WO2017078053A1 - Kit for thermosetting resin film and second protective film forming film, thermosetting resin film, first protective film forming sheet, and method for forming first protective film for semiconductor wafer - Google Patents
Kit for thermosetting resin film and second protective film forming film, thermosetting resin film, first protective film forming sheet, and method for forming first protective film for semiconductor wafer Download PDFInfo
- Publication number
- WO2017078053A1 WO2017078053A1 PCT/JP2016/082544 JP2016082544W WO2017078053A1 WO 2017078053 A1 WO2017078053 A1 WO 2017078053A1 JP 2016082544 W JP2016082544 W JP 2016082544W WO 2017078053 A1 WO2017078053 A1 WO 2017078053A1
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- WIPO (PCT)
- Prior art keywords
- film
- thermosetting resin
- protective film
- forming
- meth
- Prior art date
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 458
- 229920005989 resin Polymers 0.000 title claims abstract description 389
- 239000011347 resin Substances 0.000 title claims abstract description 389
- 230000001681 protective effect Effects 0.000 title claims abstract description 373
- 239000004065 semiconductor Substances 0.000 title claims abstract description 188
- 238000000034 method Methods 0.000 title claims abstract description 92
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 36
- 230000020169 heat generation Effects 0.000 claims description 64
- 230000015572 biosynthetic process Effects 0.000 claims description 50
- 238000001723 curing Methods 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000013007 heat curing Methods 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 188
- 239000010410 layer Substances 0.000 description 176
- 239000000203 mixture Substances 0.000 description 167
- 235000012431 wafers Nutrition 0.000 description 162
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 155
- 229940048053 acrylate Drugs 0.000 description 155
- -1 polyethylene Polymers 0.000 description 102
- 239000011342 resin composition Substances 0.000 description 74
- 150000001875 compounds Chemical class 0.000 description 60
- 239000000463 material Substances 0.000 description 54
- 239000002904 solvent Substances 0.000 description 54
- 239000003431 cross linking reagent Substances 0.000 description 50
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 49
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- 239000000654 additive Substances 0.000 description 38
- 239000011254 layer-forming composition Substances 0.000 description 37
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- 125000000524 functional group Chemical group 0.000 description 32
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- 125000003277 amino group Chemical group 0.000 description 30
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- 125000000623 heterocyclic group Chemical group 0.000 description 6
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- 230000009471 action Effects 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 5
- 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 5
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
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- IUCJMVBFZDHPDX-UHFFFAOYSA-N tretamine Chemical compound C1CN1C1=NC(N2CC2)=NC(N2CC2)=N1 IUCJMVBFZDHPDX-UHFFFAOYSA-N 0.000 description 1
- 229950001353 tretamine Drugs 0.000 description 1
- CDMIYIVDILNBIJ-UHFFFAOYSA-N triazinane-4,5,6-trithione Chemical compound SC1=NN=NC(S)=C1S CDMIYIVDILNBIJ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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 potential barriers, e.g. a 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
-
- 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
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- 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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- 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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
- H01L23/3135—Double encapsulation or coating and encapsulation
Definitions
- the present invention relates to a kit of a thermosetting resin film and a second protective film forming film, a thermosetting resin film, a first protective film forming sheet provided with the thermosetting resin film, and a first protection for a semiconductor wafer.
- the present invention relates to a film forming method.
- a projecting electrode made of eutectic solder, high-temperature solder, gold or the like is formed as a semiconductor chip on its connection pad portion.
- the flip chip mounting method has been employed in which the bumps are brought into contact with the corresponding terminal portions on the chip mounting substrate in a so-called face-down manner, and are melted / diffusion bonded. .
- a semiconductor chip used in such a mounting method can be obtained, for example, by grinding a surface opposite to the circuit surface of a semiconductor wafer having bumps formed on the circuit surface, or by dicing into individual pieces. .
- a bump forming surface is usually obtained by applying a thermosetting resin film to the bump forming surface and curing the film for the purpose of protecting the circuit surface and bump of the semiconductor wafer.
- a protective film is formed on the substrate.
- thermosetting resin film what contains the thermosetting component hardened
- thermosetting resin film a thermoplastic resin layer having a specific thermoelastic modulus is laminated on the film, and further on the uppermost layer on the thermoplastic resin layer. And a laminate of non-plastic thermoplastic resin layers at 25 ° C. is disclosed (for example, see Patent Document 1). According to Patent Document 1, this protective film forming sheet is said to be excellent in bump filling properties of the protective film, wafer processability, electrical connection reliability after resin sealing, and the like.
- thermosetting resin film is cured by heating to form a protective film on the bump forming surface of the semiconductor wafer.
- the semiconductor wafer may be warped (see FIG. 6).
- the thermosetting resin film is cured by heating, so that the semiconductor wafer 105 having the protective film 101 a formed on the surface 105 a on which the bump 151 is formed is warped in the direction in which the outer peripheral end portion 105 b faces upward. It has occurred.
- Such warpage of the semiconductor wafer 105 is considered to be caused by deformation of the semiconductor wafer due to stress F1 caused by shrinkage or the like when the thermosetting resin film is cured on the surface 105a of the semiconductor wafer 105.
- the present invention has been made in view of the above problems, and is capable of suppressing the occurrence of warpage of the semiconductor wafer when the first protective film is formed on the bump forming surface of the semiconductor wafer. It aims at providing the formation method of the kit of a resin film and the 2nd protective film formation film, the thermosetting resin film, the sheet
- thermosetting resin film to be attached to the bump forming surface of the semiconductor wafer and the second protective film to be attached to the back surface of the semiconductor wafer that is, the surface opposite to the surface on which the circuits and bumps are formed on the semiconductor wafer.
- Shrinkage when the thermosetting resin film is heat-cured by optimizing the relationship between the heat generation start temperature, heat generation peak temperature, and linear expansion coefficient with the forming layer (second protective film forming film)
- the present invention has been completed by finding that the stress applied to the semiconductor wafer due to the above is corrected by the stress when the back surface protective sheet is heated and cured.
- the present invention is a kit of a thermosetting resin film and a second protective film forming film for forming a first protective film for protecting a plurality of bumps in a semiconductor wafer
- the thermosetting resin film and A kit for forming a second protective film includes a thermosetting resin film for forming a first protective film on the surface by sticking to a surface of the semiconductor wafer having a plurality of bumps and heat curing, and the semiconductor wafer
- the thermosetting resin film and the second protective film forming film each include at least a thermosetting component, and the thermosetting resin film includes a differential scanning calorimetry (DSC).
- the exothermic start temperature measured by the method is less than the exothermic start temperature measured by the differential scanning calorimetry of the second protective film forming film.
- the exothermic peak temperatures measured by differential scanning calorimetry of the thermosetting resin film and the second protective film forming film are each 100 to 200 ° C.
- the thermosetting resin film and the Provided is a kit of a thermosetting resin film and a second protective film forming film, which is used by being attached to a semiconductor wafer, wherein the difference in the exothermic peak temperature from the second protective film forming film is less than 35 ° C.
- the kit of the thermosetting resin film and the second protective film-forming film of the present invention has the above-described configuration, wherein the thermosetting resin film has a coefficient of linear expansion (CTE) of 5 ⁇ 10 ⁇ 6 / ° C. It is preferably 80 ⁇ 10 ⁇ 6 / ° C. and the difference from the linear expansion coefficient of the second protective film forming film is preferably less than 35 ⁇ 10 ⁇ 6 / ° C.
- CTE coefficient of linear expansion
- the kit of the thermosetting resin film and the second protective film forming film of the present invention is the first protective film forming sheet, wherein the thermosetting resin film is provided on one surface of the first support sheet in the above configuration.
- the second protective film forming sheet is included in the kit of the thermosetting resin film and the second protective film forming film, and the second protective film forming film is provided on one surface of the second support sheet. As above, it may be included in the kit of the thermosetting resin film and the second protective film forming film.
- thermosetting resin film and the second protective film forming film each include at least a thermosetting component, and the thermosetting resin film is subjected to differential scanning calorimetry.
- the heat generation start temperature measured by the method is equal to or higher than the heat generation start temperature measured by the differential scanning calorimetry of the second protective film forming film, and further, the thermosetting resin film and the second protection Exothermic peak temperatures measured by differential scanning calorimetry of the film-forming film are each 100 to 200 ° C., and the thermosetting property The difference of the exothermic peak temperature of the fat film and the second protective film forming film is less than 35 ° C., to provide a thermosetting resin film.
- thermosetting resin film of the present invention has the above-described structure, wherein the thermosetting resin film has a linear expansion coefficient of 5 ⁇ 10 ⁇ 6 / ° C. to 80 ⁇ 10 ⁇ 6 / ° C., and the second protective film. It is preferable that the difference from the linear expansion coefficient of the formed film is less than 35 ⁇ 10 ⁇ 6 / ° C.
- this invention provides the sheet
- the present invention is a method for forming a first protective film for a semiconductor wafer, wherein a first protective film for protecting the plurality of bumps is formed on a surface of the semiconductor wafer having a circuit and the plurality of bumps.
- a curing step of forming the first protective film on the surface of the semiconductor wafer by heating and curing the thermosetting resin film so as to embed the gap
- the curable resin film has a heat generation start temperature measured by a differential scanning calorimetry (DSC) method equal to or higher than a heat generation start temperature measured by a differential scanning calorimetry method of the second protective film forming film, and Exothermic peak temperatures measured by differential scanning calorimetry of the thermosetting resin film and the second protective film forming film are 100 to 200 ° C., respectively, and the thermosetting resin film and the second protective film are formed.
- DSC differential scanning calorimetry
- Exothermic peak temperatures measured by differential scanning calorimetry of the thermosetting resin film and the second protective film forming film are 100 to 200 ° C., respectively, and the thermosetting resin film and the second protective film are formed.
- a method for forming a first protective film for a semiconductor wafer wherein the difference in exothermic peak temperature from the film is less than 35 ° C.
- the differential scanning calorimetry (DSC) method described in the present invention is a method of measuring the difference in calorific value between a reference material and a measured object, thereby determining the heat generation starting temperature of the measured object. This is a conventional thermal analysis method for measuring.
- thermosetting resin film According to the kit of the thermosetting resin film and the second protective film-forming film of the present invention, the thermosetting resin film, and the first protective film-forming sheet provided with the thermosetting resin film, it is attached to the surface of the semiconductor wafer.
- the thermosetting resin film is heated and cured.
