second release film) was 400 mm.
(production of composite sheet for Forming protective film)
1 set (2) of rolls each having a diameter of 5cm and a depth of 3mm from the surface thereof, and composed of heat-resistant silicone rubber having a hardness of 50 degrees were prepared.
The release film was removed from the adhesive layer of the support sheet obtained above. Further, the first release film was removed from the laminated film obtained above.
Then, the exposed surface of the adhesive layer produced by removing the release film and the exposed surface of the protective film forming film produced by removing the first release film were opposed to each other, and the support sheet and the protective film forming film were laminated to prepare a laminate, and the laminate was passed through the gap between the rolls set at 60 ℃ at a speed of 0.3 m/min, and heated and pressed at a pressure of 0.5MPa (heat lamination). Thus, a laminated sheet (composite sheet for forming a protective film before storage) having the same laminated structure as that of the composite sheet for forming a target protective film, which is formed by sequentially laminating the base material, the adhesive layer, the film for forming a protective film, and the second release film in the thickness direction thereof, was prepared.
The width of the resulting laminate sheet (in other words, the width of the support sheet) was 400 mm.
Then, the laminate sheet having the overall size of 400mm × 250m obtained as described above was wound around a core of ABS resin in a roll shape with the longitudinal direction thereof being the winding direction and under conditions of a winding tension of 160N/m, a winding speed of 50 m/min, and a taper ratio of the winding tension of 90%, and the laminate sheet was wound in such a manner that the substrate was directed outward in the radial direction of the roll (in other words, the second release film was brought into contact with the core).
Subsequently, the rolled laminate sheet was left to stand and stored at 60 ℃ for 7 days (168 hours) in an air atmosphere.
In this manner, the composite sheet for forming a protective film of the present invention having the structure shown in fig. 2 was obtained.
Next, the composite sheet for forming a protective film of the present invention after storage under such heating and pressurizing conditions was evaluated for the following items.
< evaluation of support sheet and composite sheet for formation of protective film >
(measurement of R value of adhesive agent layer)
A test piece having a size of × 3mm was cut out from 5 positions of the composite sheet for forming a protective film obtained as described above, and the cutting positions of the 5 positions were set to 1 position corresponding to the central portion of the circular film for forming a protective film and 4 positions corresponding to positions close to the peripheral portion and almost point-symmetrical with respect to the central portion, and in the cutting positions of the 5 positions, the center-to-center distance between the 1 position corresponding to the central portion and the 4 positions other than the positions close to the peripheral portion was 100 mm.
The Cross Section was formed on the test piece by using a Cross Section sample forming apparatus ("Cross Section Polisher SM-09010" manufactured by JEOL LTD., under the conditions of "in" 10 seconds "and" out "5 seconds", the ion source voltage was 3kV, and the total polishing time was 24 hours. Only 1 new cross section was formed on each 1 test piece.
The newly formed cross sections of these 5 test pieces were observed using a Scanning Electron Microscope (SEM), and the ratio of (the total of the linear distances between adjacent distinct vertices)/(the linear distance in the direction horizontal to the adhesive agent layer) of the adhesive agent layer of each test piece was determined. The observation region of the cross section of the test piece at this time was set to a region of 1mm in the width direction of the cross section.
The average value of these ratios is used as the R value of the adhesive layer. The results are shown in Table 1.
The method of measuring and determining the R value of the base material are also the same as those of the adhesive agent layer.
(evaluation of printing visibility of protective film)
The second release film was removed from the thus obtained composite sheet for forming a protective film, and the exposed surface (the surface opposite to the adhesive layer side) of the thus produced film for forming a protective film was attached to the back surface of an 8-inch semiconductor wafer. The attachment at this time can be performed using a chip mounter ("RAD 2700" manufactured by Lintec Corporation). Thus, a first laminated structure was produced in which the substrate, the adhesive layer, the protective film-forming film, and the semiconductor wafer were laminated in this order in the thickness direction.
Next, a surface (second surface) on the adhesive agent layer side of the film for forming a protective film in the first laminated structure was irradiated with laser light through the support sheet by using a laser printing apparatus ("CSM 300M" manufactured by ltd., EO technologies co., to print characters having a size of 0.3mm × 0.2.2 mm.
Next, the printing (laser printing) of the protective film-forming film was observed with the naked eye through the support sheet, and the visibility of the printing (characters) was evaluated according to the following criteria. The results are shown in Table 1. The printing visibility of the protective film-forming film evaluated here can be regarded as equivalent to that of the protective film.
A: the printed characters are clear and can be easily identified visually.
B: the printed characters are slightly blurred and cannot be easily visually recognized.
C: the printed characters are not clear and cannot be visually identified.
Then, the support sheet (base material and adhesive layer) is peeled off from the protective film-forming film. Then, the thickness of the line of the print (characters) formed on the protective film-forming film was measured using an optical microscope. As a result, the thickness of the line was 40 μm or more, and the printing was clear.
(evaluation of adhesion between base Material and adhesive agent layer)
The adhesion between the base material and the adhesive layer was tested by forming 100 grids in a 1mm square checkerboard pattern on the adhesive layer of the support sheet with a rotary cutter (rotary cutter) in accordance with JIS K5600-5-6, and after pressure-bonding an adhesive tape (Cellotape CO, manufactured by NICHIBAN CO, registered trademark) to the grid, peeling the adhesive tape at an angle of about 60 ° for 0.5 to 1.0 second, and counting the number of remaining grids in the 100 grids at that time. The adhesion was evaluated according to the following criteria. Then, the adhesion between the base material and the adhesive layer was evaluated according to the following criteria. The results are shown in Table 1.
A: the number of residual grids is more than 90.
B: the number of the residual grids is more than 70 and less than 90.
C: the number of residual grids is less than 70.
< production of composite sheet for forming support sheet and protective film, and evaluation of composite sheet for forming support sheet and protective film >
[ example 2]
In example 1, a substrate having an uneven surface on one side and a smooth surface on the other side (bright surface) was produced in the same manner as in example 1, except that the gap interval between the metal roll having an uneven surface and the metal roll having a smooth surface was adjusted to be narrower than that in example 1, when the uneven surface of the metal roll was pressed against one surface of a polypropylene film (thickness 80 μm, manufactured by Mitsubishi Plastics, inc.) while heating the uneven surface to 60 ℃. The R value of the substrate was measured on the uneven surface of the substrate, and was 2.8. A support sheet was produced and evaluated in the same manner as in example 1, except that the base material was used.
A composite sheet for forming a protective film was produced and evaluated in the same manner as in example 1, except that the support sheet was used.
The results are shown in Table 1.
[ example 3]
In example 2, a substrate having an uneven surface on one side and a smooth surface on the other side (bright surface) was produced in the same manner as in example 2, except that the gap interval between the metal roll having an uneven surface and the metal roll having a smooth surface was adjusted to be narrower than that in example 2, when the uneven surface of the metal roll was pressed against one surface of a polypropylene film (thickness 80 μm, manufactured by Mitsubishi Plastics, inc.) while heating the uneven surface to 60 ℃. The R value of the substrate was measured on the uneven surface of the substrate, and was 3.7. A support sheet was produced and evaluated in the same manner as in example 1, except that the base material was used.
A composite sheet for forming a protective film was produced and evaluated in the same manner as in example 1, except that the support sheet was used.
The results are shown in Table 1.
Comparative example 1
In example 1, a substrate having an uneven surface on one side and a smooth surface on the other side (bright surface) was produced in the same manner as in example 1, except that the gap interval between the metal roll having an uneven surface and the metal roll having a smooth surface was adjusted to be larger than that in example 1 when the uneven surface of the metal roll was pressed against one surface of a polypropylene film (thickness 80 μm, manufactured by Mitsubishi Plastics, inc.) while heating the uneven surface to 60 ℃. The R value of the substrate was measured on the uneven surface of the substrate, and the result was 1.0. A support sheet was produced and evaluated in the same manner as in example 1, except that the base material was used.
A composite sheet for forming a protective film was produced and evaluated in the same manner as in example 1, except that the support sheet was used.
The results are shown in Table 1.
Comparative example 2
In example 3, a substrate having an uneven surface on one side and a smooth surface on the other side (bright surface) was produced in the same manner as in example 3, except that in the case of heating the uneven surface of the metal roll to 60 ℃, rotating and pressing the metal roll against one surface of a polypropylene film (thickness 80 μm, manufactured by Mitsubishi Plastics, inc.) the gap interval between the metal roll having the uneven surface and the metal roll having the smooth surface was adjusted to be narrower than that in example 3. The R value of the substrate was measured on the uneven surface of the substrate, and the result was 5.7. A support sheet was produced and evaluated in the same manner as in example 1, except that the base material was used.
A composite sheet for forming a protective film was produced and evaluated in the same manner as in example 1, except that the support sheet was used.
A composite sheet for forming a protective film was produced and evaluated in the same manner as in example 1, except that the support sheet was used.
The results are shown in Table 1.
[ Table 1]
From the above results, in examples 1 to 3, the R value of the adhesive agent layer was 2 or more (2 to 4), and the adhesion between the substrate and the adhesive agent was particularly excellent. In these examples, the R value of the adhesive layer was less than 5.0(2 to 4), and the protective film-forming film were particularly excellent in printing visibility through the support sheet.
In contrast, in comparative example 1, the R value of the adhesive agent layer was 1.2, the adhesion between the substrate and the adhesive agent was insufficient, and a non-bonded region was present between the substrate and the adhesive agent.
In comparative example 2, the R value of the adhesive layer was 6.0, and an extremely thick region was present in the adhesive layer. Therefore, the protective film (protective film-forming film) having a supporting sheet interposed therebetween has poor printing visibility.