- the stress applied to the semiconductor wafer due to shrinkage or the like is corrected by the stress when the second protective film forming film is heated and cured. Thereby, it is possible to suppress the warpage of the semiconductor wafer, and it is possible to manufacture a highly reliable semiconductor package.
- thermosetting resin film on the front surface side of the semiconductor wafer and the second protective film forming film on the back surface side. Since the relationship between the start temperature and the exothermic peak temperature is optimized, it is possible to suppress the warpage of the semiconductor wafer in the curing step of forming the first protective film on the surface of the semiconductor wafer. A semiconductor package having excellent reliability can be manufactured.
- FIG. 1 It is sectional drawing which shows typically an example of the process of forming a 1st protective film on the bump formation surface of a semiconductor wafer using the kit of the thermosetting resin film and 2nd protective film formation film which concern on this invention, A step of dicing the semiconductor wafer on which the first protective film and the second protective film are formed in units of chips, and then removing the semiconductor wafer divided in units of chips from a wafer dicing ring frame (not shown) and removing the dicing tape.
- FIG. It is sectional drawing which shows typically an example of the layer structure of the thermosetting resin film which concerns on this invention, and the sheet
- thermosetting resin film which concerns on this invention, and the sheet
- thermosetting resin film and a second protective film forming film kit a thermosetting resin film, a first protective film forming sheet, and a method for forming a first protective film for a semiconductor wafer according to the present invention will be described.
- the form will be described in detail with reference to the present invention shown in FIGS. 1A to 1D and FIGS. 2 to 5 and the conventional view shown in FIG. 6 as necessary.
- 1A to 1D show a first protective film formed on a bump forming surface of a semiconductor wafer and a second protective film on the back surface side using the kit of the thermosetting resin film and the second protective film forming film of the present invention.
- FIG. 4 are cross-sectional views schematically showing examples of layer structures of a thermosetting resin film and a first protective film forming sheet, respectively. It is.
- FIG. 5 is a cross-sectional view schematically showing an example of the second protective film forming film and the second protective film forming sheet provided in the kit of the thermosetting resin film and the second protective film forming film.
- FIG. 6 is a figure which shows the example which formed the 1st protective film in the bump formation surface of the semiconductor wafer using the conventional thermosetting resin film.
- the drawings used in the following description may show the main parts in an enlarged manner for the sake of convenience in order to make the features of the present invention easier to understand, and the dimensional ratios and the like of each component are actual ones. And may be different.
- the above-mentioned “film” may be referred to as a “layer”.
- thermosetting resin film and second protective film forming film kit 10 (hereinafter sometimes simply referred to as film kit 10) according to the present invention includes a plurality of semiconductor wafers 5.
- the thermosetting resin film 1 adhered to the bump forming surface (front surface) 5a of the semiconductor wafer 5 and the back surface 5b of the semiconductor wafer 5 are formed.
- thermosetting resin film 1 according to the present invention exemplified in FIGS. 2 to 4 constitutes the film kit 10 as described above, and is composed of a film containing at least a thermosetting component.
- thermosetting resin film 1 of this invention is used in combination with the 2nd protective film formation film 2 stuck on the back surface 5b side of the semiconductor wafer 5, and comprises said film kit 10.
- the 2nd protective film formation film 2 which comprises the film kit 10 consists of a film
- the first protective film-forming sheet 1A is provided with the thermosetting resin film 1 on one surface 11a of the support sheet 11 as shown in FIG. That is, the first protective film forming sheet 1 ⁇ / b> A transports, for example, the thermosetting resin film 1 as a product package before the thermosetting resin film 1 is attached to the semiconductor wafer 5, or When the thermosetting resin film 1 is transported in the process, the thermosetting resin film 1 is stably supported and protected by the support sheet 11.
- the film kit 10 of the present invention and the first protective film forming sheet 1A are both configured to include the thermosetting resin film 1 of the present invention.
- the structure of the thermosetting resin film of this invention and the kit 10 of a 2nd protective film formation film, the thermosetting resin film 1, and 1A of 1st protective film formation sheets is explained in full detail one by one.
- the film kit 10 includes the first protective film 1a (see FIGS. 1C and 1D) for protecting the plurality of bumps 5 in the semiconductor wafer 5. It is for forming.
- the film kit 10 is a surface having a plurality of bumps 51 on the semiconductor wafer 5 as shown in FIGS. 1A to 1D (in this embodiment, referred to as “circuit surface” or “bump formation surface”).
- the thermosetting resin film 1 for forming the first protective film 1a on the surface 5a by being affixed to 5a and heat-cured, and the second protective film to be affixed to the back surface 5b side of the semiconductor wafer 5 It includes the formed film 2 and is generally configured.
- Each of the thermosetting resin film 1 and the second protective film forming film 2 has a component composition including at least a thermosetting component.
- thermosetting resin film 1 provided in the film kit 10 of the present invention is used by being attached to the surface 5 a having the bumps 51 of the semiconductor wafer 5. And after the pasting, the thermosetting resin film 1 has increased fluidity by heating, spreads between the plurality of bumps 51 so as to cover the bumps 51, adheres to the surface (circuit surface) 5 a, and The bumps 51 are embedded while covering the surface 51a, particularly the vicinity of the surface 5a of the semiconductor wafer 5. The thermosetting resin film 1 in this state is further cured by being heated to finally form the first protective film 1a, and the bumps 51 are in close contact with the surface 51a on the surface 5a. Protect.
- the semiconductor wafer 5 after the thermosetting resin film 1 is pasted is ground on a surface (back surface 5b) opposite to the surface 5a serving as a circuit surface, and then a support sheet (first protection shown in FIG. 2).
- the support sheet 11 provided in the film forming sheet 1A) is removed.
- the bump 51 is embedded and the first protective film 1a is formed by heating the thermosetting resin film 1, and finally the semiconductor device (not shown) is provided with the first protective film 1a. Incorporated.
- a plurality of bumps 51 are provided on the surface 5a which is the circuit surface of the semiconductor wafer 5 shown in FIGS. 1A to 1D.
- the bump 51 has a shape in which a part of a sphere is cut out by a flat surface, and a flat surface corresponding to the cut and exposed portion is in contact with the surface 5 a of the semiconductor wafer 5.
- the first protective film 1 a is formed using the thermosetting resin film 1 of the present invention, covers the surface 5 a of the semiconductor wafer 5, and further, the bump 51 has a surface other than the top and the vicinity thereof. 51a is covered.
- the first protective film 1a is in close contact with the surface 51a of the bump 51 other than the top of the bump 51 and the vicinity thereof, and is also in close contact with the surface (circuit surface) 5a of the semiconductor wafer 5.
- the bump 51 is embedded.
- the bump has a substantially spherical shape (a shape in which a part of the sphere is cut out by a plane) as described above, but according to the present invention.
- the shape of the bump that can be protected by the first protective film 1a formed from the curable resin film 1 is not limited to this. For example, as shown in FIGS.
- a substantially spherical bump is stretched in the height direction (the direction perpendicular to the surface 5a of the semiconductor wafer 5 in FIGS. 1A and 1B). That is, a bump having a substantially elliptical spheroid shape (a shape in which a portion including one end of the major axis direction of the elliptical spheroid is cut out by a plane) or a substantially spherical shape as described above.
- a shape formed by crushing the shape in the height direction that is, a shape of a spheroid that is almost oblate (a shape that includes a portion including one end of the oblate spheroid in the short axis direction)
- This bump is also exemplified as a bump having a preferable shape.
- the first protective film 1a formed by the curable resin film 1 according to the present invention can be applied to bumps having any other shape.
- the shape of the bump is spherical as described above.
- the effect of protecting the surface of the semiconductor wafer and the bumps is remarkably obtained.
- the film kit 10 of this invention is the 2nd protective film by which the heat_generation
- the film kit 10 has an exothermic peak temperature measured by differential scanning calorimetry of the thermosetting resin film 1 and the second protective film forming film 2 of 100 to 200 ° C., respectively, and the thermosetting resin film 1 And the second protective film forming film 2 have a difference in exothermic peak temperature of less than 35 ° C.
- the linear expansion coefficient of the thermosetting resin film 1 is 5 to 80 ( ⁇ 10 ⁇ 6 / ° C.), and the difference from the linear expansion coefficient of the second protective film forming film 2 is 35.
- the structure may be less than ( ⁇ 10 ⁇ 6 / ° C.).
- the film kit 10 of the present invention is a second protective film forming film in which the heat generation start temperature of the thermosetting resin film 1 to be applied to the front surface 5a of the semiconductor wafer 5 is applied to the back surface 5b side of the semiconductor wafer 5.
- the thermosetting resin film 1 is applied to the semiconductor wafer 5 by shrinkage or the like when the first protective film 1a is formed by heat curing.
- the stress is corrected by the stress due to shrinkage or the like when the second protective film-forming film 2 is heated and cured to form the second protective film.
- the exothermic peak temperatures of the thermosetting resin film 1 and the second protective film forming film 2 are set to 100 to 200 ° C., and the difference between the exothermic peak temperatures of these films is set to less than 35 ° C.
- the stress applied to the semiconductor wafer 5 due to shrinkage or the like when the thermosetting resin film 1 is heat-cured is stress caused by shrinkage or the like when the second protective film forming film 2 is heat-cured. A corrective action is obtained.
- thermosetting resin film 1 The linear expansion coefficient is 5 to 80 ( ⁇ 10 ⁇ 6 / ° C.), and the difference from the linear expansion coefficient of the second protective film forming film 2 is less than 35 ( ⁇ 10 ⁇ 6 / ° C.). Can be adopted. As a result, as described above, an effect is obtained in which the stress applied to the semiconductor wafer 5 when the thermosetting resin film 1 is heat-cured is corrected by the stress when the second protective film forming film 2 is heat-cured. .
- the correction of the stress applied to the semiconductor wafer 5 as described above can suppress the occurrence of warping of the laminate including the semiconductor wafer 5, and thus reliability. This makes it possible to manufacture a semiconductor package that is superior to the above.
- the end 5c of the semiconductor wafer 5 is directed upward in the drawing, that is, thermosetting. Stress F1 is generated in the direction in which the resin film 1 is pulled.
- the present invention by adopting the relationship between the heat generation start temperature, the heat generation peak temperature, and the linear expansion coefficient as described above, when the semiconductor wafer 5 is heated, the second is more than the curing of the thermosetting resin film 1. Curing of the protective film forming film 2 is started earlier. As a result, the semiconductor wafer 5 has the end 5c of the semiconductor wafer 5 directed downward in FIG.
- the heat generation start temperature of the thermosetting resin film 1 is equal to or higher than the heat generation start temperature of the second protective film forming film 2, and the heat generation peak temperature of both films is 100 to 200 ° C., and The difference between the exothermic peak temperatures of both films is less than 35 ° C., and the difference between the linear expansion coefficients of both films is less than 35 ( ⁇ 10 ⁇ 6 / ° C.). Even if it is a case where it preserve
- thermosetting resin film 1 is heated and cured as described above.
- the stress applied to the semiconductor wafer 5 is corrected, and a remarkable effect of suppressing the warpage of the semiconductor wafer 5 is obtained.
- the exothermic peak temperature of the thermosetting resin film 1 and the second protective film forming film 2 is 120 to 200 ° C. It is particularly preferably 130 to 200 ° C, and most preferably 185 to 200 ° C.
- the difference in exothermic peak temperature between the thermosetting resin film 1 and the second protective film forming film 2 is more preferably 0 to 30 ° C., and particularly preferably 0 to 25 ° C.
- thermosetting resin film 1 As the method for measuring the heat generation start temperature and the heat generation peak temperature of the thermosetting resin film 1 in the above, a measurement method using a conventionally known differential scanning calorimetry (DSC) apparatus can be employed without any limitation.
- DSC differential scanning calorimetry
- the linear expansion coefficient of the thermosetting resin film 1 is 5 to 80 ( ⁇ 10 ⁇ 6 / ° C.), and the second protective film-forming film 2
- the linear expansion coefficient of the second protective film-forming film 2 is the same as the linear expansion coefficient of the thermosetting resin film 1 or less than 35 ( ⁇ 10 ⁇ 6 / ° C.). Or, a configuration lower than that is adopted.
- the linear expansion of the thermosetting resin film 1 is further performed after optimizing the relationship between the heat generation start temperature and the heat generation peak temperature between the thermosetting resin film 1 and the second protective film forming film 2, the linear expansion of the thermosetting resin film 1 is further performed.
- the semiconductor wafer 5 is caused by shrinkage or the like when the thermosetting resin film 1 is thermally cured.
- amend the stress provided to is more effectively acquired. Therefore, the effect of suppressing the warpage of the semiconductor wafer 5 can be obtained more remarkably.
- the linear expansion coefficient of the thermosetting resin film 1 is more preferably 5 to 60 ( ⁇ 10 ⁇ 6 / ° C.) from the viewpoint that the above-described effects can be obtained more remarkably. It is particularly preferably 50 to 50 ( ⁇ 10 ⁇ 6 / ° C.).
- the linear expansion coefficient of the second protective film-forming film 2 is also preferably in the same range as the linear expansion coefficient of the thermosetting resin film 1 described above.
- the difference in linear expansion coefficient between the thermosetting resin film 1 and the second protective film forming film 2 may be 0 ( ⁇ 10 ⁇ 6 / ° C.) or more and less than 30 ( ⁇ 10 ⁇ 6 / ° C.). It is more preferably 0 ( ⁇ 10 ⁇ 6 / ° C.) or more and less than 25 ( ⁇ 10 ⁇ 6 / ° C.).
- thermomechanical analysis (TMA) apparatus As a method for measuring the coefficient of thermal expansion (CTE) of the thermosetting resin film 1 in the above, any conventional measuring method using a thermomechanical analysis (TMA) apparatus can be employed without any limitation.
- CTE coefficient of thermal expansion
- TMA thermomechanical analysis
- the above-described heat generation start temperature, heat generation peak temperature, and linear expansion coefficient of each film can be optimized by adjusting the composition and content of the curing catalyst described later.
- the thickness of the first protective film 1a after curing is not particularly limited, and the overall average thickness may be set in consideration of the protective ability of the surface 5a of the semiconductor wafer 5 and the bumps 51.
- the thickness of the first protective film 1a after curing is, for example, preferably about 1 to 100 ⁇ m, more preferably about 5 to 75 ⁇ m, and most preferably about 5 to 50 ⁇ m.
- the thickness of the 1st protective film 1a after hardening can be calculated
- FIG. 6 schematically shows a cross section in a state in which the protective film 101a is formed on the surface 105a which is the bump forming surface of the semiconductor wafer 105 by a conventional method using a thermosetting resin film.
- a thermosetting resin film having a conventional configuration is used, and between the thermosetting resin film and the second protective film forming film 102 attached to the back surface 105 b side of the semiconductor wafer 105.
- the stress F1 FIG. 1C and FIG. Therefore, the semiconductor wafer 105 is easily deformed and warped.
- the film kit 10 according to the present invention, as described above, the relationship between the heat generation start temperature and the heat generation peak temperature between the thermosetting resin film 1 and the second protective film forming film 2 is optimized. By doing so, the action of correcting the stress applied to the semiconductor wafer 5 can be obtained, and the warpage of the semiconductor wafer 5 can be suppressed.
- a method for forming a first protective film for a semiconductor wafer according to the present invention is for protecting a plurality of bumps 51 on a surface 5a having a plurality of bumps 51 on a semiconductor wafer 5.
- This is a method of forming the first protective film 1a.
- the method for forming a first protective film for a semiconductor wafer according to the present invention includes, for example, a semiconductor wafer using the film kit 10, the thermosetting resin film 1, or the first protective film forming sheet 1A according to the present invention having the above-described configuration.
- a first protective film 1 a is formed on the surface 5 a of 5.
- the method for forming a first protective film for a semiconductor wafer according to the present invention includes a laminating step for forming a laminated body 50 in which a second protective film forming film 2, a semiconductor wafer 5, and a thermosetting resin film 1 are sequentially laminated, and a semiconductor wafer. And a curing step for forming the first protective film 1a on the surface 5a of the substrate 5.
- the second protective film forming film 2 is attached to the surface of the semiconductor wafer 5 opposite to the front surface 5a on which the circuits and bumps 51 are formed, that is, the back surface 5b side.
- a thermosetting resin film is provided so as to cover a plurality of bumps 51 on the front surface 5a of the semiconductor wafer 5 with the second protective film forming film 2 attached to the back surface 5b side.
- a laminated body 50 in which the second protective film forming film 2, the semiconductor wafer 5, and the thermosetting resin film 1 are sequentially laminated is formed.
- a dicing tape not shown in FIG. 1A is attached to the exposed surface of the second protective film forming film 2.
- the laminated body 50 is fixed on a ring frame for wafer dicing (not shown) using a dicing tape 60.
- a dicing tape 60 is adhered to the second protective film forming film 2, and the adhesive surface of the dicing tape 60 (corresponding to the outer peripheral portion of the second protective film forming film 2).
- the laminate 50 can be adhered and fixed to a ring frame (not shown).
- the laminated body 50 (see FIG. 1A) obtained in the above-described lamination step is heated while being pressed using, for example, a conventionally known pressure heating and curing apparatus. To do.
- the plurality of bumps 51 are penetrated through the thermosetting resin film 1, and the thermosetting resin film 1 is heat-cured so as to be embedded between each of the plurality of bumps 51.
- a first protective film 1a is formed on the surface 5a.
- the second protective film 2 a is formed on the back surface 5 b of the semiconductor wafer 5 by curing the second protective film forming film 2.
- the heat generation start temperature measured by the differential scanning calorimetry method is the same as that of the thermosetting resin film 1, and the heat generation start of the second protective film formation film 2 is the same.
- a temperature equal to or higher than the temperature, and the exothermic peak temperature measured by differential scanning calorimetry of the thermosetting resin film 1 and the second protective film forming film 2 is 100 to 200 ° C., and The conditions under which the difference in exothermic peak temperature between the thermosetting resin film 1 and the second protective film forming film 2 is less than 35 ° C. are employed.
- the thermosetting resin film 1 has a linear expansion coefficient of 5 to 80 ( ⁇ 10 ⁇ 6 / ° C.), and the thermosetting resin film 1 A condition in which the difference in linear expansion coefficient from the second protective film-forming film 2 is less than 35 ( ⁇ 10 ⁇ 6 / ° C.) can be employed.
- the first protective film 1a in the present invention According to the method of forming the first protective film 1a in the present invention, as described above, between the thermosetting resin film 1 on the front surface 5a side of the semiconductor wafer 5 and the second protective film forming film 2 on the back surface 5b side, Since the first protective film 1a is formed on the surface 5a of the semiconductor wafer 5 under the condition that the relationship between the heat generation start temperature and the heat generation peak temperature is optimized, it is possible to suppress warping of the semiconductor wafer in the curing step. be able to. Thereby, like the above, it becomes possible to manufacture a semiconductor package having excellent reliability.
- thermosetting resin film 1 of the present invention is softened and cured by heating
- the heating temperature at which the thermosetting resin film 1 of the present invention is softened and cured by heating may be appropriately adjusted according to the constituent components of the thermosetting resin film 1 and is not particularly limited. It is preferable that it is 200 degreeC.
- thermosetting resin film 1 is included in the film kit 10 as the first protective film forming sheet 1 ⁇ / b> A provided on one surface 11 a of the first support sheet 11. Can be adopted. Below, each structure of 1 A of 1st sheets for protective film formation, and the thermosetting resin film 1 contained in it is explained in full detail.
- the first support sheet 11 provided in the first protective film-forming sheet 1A may be composed of one layer (single layer) or may be composed of two or more layers.
- the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of these layers is not particularly limited as long as the effects of the present invention are not impaired. Not.
- a first adhesive layer is laminated on a first substrate, a first intermediate layer is laminated on a first substrate, and a first intermediate layer is formed on the first intermediate layer.
- a first adhesive layer is laminated on a first substrate, a first intermediate layer is laminated on a first substrate, and a first intermediate layer is formed on the first intermediate layer.
- Examples include one in which one pressure-sensitive adhesive layer is laminated, one made only of a first base material, and the like.
- FIG. 2 is a cross-sectional view schematically showing an example of the first protective film-forming sheet of the present invention.
- a first protective film-forming sheet 1A shown in FIG. 2 uses a first support sheet 11 in which a first pressure-sensitive adhesive layer 13 is laminated on a first substrate 12. That is, the first protective film forming sheet 1 ⁇ / b> A includes the first pressure-sensitive adhesive layer 13 on the first base material 12, and includes the thermosetting resin film 1 including a thermosetting component on the first pressure-sensitive adhesive layer 13. Configured.
- the first support sheet 11 is a laminate of the first base material 12 and the first pressure-sensitive adhesive layer 13, and is on one surface 11 a of the first support sheet 11, that is, one surface 13 a of the first pressure-sensitive adhesive layer 13.