Industrial applicability
The invention can be used for manufacturing semiconductor devices.
Description of the reference numerals
1A, 1B, 1C: a composite sheet for forming a protective film; 10: a support sheet; 10 a: a surface (first surface) of the support sheet on the side of the protective film forming film; 11: a substrate; 11 a: the surface (first surface, uneven surface) on the adhesive layer side of the substrate; 12: an adhesive layer; 12 a: a surface (first surface) of the adhesive layer opposite to the substrate side; 12 b: a surface (second surface) of the adhesive layer on the substrate side; 13. 23: a protective film-forming film; 13 b: a surface (second surface) on the adhesive layer side of the protective film-forming film; l isa1、Lb1、La2、Lb2: the linear distance between adjacent distinct vertices; l is1、L2: a line segment projected on a plane in a direction horizontal to the adhesive layer; t isa: thickness of the adhesive layer; t isa1: a minimum value of the thickness of the adhesive layer; t isa2: the maximum value of the thickness of the adhesive layer.
Claims (3)
1. A support sheet comprising a base material and an adhesive layer provided on the base material, wherein,
the surface of the base material on the adhesive layer side is a concave-convex surface,
when a test piece is cut from 5 of the support sheet and the cross section of the adhesive agent layer in the 5 test pieces is observed, the average value of the ratio of (the sum of the linear distances between adjacent sharp vertices)/(the linear distance in the direction horizontal to the adhesive agent layer) is 1.5 or more and less than 5.0.
2. The support sheet of claim 1, wherein the adhesive layer is in direct contact with the relief surface of the substrate.
3. A composite sheet for forming a protective film, which comprises a film for forming a protective film on the adhesive layer in the support sheet according to claim 1 or 2.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2018/013569 WO2019186992A1 (en) | 2018-03-30 | 2018-03-30 | Support sheet and composite sheet for protective film formation |
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| CN111373509A true CN111373509A (en) | 2020-07-03 |
| CN111373509B CN111373509B (en) | 2024-01-30 |
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| JP (1) | JP6445747B1 (en) |
| KR (1) | KR102388900B1 (en) |
| CN (1) | CN111373509B (en) |
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| WO (1) | WO2019186992A1 (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450971A (en) * | 2000-09-04 | 2003-10-22 | 旭化成株式会社 | Adhesive wrap film |
| JP2010042665A (en) * | 2008-07-15 | 2010-02-25 | San Totsukusu Kk | Base film |
| JP2016188344A (en) * | 2015-03-30 | 2016-11-04 | リンテック株式会社 | Release film, adhesive sheet, and method for producing release film |
| JP6298226B1 (en) * | 2017-03-30 | 2018-03-20 | リンテック株式会社 | Composite sheet for protective film formation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5432853B2 (en) | 1971-10-11 | 1979-10-17 | ||
| JP4517572B2 (en) * | 2002-11-15 | 2010-08-04 | Ｄｉｃ株式会社 | Reflective / shading adhesive tape |
| JP5432853B2 (en) * | 2010-07-30 | 2014-03-05 | 日東電工株式会社 | Dicing tape-integrated film for semiconductor back surface, manufacturing method thereof, and manufacturing method of semiconductor device |
| CN104755259A (en) * | 2012-10-22 | 2015-07-01 | 三菱丽阳株式会社 | Layered structure and method for manufacturing same, and article |
| JP2015196313A (en) * | 2014-03-31 | 2015-11-09 | ソニー株式会社 | Protective film, laminate, display device, and film-attaching unit |
| KR20180066043A (en) * | 2015-10-05 | 2018-06-18 | 린텍 가부시키가이샤 | Semiconductor processing sheet |
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2018
- 2018-03-30 WO PCT/JP2018/013569 patent/WO2019186992A1/en active Application Filing
- 2018-03-30 JP JP2018538918A patent/JP6445747B1/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450971A (en) * | 2000-09-04 | 2003-10-22 | 旭化成株式会社 | Adhesive wrap film |
| JP2010042665A (en) * | 2008-07-15 | 2010-02-25 | San Totsukusu Kk | Base film |
| JP2016188344A (en) * | 2015-03-30 | 2016-11-04 | リンテック株式会社 | Release film, adhesive sheet, and method for producing release film |
| JP6298226B1 (en) * | 2017-03-30 | 2018-03-20 | リンテック株式会社 | Composite sheet for protective film formation |
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| TWI788543B (en) | 2023-01-01 |
| WO2019186992A1 (en) | 2019-10-03 |
| JP6445747B1 (en) | 2018-12-26 |
| CN111373509B (en) | 2024-01-30 |
| TW202003251A (en) | 2020-01-16 |
| JPWO2019186992A1 (en) | 2020-04-30 |
| KR20200138148A (en) | 2020-12-09 |
| KR102388900B1 (en) | 2022-04-20 |
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