- a thermosetting resin film 1 is provided on the top.
- the thermosetting resin film 1 is used by being attached to the bump forming surface of the semiconductor wafer, and is attached to the back surface of the semiconductor wafer. The relationship between the heat generation start temperature, the heat generation peak temperature, and the linear expansion coefficient is optimized.
- FIG. 3 is a cross-sectional view schematically showing another example of the first protective film-forming sheet of the present invention.
- a first protective film-forming sheet 1B shown in FIG. 3 is formed by laminating a first intermediate layer on a first base material and laminating a first adhesive layer on the first intermediate layer as a first support sheet.
- the first protective film forming sheet 1 ⁇ / b> B includes the first intermediate layer 14 on the first substrate 12, the first adhesive layer 13 on the first intermediate layer 14, and the first adhesive layer 13 on the first adhesive layer 13.
- 11A of 1st support sheets are the laminated bodies in which the 1st base material 12, the 1st intermediate
- the thermosetting resin film 1 is provided on one surface 13 a of the first pressure-sensitive adhesive layer 13.
- the first protective film forming sheet 1B further includes a first intermediate layer 14 between the first base material 12 and the first pressure-sensitive adhesive layer 13. It is equipped with.
- thermosetting resin film 1 is used by being attached to the bump forming surface of the semiconductor wafer, and is attached to the back surface of the semiconductor wafer.
- the relationship between the heat generation start temperature, the heat generation peak temperature, and the linear expansion coefficient is optimized.
- FIG. 4 is a cross-sectional view schematically showing still another example of the first protective film-forming sheet of the present invention.
- the first protective film-forming sheet 1C shown in FIG. 4 a sheet made of only the first substrate is used as the first support sheet. That is, the first protective film forming sheet 1 ⁇ / b> C includes the thermosetting resin film 1 on the first substrate 12.
- the 1st support sheet 11B is comprised only from the 1st base material 12, and the thermosetting resin film 1 is on the one surface 11a of the 1st support sheet 11B, ie, the one surface 12a of the 1st base material 12. Provided in direct contact.
- the first protective film forming sheet 1C is obtained by removing the first pressure-sensitive adhesive layer 13 from the first protective film forming sheet 1A shown in FIG.
- the thermosetting resin film 1 is used by being attached to the bump forming surface of the semiconductor wafer, and is attached to the back surface of the semiconductor wafer. The relationship between the heat generation start temperature, the heat generation peak temperature, and the linear expansion coefficient is optimized. Below, each structure of a 1st support sheet is explained in full detail.
- the 1st base material with which a 1st support sheet is provided is a sheet form or a film form, and the following various resin is mentioned as the constituent material, for example.
- the resin constituting the first substrate include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene.
- Polyolefins other than polyethylene such as resins; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer Polymer (copolymer obtained using ethylene as monomer); Vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as monomer); Polystyrene; Polycyclo Olefin; polyethylene terephthalate, poly Polyesters such as tylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all the structural units have aromatic cyclic groups; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Flu
- the polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
- the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.
- (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”.
- (meth) acrylate is a concept including both “acrylate” and “methacrylate”
- (meth) acryloyl group” Is a concept including both an “acryloyl group” and a “methacryloyl group”.
- the resin constituting the first substrate may be only one kind or two or more kinds. When the number of resins constituting the first base material is two or more, their combination and ratio can be arbitrarily selected.
- the first substrate may be only one layer (single layer) or a plurality of layers of two or more layers.
- the plurality of layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
- the thickness of the first base material is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, further preferably 15 to 300 ⁇ m, and particularly preferably 20 to 150 ⁇ m.
- the “thickness of the first base material” means the thickness of the entire first base material.
- the thickness of the first base material composed of a plurality of layers means all of the first base material. Means the total thickness of the layers.
- the first base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part.
- materials that can be used to construct the first base material having such a high thickness precision include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. Examples include coalescence.
- the first base material contains 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 materials such as the resin. You may do it.
- the first substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
- a 1st base material is a thing which permeate
- the first substrate can be manufactured by a known method.
- the 1st base material containing resin can be manufactured by shape
- a 1st adhesive layer is a sheet form or a film form, and contains an adhesive.
- the pressure-sensitive adhesive include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber resin (a resin having a rubber structure). ), Silicone resins (adhesives composed of resins having a siloxane bond), epoxy resins (adhesives composed of resins having an epoxy group), polyvinyl ether, polycarbonate, and other adhesive resins. Based resins are preferred.
- the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin.
- the resin itself has an adhesive property
- resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water.
- the first pressure-sensitive adhesive layer may be only one layer (single layer) or a plurality of layers of two or more layers. When the first pressure-sensitive adhesive layer is a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
- the thickness of the first pressure-sensitive adhesive layer is preferably 1 to 1000 ⁇ m, more preferably 5 to 500 ⁇ m, and particularly preferably 10 to 100 ⁇ m.
- the “thickness of the first pressure-sensitive adhesive layer” means the thickness of the entire first pressure-sensitive adhesive layer.
- the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers means the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.
- the first pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive.
- the first pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
- “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or an LED as an ultraviolet ray source.
- the electron beam can be emitted by an electron beam accelerator or the like.
- energy ray curable means the property of being cured by irradiation with energy rays
- non-energy ray curable means the property of not being cured even when irradiated with energy rays.
- a 1st adhesive layer can be formed using the 1st adhesive composition containing an adhesive.
- a 1st adhesive layer can be formed in the target site
- a more specific method for forming the first pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers.
- the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the first pressure-sensitive adhesive layer.
- “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
- the first pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
- the drying conditions of the first pressure-sensitive adhesive composition are not particularly limited, but when the first pressure-sensitive adhesive composition contains a solvent described later, it is preferably heat-dried. In this case, for example, 70 to 130 ° C. It is preferable to dry under conditions of 10 seconds to 5 minutes.
- the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive is, for example, non-energy First pressure-sensitive adhesive composition containing a linear curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound (I-1): 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-1a) (hereinafter referred to as “adhesiveness”)
- a first pressure-sensitive adhesive composition (I-2) which may be abbreviated as “resin (I-2a)”; the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound; Examples thereof include the first pressure-sensitive adhesive composition (I-3).
- the first pressure-sensitive adhesive composition (I-1) contains the non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and the energy ray-curable compound.
- the adhesive resin (I-1a) is preferably an acrylic resin.
- the acrylic resin the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
- the acrylic resin may have only one type of structural unit, or two or more types of structural units. When the acrylic resin has two or more structural units, the combination and ratio thereof can be arbitrarily selected.
- Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred. More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-
- the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms.
- the alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
- the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
- the acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
- the functional group-containing monomer for example, the functional group reacts with a crosslinking agent to be described later to become a starting point of crosslinking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound, The thing which enables introduction
- Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
- hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
- Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
- monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
- fumaric acid, itaconic acid maleic acid, citracone
- Ethylenically unsaturated dicarboxylic acids such as acids (dica
- the functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
- the functional group-containing monomer constituting the acrylic polymer may be only one type or two or more types. When there are two or more functional group-containing monomers constituting the acrylic polymer, their combination and ratio can be arbitrarily selected.
- the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass and more preferably 3 to 32% by mass with respect to the total mass of the structural unit.
- the content is preferably 5 to 30% by mass.
- the acrylic polymer may further have a structural unit derived from another monomer.
- the other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
- the other monomer include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
- the other monomer constituting the acrylic polymer may be one kind or two or more kinds.
- the said other monomer which comprises the said acrylic polymer is 2 or more types, those combinations and ratios can be selected arbitrarily.
- the acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
- the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).
- energy beam polymerizability means a property of polymerizing by irradiation with energy rays.
- the pressure-sensitive adhesive resin (I-1a) contained in the first pressure-sensitive adhesive composition (I-1) may be one type or two or more types.
- the combination and ratio thereof can be arbitrarily selected.
- the content of the pressure-sensitive adhesive resin (I-1a) is 5 to 99% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-1). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.
- Examples of the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
- examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4.
- Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
- examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
- the energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the first pressure-sensitive adhesive layer is difficult to be lowered.
- the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) may be one kind or two or more kinds.
- the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) is two or more, the combination and ratio thereof can be arbitrarily selected.
- the content of the energy ray-curable compound is 1 to 95% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-1). It is preferably 5 to 90% by mass, more preferably 10 to 85% by mass.
- the first pressure-sensitive adhesive composition preferably further contains a crosslinking agent.
- the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
- a crosslinking agent for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( Cross-linking agent having a glycidyl group); Aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent (
- the cross-linking agent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-1a).
- the content is more preferably 0.1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass.
- the first pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
- the first pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
- photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc.
- benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethy
- ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; , Dibenzyl, benzophenone, 2,4-diethylthioxanthone, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2-chloroanthraquinone and the like.
- a quinone compound such as 1-chloroanthraquinone
- a photosensitizer such as amine
- the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-1) may be one kind or two or more kinds.
- the first pressure-sensitive adhesive composition (I-1) contains two or more photopolymerization initiators, the combination and ratio thereof can be arbitrarily selected.
- the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound.
- the amount is more preferably 0.03 to 10 parts by weight, and particularly preferably 0.05 to 5 parts by weight.
- the first pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers.
- known additives such as reaction retarders and crosslinking accelerators (catalysts).
- the reaction retarding agent means, for example, the purpose of the first pressure-sensitive adhesive composition (I-1) during storage due to the action of the catalyst mixed in the first pressure-sensitive adhesive composition (I-1).
- reaction retarder examples include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C ( ⁇ O) —) in one molecule. Can be mentioned.
- the other additive contained in the first pressure-sensitive adhesive composition (I-1) may be one kind or two or more kinds. When there are two or more other additives contained in the first pressure-sensitive adhesive composition (I-1), the combination and ratio thereof can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected depending on the type.
- the first pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the first pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
- the solvent is preferably an organic solvent.
- organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane and n-hexane and the like.
- ketones such as methyl ethyl ketone and
- the solvent for example, the one used in the production of the adhesive resin (I-1a) is used as it is in the first adhesive composition (I-1) without being removed from the adhesive resin (I-1a).
- the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the first pressure-sensitive adhesive composition (I-1).
- the solvent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type or two or more types.
- the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited, and may be adjusted as appropriate.
- the first pressure-sensitive adhesive composition (I-2) is an energy ray-curable pressure-sensitive adhesive having an unsaturated group introduced in the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). Resin (I-2a) is contained.
- the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
- the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.
- a compound having a group examples include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
- Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, 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 carboxy group or an epoxy group. Etc.
- 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 first adhesive composition (I-2) may be only one type or two or more types.
- the pressure-sensitive adhesive composition (I-2a) contained in the first pressure-sensitive adhesive composition (I-2) is two or more, the combination and ratio thereof can be arbitrarily selected.
- the content of the pressure-sensitive adhesive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-2). It is preferably 10 to 95% by mass, more preferably 10 to 90% by mass.
- the first adhesive composition may further contain a crosslinking agent.
- Examples of the crosslinking agent in the first pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the first pressure-sensitive adhesive composition (I-1).
- the crosslinking agent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type or two or more types.
- the first pressure-sensitive adhesive composition (I-2) contains two or more crosslinking agents, the combination and ratio thereof can be arbitrarily selected.
- the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a).
- the content is more preferably 0.1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass.
- the first pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
- the first pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
- Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the first pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-2) may be one kind or two or more kinds.
- the first pressure-sensitive adhesive composition (I-2) contains two or more photopolymerization initiators, their combination and ratio can be arbitrarily selected.
- the content of the photopolymerization initiator is 0.01 to 20 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). Is preferable, 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
- the first pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- Examples of the other additive in the first pressure-sensitive adhesive composition (I-2) include the same additives as those in the first pressure-sensitive adhesive composition (I-1).
- the other additive contained in the first pressure-sensitive adhesive composition (I-2) may be one kind or two or more kinds. When there are two or more other additives contained in the first pressure-sensitive adhesive composition (I-2), their combination and ratio can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected according to the type.
- the first pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the first pressure-sensitive adhesive composition (I-2) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
- the solvent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited, and may be adjusted as appropriate.
- the first pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound.
- the content of the pressure-sensitive adhesive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-3). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.
- Examples of the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) include monomers and oligomers that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays. And the same energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1).
- the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. When the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) is two or more kinds, the combination and ratio thereof can be arbitrarily selected.
- the content of the energy ray-curable low molecular weight compound is 0.01 to 300 masses with respect to 100 mass parts of the pressure-sensitive adhesive resin (I-2a). Part is preferable, 0.03 to 200 parts by weight is more preferable, and 0.05 to 100 parts by weight is particularly preferable.
- the first pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
- the first pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
- Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators as those in the first pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. When there are two or more photopolymerization initiators in the first pressure-sensitive adhesive composition (I-3), their combination and ratio can be arbitrarily selected.
- the content of the photopolymerization initiator is based on 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable low molecular weight compound.
- the amount 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.
- the first pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range that does not impair the effects of the present invention.
- the other additives include the same additives as the other additives in the first pressure-sensitive adhesive composition (I-1).
- the other additive contained in the first pressure-sensitive adhesive composition (I-3) may be only one kind or two or more kinds. When there are two or more other additives contained in the first pressure-sensitive adhesive composition (I-3), the combination and ratio thereof can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected depending on the type.
- the first pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the first pressure-sensitive adhesive composition (I-3) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
- the solvent contained in the first pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. In the case where the first pressure-sensitive adhesive composition (I-3) contains two or more solvents, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited and may be appropriately adjusted.
- first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) So far, the first pressure-sensitive adhesive composition (I-1), the first pressure-sensitive adhesive composition (I-2), and the first pressure-sensitive adhesive composition (I-3) have been mainly described.
- the first pressure-sensitive adhesive composition other than these three types of the first pressure-sensitive adhesive compositions in this embodiment, “first pressure-sensitive adhesive compositions (I-1) to (I- It is also possible to use the same in the first pressure-sensitive adhesive composition other than 3).
- the first non-energy ray-curable first composition is used as the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3).
- the first non-energy ray-curable first composition is used as the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3).
- An adhesive composition is also mentioned.
- the non-energy ray curable first pressure-sensitive adhesive composition include acrylic resins (resins having a (meth) acryloyl group), urethane resins (resins having a urethane bond), and rubber resins (having a rubber structure).
- Resins silicone resins (resins having a siloxane bond), epoxy resins (resins having an epoxy group), polyvinyl ethers, or those containing adhesive resins such as polycarbonates, and those containing acrylic resins Is preferred.
- the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more crosslinking agents, and the content thereof is as described above. This can be the same as in the case of the first pressure-sensitive adhesive composition (I-1) and the like.
- the first pressure-sensitive adhesive composition such as the first pressure-sensitive adhesive compositions (I-1) to (I-3) includes the first pressure-sensitive adhesive, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive as necessary. It is obtained by blending each component for constituting the composition. The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
- the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
- the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
- the first intermediate layer is in the form of a sheet or film, and the constituent material may be appropriately selected according to the purpose, and is not particularly limited.
- the first protective film covering the semiconductor surface reflects the shape of the bumps existing on the semiconductor surface and is intended to prevent the first protective film from being deformed
- the first intermediate layer Examples of preferable constituent materials include urethane (meth) acrylate and the like from the viewpoint that the adhesiveness of the first intermediate layer is further improved.
- the first intermediate layer may be only one layer (single layer) or a plurality of layers of two or more layers. When the first intermediate layer is a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
- the thickness of the first intermediate layer can be adjusted as appropriate according to the height of the bump on the surface of the semiconductor to be protected.
- the thickness of the first intermediate layer is 50 to 600 ⁇ m because the influence of the relatively high bump can be easily absorbed. It is preferably 70 to 500 ⁇ m, more preferably 80 to 400 ⁇ m.
- the “thickness of the first intermediate layer” means the thickness of the entire first intermediate layer.
- the thickness of the first intermediate layer composed of a plurality of layers means all of the first intermediate layer. Means the total thickness of the layers.
- middle layer can be formed using the composition for 1st intermediate
- the first intermediate layer-forming composition is applied to the surface of the first intermediate layer and dried as necessary, or cured by irradiation with energy rays, so that the first intermediate layer is formed on the target site. Layers can be formed. A more specific method for forming the first intermediate layer will be described in detail later along with methods for forming other layers.
- the ratio of the content of components that do not vaporize at room temperature in the first intermediate layer forming composition is usually the same as the content ratio of the components of the first intermediate layer.
- “normal temperature” is as described above.
- the first intermediate layer forming composition may be applied by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife.
- a method using various coaters such as a coater, a screen coater, a Meyer bar coater, and a kiss coater.
- the drying conditions for the first intermediate layer forming composition are not particularly limited, but when the first intermediate layer forming composition contains a solvent to be described later, it is preferably heat-dried. Drying is preferably performed at 70 to 130 ° C. for 10 seconds to 5 minutes.
- the composition for forming the first intermediate layer has energy ray curability, it is preferably cured by irradiation with energy rays after drying.
- Examples of the first intermediate layer forming composition include a first intermediate layer forming composition (II-1) containing urethane (meth) acrylate.
- First intermediate layer forming composition (II-1) contains urethane (meth) acrylate.
- Urethane (meth) acrylate is a compound having at least a (meth) acryloyl group and a urethane bond in one molecule, and has energy ray polymerizability.
- the urethane (meth) acrylate may be monofunctional (having only one (meth) acryloyl group in one molecule) or bifunctional or more ((meth) acryloyl group in one molecule). Having two or more), i.e., polyfunctional, it is preferable to use at least monofunctional.
- Examples of the urethane (meth) acrylate contained in the first intermediate layer forming composition include, for example, a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound and a polyvalent isocyanate compound, a hydroxyl group and What was obtained by making the (meth) acrylic-type compound which has a (meth) acryloyl group react is mentioned.
- the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.
- the urethane (meth) acrylate contained in the first intermediate layer forming composition (II-1) may be one type or two or more types.
- the combination and ratio thereof can be arbitrarily selected.
- the polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.
- the said polyol compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as said polyol compound, those combinations and ratios can be selected arbitrarily.
- polyol compound examples include alkylene diol, polyether type polyol, polyester type polyol, and polycarbonate type polyol.
- the polyol compound may be any of a bifunctional diol, a trifunctional triol, a tetrafunctional or higher polyol, etc., but a diol is preferable in terms of easy availability and excellent versatility and reactivity. .
- the polyether type polyol is not particularly limited, but is preferably a polyether type diol, and examples of the polyether type diol include compounds represented by the following general formula (1). It is done.
- n is an integer greater than or equal to 2; R is a bivalent hydrocarbon group, and several R may mutually be same or different.
- n represents the number of repeating units of the group represented by the general formula “—R—O—” and is not particularly limited as long as it is an integer of 2 or more. Among these, n is preferably 10 to 250, more preferably 25 to 205, and particularly preferably 40 to 185.
- R is not particularly limited as long as it is a divalent hydrocarbon group, but is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, an ethylene group, A propylene group or a tetramethylene group is more preferable, and a propylene group or a tetramethylene group is particularly preferable.
- the compound represented by the above formula (1) is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, more preferably polypropylene glycol or polytetramethylene glycol.
- the terminal isocyanate urethane prepolymer having an ether bond represented by the following general formula (1a) is obtained.
- the urethane (meth) acrylate has the ether bond part, that is, the structural unit derived from the polyether type diol. .
- polyester type polyol is not specifically limited, For example, what was obtained by performing esterification reaction using a polybasic acid or its derivative (s), etc. are mentioned.
- the “derivative” means one obtained by substituting one or more groups of the original compound with other groups (substituents) unless otherwise specified.
- the “group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.
- polybasic acid and its derivative As said polybasic acid and its derivative (s), the polybasic acid normally used as a manufacturing raw material of polyester and its derivative (s) are mentioned.
- the polybasic acid include saturated aliphatic polybasic acids, unsaturated aliphatic polybasic acids, aromatic polybasic acids, and the like, and dimer acids corresponding to any of these may be used.
- saturated aliphatic polybasic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and saturated aliphatic dibasic acids such as sebacic acid. It is done.
- unsaturated aliphatic polybasic acid examples include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.
- aromatic polybasic acid examples include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid; aromatic tribasic acids such as trimellitic acid; pyromellitic acid and the like And aromatic tetrabasic acids.
- Examples of the derivative of the polybasic acid include the above-mentioned saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid and acid anhydride of aromatic polybasic acid, and hydrogenated dimer acid.
- polybasic acids or derivatives thereof may be used alone or in combination of two or more.
- those combinations and ratios can be selected arbitrarily.
- the polybasic acid is preferably an aromatic polybasic acid in that it is suitable for forming a coating film having an appropriate hardness.
- a known catalyst may be used as necessary.
- the catalyst include tin compounds such as dibutyltin oxide and stannous octylate; alkoxy titanium such as tetrabutyl titanate and tetrapropyl titanate.
- Polycarbonate-type polyol The polycarbonate-type polyol is not particularly limited, and examples thereof include those obtained by reacting the same glycol as the compound represented by the above formula (1) with an alkylene carbonate.
- each of glycol and alkylene carbonate may be used alone or in combination of two or more.
- those combinations and ratios can be arbitrarily selected.
- the number average molecular weight calculated from the hydroxyl value of the polyol compound is preferably 1000 to 10,000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000.
- the number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.
- the polyol compound is preferably a polyether type polyol, and more preferably a polyether type diol.
- polyvalent isocyanate compound The polyvalent isocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.
- a polyvalent isocyanate compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as a polyvalent isocyanate compound, those combinations and ratios can be selected arbitrarily.
- polyvalent isocyanate compound examples include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2.
- chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate
- isophorone diisocyanate norbornane diisocyanate
- dicyclohexylmethane-4,4′-diisocyanate dicyclohexylmethane-2.
- Cycloaliphatic diisocyanates such as 4,4′-diisocyanate, ⁇ , ⁇ ′-diisocyanate dimethylcyclohexane, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1, And aromatic diisocyanates such as 5-diisocyanate.
- the polyvalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylylene diisocyanate from the viewpoint of handleability.
- the (meth) acrylic compound to be reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in one molecule. .
- the said (meth) acrylic-type compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as said (meth) acrylic-type compound, those combinations and ratios can be selected arbitrarily.
- Examples of the (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyl-3-phenyloxypropyl, hydroxyl group-containing (meth) acrylate such as pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; N-methylol (meth) acrylamid Hydroxyl group-containing (meth) acrylamide and the like; vinyl alcohol, vinyl phenol or bisphenol A diglycidyl ether (
- the (meth) acrylic compound is preferably a hydroxyl group-containing (meth) acrylic ester, more preferably a hydroxyl group-containing (meth) acrylic acid alkyl ester, and (meth) acrylic acid 2- Particularly preferred is hydroxyethyl.
- the reaction between the terminal isocyanate urethane prepolymer and the (meth) acrylic compound may be performed using a solvent, a catalyst, or the like, if necessary.
- Conditions for reacting the terminal isocyanate urethane prepolymer with the (meth) acrylic compound may be appropriately adjusted.
- the reaction temperature is preferably 60 to 100 ° C.
- the reaction time is 1 to It is preferably 4 hours.
- the urethane (meth) acrylate may be an oligomer, a polymer, or a mixture of an oligomer and a polymer, but is preferably an oligomer.
- the urethane (meth) acrylate has a weight average molecular weight of preferably from 1,000 to 100,000, more preferably from 3000 to 80,000, and particularly preferably from 5,000 to 65,000. Due to the intermolecular force between the structures derived from urethane (meth) acrylate in the polymer of urethane (meth) acrylate and a polymerizable monomer described later, the weight average molecular weight is 1000 or more. Optimization of layer hardness is facilitated.
- the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
- the first intermediate layer forming composition (II-1) may contain a polymerizable monomer in addition to the urethane (meth) acrylate, from the viewpoint of further improving the film forming property.
- the polymerizable monomer is a compound having energy ray polymerizability and excluding oligomers and polymers having a weight average molecular weight of 1000 or more and having at least one (meth) acryloyl group in one molecule. It is preferable.
- Examples of the polymerizable monomer include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester is a chain having 1 to 30 carbon atoms; a hydroxyl group, an amide group, an amino group, an epoxy group, or the like (Meth) acrylic compound having a functional group of (meth) acrylic ester having an aliphatic cyclic group; (meth) acrylic ester having an aromatic hydrocarbon group; having a heterocyclic group ( (Meth) acrylic acid ester; compound having vinyl group; compound having allyl group.
- Examples of the (meth) acrylic acid alkyl ester having a chain alkyl group having 1 to 30 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( Isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic acid Isononyl, decy
- Examples of the functional group-containing (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid.
- Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (Meth) acrylamides such as N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and the like
- a derivative having an amino group ( A) Acrylic acid ester hereinafter sometimes referred to as “amino group-containing (meth) acrylic acid
- amino group-containing (meth) acrylic acid ester means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with an amino group (—NH 2 ).
- monosubstituted amino group-containing (meth) acrylic acid ester means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a monosubstituted amino group
- disubstituted amino group-containing (meth) acrylic acid ester means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a disubstituted amino group.
- the group other than the hydrogen atom in which the hydrogen atom is substituted in the “monosubstituted amino group” and the “disubstituted amino group” include an alkyl group.
- Examples of the (meth) acrylic acid ester having an aliphatic cyclic group include, for example, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and (meth) acrylic acid. Examples include dicyclopentenyloxyethyl, cyclohexyl (meth) acrylate, and adamantyl (meth) acrylate.
- Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenylhydroxypropyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Can be mentioned.
- the heterocyclic group in the (meth) acrylic acid ester having a heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group.
- Examples of the (meth) acrylic acid ester having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryloylmorpholine.
- Examples of the compound having a vinyl group include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinyl pyrrolidone, N-vinyl caprolactam and the like.
- Examples of the compound having an allyl group include allyl glycidyl ether.
- the polymerizable monomer preferably has a relatively bulky group from the viewpoint of good compatibility with the urethane (meth) acrylate, and such a monomer has an aliphatic cyclic group (meta ) Acrylic acid ester, (meth) acrylic acid ester having an aromatic hydrocarbon group, (meth) acrylic acid ester having a heterocyclic group, and (meth) acrylic acid ester having an aliphatic cyclic group are more preferable. preferable.
- the polymerizable monomer contained in the first intermediate layer forming composition (II-1) may be only one type or two or more types. When there are two or more polymerizable monomers contained in the first intermediate layer forming composition (II-1), the combination and ratio thereof can be arbitrarily selected.
- the content of the polymerizable monomer is 10 to 99% by mass with respect to the total mass of the first intermediate layer forming composition (II-1). It is preferably 15 to 95% by mass, more preferably 20 to 90% by mass, and particularly preferably 25 to 80% by mass.
- the first intermediate layer forming composition (II-1) may contain a photopolymerization initiator in addition to the urethane (meth) acrylate and the polymerizable monomer.
- the first intermediate layer-forming composition (II-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
- Examples of the photopolymerization initiator in the first intermediate layer forming composition (II-1) include the same photopolymerization initiator as in the first pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the first intermediate layer forming composition (II-1) may be one kind or two or more kinds. When two or more photopolymerization initiators are contained in the first intermediate layer forming composition (II-1), the combination and ratio thereof can be arbitrarily selected.
- the content of the photopolymerization initiator is 0.01 to 20 with respect to 100 parts by mass of the total content of the urethane (meth) acrylate and the polymerizable monomer.
- the amount is preferably part by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the first intermediate layer forming composition (II-1) may contain a resin component other than the urethane (meth) acrylate as long as the effects of the present invention are not impaired.
- the kind of the resin component and the content in the first intermediate layer forming composition (II-1) may be appropriately selected according to the purpose, and are not particularly limited.
- the first intermediate layer forming composition (II-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- the other additives include known crosslinking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), and the like.
- An additive is mentioned.
- the chain transfer agent includes a thiol compound having at least one thiol group (mercapto group) in one molecule.
- thiol compound examples include nonyl mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, triazinetrithiol, 1,2,3-propanetrithiol, Tetraethylene glycol-bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakisthioglucorate, dipentaerythritol hexa Kiss (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,4-bis (3-mercaptobutyryloxy) butane, pen Erythritol tetrakis (3-mercapt
- the other additive contained in the first intermediate layer forming composition (II-1) may be one kind or two or more kinds.
- the combination and ratio thereof can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected depending on the type.
- the first intermediate layer forming composition (II-1) may contain a solvent. Since the first intermediate layer forming composition (II-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
- the first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) can be obtained by blending the components for constituting the first intermediate layer forming composition.
- the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
- the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
- the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
- the thermosetting resin film 1 of the present invention is made of a thermosetting resin composition, and as described above, the surface (circuit surface) 5a of the semiconductor wafer 5 and the plurality of bumps 51 provided in the shape of the surface 5a.
- the first protective film 1a is formed by thermosetting. By forming the first protective film 1a using the thermosetting resin film 1 of the present invention, the surface (circuit surface) 5a of the semiconductor wafer 5 and the portion near the surface 5a of the bump 51, that is, the base, are One protective film 1a is sufficiently protected.
- the heat generation start temperature measured by the differential scanning calorimetry is equal to or higher than the heat generation start temperature of the second protective film forming film 2.
- the thermosetting resin film 1 has an exothermic peak temperature of 100 to 200 ° C., and the difference in exothermic peak temperature between the thermosetting resin film 1 and the second protective film forming film 2 is less than 35 ° C. It is comprised so that it may become.
- the thermosetting resin film 1 has a linear expansion coefficient of 5 to 80 ( ⁇ 10 ⁇ 6 / ° C.), and a difference from the linear expansion coefficient of the second protective film forming film 2 is 35 ( ⁇ 10 ( ⁇ 6 / ° C.).
- thermosetting resin film 1 can be formed using a thermosetting resin composition containing the constituent materials.
- This thermosetting resin composition contains at least a thermosetting component. Therefore, the heat generation starting temperature, the heat generation peak temperature, and the linear expansion coefficient measured by the differential scanning calorimetry of the thermosetting resin film 1 are any one of the types and amounts of the components contained in the thermosetting resin composition, or It can be adjusted by adjusting both.
- the thermosetting resin composition and the manufacturing method thereof will be described in detail later.
- thermosetting resin composition in particular, by increasing or decreasing the content of the thermosetting component in the composition, the heat generation start temperature and the heat generation peak temperature of the thermosetting resin film 1, Furthermore, the linear expansion coefficient can be adjusted to a preferred range.
- thermosetting resin film 1 examples include those containing a polymer component (A) and a thermosetting component (B).
- the polymer component (A) is a component that can be regarded as formed by polymerization reaction of the polymerizable compound.
- the thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger.
- the polymerization reaction includes a polycondensation reaction.
- the thermosetting resin film 1 may be composed of only one layer (single layer), or may be composed of two or more layers. When the thermosetting resin film 1 has a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited. When the thermosetting resin film 1 has a plurality of layers, all the layers constituting the thermosetting resin film 1 may satisfy the above-described conditions for the heat generation start temperature and the heat generation peak temperature.
- the thickness of the thermosetting resin film 1 is not particularly limited.
- the thickness is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
- the “thickness of the thermosetting resin film” means the thickness of the entire thermosetting resin film 1.
- the thickness of the thermosetting resin film 1 composed of a plurality of layers is thermosetting. It means the total thickness of all the layers constituting the resin film 1.
- thermosetting resin composition The thermosetting resin film 1 can be formed using a thermosetting resin composition containing the constituent material, that is, a thermosetting resin composition containing at least a thermosetting component.
- a thermosetting resin composition containing at least a thermosetting component For example, the thermosetting resin film 1 can be formed in the target site
- the ratio of the content of components that do not vaporize at normal temperature is usually the same as the ratio of the content of the components of the thermosetting resin film 1.
- “normal temperature” is as described above.
- thermosetting resin composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
- thermosetting resin composition is preferably heat-dried when it contains a solvent described later. In this case, for example, 70 to 130 ° C. It is preferable to dry under conditions of 10 seconds to 5 minutes.
- thermosetting resin composition (III-1) examples include a thermosetting resin composition (III-1) containing a polymer component (A) and a thermosetting component (B).
- the polymer component (A) is a polymer compound for imparting film forming property, flexibility, and the like to the thermosetting resin film 1.
- the polymer component (A) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one kind or two or more kinds.
- the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more polymer components (A), the combination and ratio thereof can be arbitrarily selected.
- Examples of the polymer component (A) include an acrylic resin (a resin having a (meth) acryloyl group), a polyester, a urethane resin (a resin having a urethane bond), an acrylic urethane resin, and a silicone resin (having a siloxane bond). Resin), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide and the like, and acrylic resin is preferable.
- the weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000.
- Mw weight average molecular weight of the acrylic resin
- the shape stability (time stability during storage) of the thermosetting resin film 1 is improved.
- production of a void etc. is suppressed more between 1 is acquired.
- the glass transition temperature (Tg) of the acrylic resin is preferably ⁇ 60 to 70 ° C., and more preferably ⁇ 30 to 50 ° C.
- Tg of the acrylic resin is equal to or higher than the lower limit, the adhesive force between the first protective film 1a and the first support sheet is suppressed, and the peelability of the first support sheet is improved.
- the adhesive force with the to-be-adhered body of the thermosetting resin film 1 and the 1st protective film 1a improves because Tg of acrylic resin is below said upper limit.
- the acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. Examples include copolymers of two or more monomers.
- Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (me
- the acrylic resin is, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like in addition to the (meth) acrylic ester. May be obtained by copolymerization.
- the monomer constituting the acrylic resin may be only one type or two or more types. When there are two or more monomers constituting the acrylic resin, their combination and ratio can be arbitrarily selected.
- the acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group.
- the functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). .
- F cross-linking agent
- thermoplastic resin other than an acrylic resin
- thermoplastic resin is used alone without using an acrylic resin.
- it may be used in combination with an acrylic resin.
- thermoplastic resin By using the thermoplastic resin, the peelability of the first protective film 1a from the first support sheet 11 is improved, and the thermosetting resin film 1 can easily follow the uneven surface of the adherend. Generation of voids or the like may be further suppressed between the body and the thermosetting resin film 1.
- the weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.
- the glass transition temperature (Tg) of the thermoplastic resin is preferably ⁇ 30 to 150 ° C., and more preferably ⁇ 20 to 120 ° C.
- the glass transition temperature (Tg) can be measured by the above-described differential scanning calorimetry (DSC) method.
- thermoplastic resin examples include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.
- thermoplastic resin contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types. When the thermoplastic resins contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 are two or more, the combination and ratio thereof can be arbitrarily selected.
- the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component (A )) Is preferably 5 to 85% by mass, more preferably 5 to 80% by mass, regardless of the type of the polymer component (A).
- the polymer component (A) may also correspond to the thermosetting component (B).
- the thermosetting resin composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B)
- the thermosetting resin The composition (III-1) is considered to contain a polymer component (A) and a thermosetting component (B).
- thermosetting component (B) The thermosetting component (B) is a component for curing the thermosetting resin film 1 to form the hard first protective film 1a.
- the thermosetting component (B) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types. When there are two or more thermosetting components (B) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1, the combination and ratio thereof can be arbitrarily selected.
- thermosetting component (B) examples include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferable.
- the epoxy thermosetting resin comprises an epoxy resin (B1) and a thermosetting agent (B2).
- the epoxy thermosetting resin contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types.
- the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more epoxy thermosetting resins, the combination and ratio thereof can be arbitrarily selected.
- Epoxy resin (B1) examples include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Examples thereof include bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.
- an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (B1).
- An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the thermosetting resin film is improved by using an epoxy resin having an unsaturated hydrocarbon group.
- Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin 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 to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
- the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.
- the number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30000 in view of curability of the thermosetting resin film 1 and strength and heat resistance of the first protective film 1a after curing. Is more preferable, 400 to 10,000 is more preferable, and 500 to 3000 is particularly preferable.
- the number average molecular weight of the epoxy resin (B1) can be measured by a conventionally known gel permeation chromatography (GPC) method (styrene standard).
- GPC gel permeation chromatography
- the epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.
- the epoxy equivalent of an epoxy resin (B1) can be measured by the method based on JISK7236: 2001.
- the epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.
- thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
- a thermosetting agent (B2) the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example.
- the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
- thermosetting agents (B2) examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins.
- examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
- the thermosetting agent (B2) may have an unsaturated hydrocarbon group.
- examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
- the unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.
- thermosetting agent (B2) In the case where a phenolic curing agent is used as the thermosetting agent (B2), the thermosetting agent (B2) is a softening point or a glass transition temperature because the peelability of the first protective film 1a from the first support sheet is improved. High is preferred.
- the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
- the number average molecular weight can also be measured by a conventionally known gel permeation chromatography (GPC) method (styrene standard).
- GPC gel permeation chromatography
- the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
- thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as a thermosetting agent (B2), those combinations and ratios can be selected arbitrarily.
- the content of the thermosetting agent (B2) is from 0.1 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (B1).
- the amount is preferably 500 parts by mass, and more preferably 1 to 200 parts by mass.
- content of a thermosetting agent (B2) is more than said lower limit, hardening of the thermosetting resin film 1 will advance more easily.
- the moisture absorption rate of the thermosetting resin film 1 is reduced because the content of the thermosetting agent (B2) is not more than the above upper limit value, and the package obtained using the thermosetting resin film 1 Reliability is further improved.
- thermosetting resin composition (III-1) and thermosetting resin film 1 content of thermosetting component (B) (for example, total content of epoxy resin (B1) and thermosetting agent (B2)) Is preferably 50 to 1000 parts by weight, more preferably 100 to 900 parts by weight, and more preferably 150 to 800 parts by weight with respect to 100 parts by weight of the polymer component (A). Particularly preferred.
- content of the thermosetting component (B) is in such a range, the adhesive force between the first protective film 1a and the first support sheet is suppressed, and the peelability of the first support sheet is improved.
- the thermosetting resin composition (III-1) and the thermosetting resin film 1 may contain a curing accelerator (C).
- the curing accelerator (C) is a component for adjusting the curing rate of the thermosetting resin composition (III-1).
- Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms)
- the curing accelerator (C) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types.
- the combination and ratio thereof can be arbitrarily selected.
- the content of the curing accelerator (C) in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is the content of the thermosetting component (B).
- the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.
- the effect by using a hardening accelerator (C) is acquired more notably because content of a hardening accelerator (C) is more than said lower limit.
- content of a hardening accelerator (C) is below said upper limit, for example, a highly polar hardening accelerator (C) is in the thermosetting resin film 1 under high temperature and high humidity conditions. The effect of suppressing segregation by moving toward the adhesion interface with the adherend is increased, and the reliability of the package obtained using the thermosetting resin film 1 is further improved.
- thermosetting resin composition (III-1) and the thermosetting resin film 1 may contain a filler (D).
- the thermosetting resin film 1 contains the filler (D)
- the first protective film 1a obtained by curing the thermosetting resin film 1 can easily adjust the thermal expansion coefficient to the above range.
- the thermosetting resin film 1 containing a filler (D) can also reduce the moisture absorption rate of the 1st protective film 1a, or can improve heat dissipation.
- the filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
- Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
- the inorganic filler is preferably silica or alumina.
- the filler (D) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types.
- the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more fillers (D), the combination and ratio thereof can be arbitrarily selected.
- the ratio of the content of the filler (D) to the total content of all components other than the solvent in the thermosetting resin composition (III-1) that is, the thermosetting resin
- the content of the filler (D) in the film 1 is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. Adjustment of said thermal expansion coefficient becomes easier because content of a filler (D) is such a range.
- thermosetting resin composition (III-1) and the thermosetting resin film 1 may contain a coupling agent (E).
- a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound it is possible to improve adhesion and adhesion to the adherend of the thermosetting resin film 1.
- water resistance improves the 1st protective film 1a obtained by hardening
- the coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred. Preferred examples of the 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-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenyla
- the coupling agent (E) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types.
- the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more coupling agents (E), their combination and ratio can be arbitrarily selected.
- the content of the coupling agent (E) in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is the polymer component (A) and the thermosetting resin. It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content of the sex component (B) It is particularly preferred that When the content of the coupling agent (E) is not less than the above lower limit, the dispersibility of the filler (D) in the resin is improved, and the adhesiveness of the thermosetting resin film 1 to the adherend is improved. The effect of using the coupling agent (E) such as improvement can be obtained more remarkably. Moreover, generation
- thermosetting resin composition (III-1) and the thermosetting resin film 1 may contain a crosslinking agent (F) for bonding the functional group with another compound to crosslink. .
- crosslinking agent (F) By crosslinking using the crosslinking agent (F), the initial adhesive force and cohesive force of the thermosetting resin film 1 can be adjusted.
- crosslinking agent (F) examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.
- organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”).
- a trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc.
- the “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later.
- the “terminal isocyanate urethane prepolymer” is as described above.
- organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.
- a polyol such as propane.
- organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and tetramethylolmethane.
- -Tri- ⁇ -aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
- the crosslinking agent (F) When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A).
- the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the thermosetting resin film 1 has a crosslinked structure by a reaction between the crosslinking agent (F) and the polymer component (A). Can be easily introduced.
- the crosslinking agent (F) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types.
- the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more crosslinking agents (F), the combination and ratio thereof can be arbitrarily selected.
- the content of the cross-linking agent (F) in the thermosetting resin composition (III-1) is 0. 0 with respect to 100 parts by mass of the polymer component (A).
- the amount is preferably 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.
- the effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit.
- the excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.
- thermosetting resin composition (III-1) and the thermosetting resin film 1 may contain a general-purpose additive (I) as long as the effects of the present invention are not impaired.
- the general-purpose additive (I) may be a known one, and can be arbitrarily selected according to the purpose.
- the general-purpose additive (I) is not particularly limited, but preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye Pigments), gettering agents and the like.
- the general-purpose additive (I) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be only one type or two or more types. When the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more general-purpose additives (I), the combination and ratio thereof can be arbitrarily selected.
- the contents of the general-purpose additive (I) in the thermosetting resin composition (III-1) and the thermosetting resin film 1 are not particularly limited, and may be appropriately selected depending on the purpose.
- thermosetting resin composition (III-1) preferably further contains a solvent.
- the thermosetting resin composition (III-1) containing a solvent has good handleability.
- the solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-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 thermosetting resin composition (III-1) may be only one type or two or more types. When the thermosetting resin composition (III-1) contains two or more solvents, the combination and ratio thereof can be arbitrarily selected.
- the solvent contained in the thermosetting resin composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the thermosetting resin composition (III-1) can be more uniformly mixed.
- thermosetting resin composition such as the thermosetting resin composition (III-1) can be obtained by blending each component for constituting the composition.
- the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
- the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
- the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
- the first protective film forming sheet 1A can be manufactured by sequentially laminating the above-described layers so as to have a corresponding positional relationship.
- the method for forming each layer is as described above.
- the 1st support sheet 11 when laminating
- middle layer can be laminated
- thermosetting resin film when a thermosetting resin film is further laminated on the first pressure-sensitive adhesive layer laminated on the first base material, the thermosetting resin composition or energy on the first pressure-sensitive adhesive layer. It is possible to directly form a thermosetting resin film by applying a composition for forming a linear curable protective film. Similarly, when further laminating the first pressure-sensitive adhesive layer on the first intermediate layer already laminated on the first base material, the first pressure-sensitive adhesive composition is applied on the first intermediate layer. The first pressure-sensitive adhesive layer can be directly formed. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed.
- the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed.
- the composition is preferably applied to the release-treated surface of the release film.
- the release film may be removed as necessary after forming the laminated structure.
- a first protective film-forming sheet (a first support sheet 11 is a first layer) in which a first pressure-sensitive adhesive layer is laminated on a first base material and a curable resin layer is laminated on the first pressure-sensitive adhesive layer.
- a first protective film-forming sheet 1A which is a laminate of a base material and a first pressure-sensitive adhesive layer
- the first pressure-sensitive adhesive composition is applied on the first base material
- the first pressure-sensitive adhesive layer is laminated on the first base material by drying according to the above or irradiating energy rays.
- thermosetting resin composition or an energy ray-curable protective film-forming composition is applied onto a release film, and dried as necessary, so that heat containing a thermosetting component on the release film is obtained.
- a curable resin film 1 is formed. And the exposed surface of this thermosetting resin film 1 is bonded together with the exposed surface of the 1st adhesive layer already laminated
- the first intermediate layer is formed on the first base material by applying the composition for forming the first intermediate layer on one base material and drying it as necessary or irradiating it with energy rays. .
- a 1st adhesive layer is formed on a peeling film separately by apply
- thermosetting resin composition or an energy ray-curable protective film-forming composition is further applied onto the release film, and dried as necessary, so that the thermosetting property is applied to the release film.
- a thermosetting resin film 1 containing components is formed.
- thermosetting resin film 1 is bonded together with the exposed surface of the 1st adhesive layer laminated
- the first protective film forming sheet 1A is obtained.
- the first pressure-sensitive adhesive composition or the first intermediate layer-forming composition is applied on the release film, and is dried or irradiated with energy rays as necessary.
- the first pressure-sensitive adhesive layer or the first intermediate layer is formed on the release film, and the exposed surface of these layers is bonded to one surface of the first base material, whereby the first pressure-sensitive adhesive layer or the first intermediate layer is bonded.
- An intermediate layer may be laminated on the substrate. In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.
- the first protective film-forming sheet 1A may be manufactured by appropriately selecting a layer that employs such a process as necessary.
- the first protective film-forming sheet 1A is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, the thermosetting resin film 1) opposite to the first support sheet 11.
- a composition for forming a layer constituting the outermost layer such as a thermosetting resin composition or an energy ray-curable protective film forming composition, on this release film (preferably its release-treated surface).
- a layer constituting the outermost layer is formed on the release film, and the layer remains on the exposed surface opposite to the side in contact with the release film.
- the first protective film-forming sheet 1A can also be obtained by laminating each of the above layers by any one of the methods described above and leaving the layers bonded together without removing the release film.
- a second protective film forming film 2 is further provided on one surface 21 a of the second support sheet 21 as shown in FIG. 5.
- the structure contained in the film kit 10 (refer FIG. 1A etc.) is employable.
- the second support sheet 21 is not particularly limited, and has the same material and thickness as the first support sheets 11, 11A, 11B provided in the first protective film forming sheets 1A, 1B, 1C as described above. Things can be adopted. That is, although detailed illustration is omitted in FIG. 5, the second support sheet 21 may be configured such that the second protective film forming film 2 is in direct contact with the first base material. Alternatively, it is also possible to employ a film in which a first intermediate layer and a first pressure-sensitive adhesive layer are further provided between the first base material and the second protective film forming film 2.
- the second protective film-forming film 2 is a film for forming the second protective film 2a that protects the back surface 5b side of the semiconductor wafer 5, and is at least thermally cured in the same manner as the thermosetting resin film 1. Consists of sex components. And as the 2nd protective film formation film 2, what consists of a composition similar to the thermosetting resin film 1 as mentioned above is employable.
- the 2nd protective film formation film 2 it can be set as the structure which contains a coloring agent further.
- a coloring agent organic or inorganic pigments and dyes can be used.
- the dye for example, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used.
- limit especially as a pigment It can select from a well-known pigment suitably and can be used.
- black pigment examples include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like. From the viewpoint of improving the reliability of the semiconductor chip, carbon black is preferable. In addition, you may use these colorants individually or in combination of 2 or more types.
- the content of the colorant in the second protective film-forming film 2 is preferably 0.01 to 30% by mass with respect to the total mass (100% by mass) of the composition forming the second protective film-forming film 2.
- the amount is preferably 0.05 to 25% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.15 to 5% by mass.
- the thickness of the second protective film forming film 2 may be approximately the same as that of the thermosetting resin film 1 as described above.
- thermosetting resin film and the second protective film forming film, the thermosetting resin film, and the first protective film forming sheet provided with the thermosetting resin film according to the present invention are optimized by optimizing the relationship between the heat generation start temperature and the heat generation peak temperature between the thermosetting resin film attached to the surface of the semiconductor wafer and the second protective film forming film attached to the back surface.
- the stress applied to the semiconductor wafer due to shrinkage or the like when the film is heat-cured is corrected by the stress when the second protective film forming film is heat-cured. Thereby, it is possible to suppress the warpage of the semiconductor wafer, and it is possible to manufacture a highly reliable semiconductor package.
- thermosetting resin film on the front surface side of the semiconductor wafer and the second protective film forming film on the back surface side Since the relationship between the heat generation start temperature and the heat generation peak temperature is optimized, warping of the semiconductor wafer can be suppressed during the curing step of forming a protective film on the surface of the semiconductor wafer. It becomes possible to manufacture a semiconductor package having excellent properties.
- the heat generation starting temperature of the thermosetting resin film 1 measured by the differential scanning calorimetry (DSC) method is the differential scanning calorimetry.
- thermosetting resin film 1 and the second protection which are equal to or higher than the heat generation starting temperature measured by the differential scanning calorimetry of the second protective film forming film 2 measured by the method, and further measured by the differential scanning calorimetry
- the exothermic peak temperatures of the film-forming film 2 measured by differential scanning calorimetry are 185 to 200 ° C., respectively, and the difference in the exothermic peak temperatures between the thermosetting resin film 1 and the second protective film-forming film 2 is A configuration in the range of 0 to 10 ° C. can be adopted.
- the linear expansion coefficient of the thermosetting resin film 1 is in the range of 47 to 80 ( ⁇ 10 ⁇ 6 / ° C.).
- a configuration in which the difference from the linear expansion coefficient of the second protective film forming film 2 is in the range of 3 to 30 ( ⁇ 10 ⁇ 6 / ° C.) can be employed.
- thermosetting resin film and the second protective film forming film, the thermosetting resin film, and the first protective film forming according to the present invention.
- the method for forming the sheet and the first protective film for the semiconductor wafer can be appropriately changed and implemented without departing from the scope of the present invention.
- Polymer component Polymer component (A) -1 butyl acrylate (hereinafter abbreviated as “BA”) (55 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) (10 parts by mass)
- BA butyl acrylate
- MA methyl acrylate
- GMA glycidyl methacrylate
- HOA 2-hydroxyethyl acrylate
- Resin weight average molecular weight 800,000, glass transition temperature -28 ° C.
- the compounding ratio of each component is shown in Table 1 below.
- Epoxy resin (B1) -1 Liquid bisphenol F type epoxy resin ("YL983U” manufactured by Mitsubishi Chemical Corporation)
- Epoxy resin (B1) -2 Multifunctional aromatic epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)
- Epoxy resin (B1) -3 Dicyclopentadiene type epoxy resin (“EPICLON HP-7200” manufactured by DIC) ⁇
- thermosetting resin composition Polymer component (A) -1, epoxy resin (B1) -1, epoxy resin (B1) -2, epoxy resin (B1) -3, thermosetting agent (B2) -1, curing accelerator (C) -1 , And the filler (D) -1 is the value shown in the following Table 1 with respect to the total content of all components other than the solvent (described as “content ratio” in Table 1)
- a thermosetting resin composition (III-1) having a solid content concentration of 55% by mass is obtained as a thermosetting resin composition. It was.
- the description of “-” in the column of the contained component in Table 1 below means that the thermosetting resin composition does not contain the component.
- first pressure-sensitive adhesive composition For the adhesive resin (I-2a) (100 parts by mass) obtained above, a tolylene diisocyanate trimer adduct of trimethylolpropane (“Coronate L” manufactured by Tosoh Corporation) (as an isocyanate crosslinking agent) ( 0.5 parts by mass) was added and stirred at 23 ° C. to obtain a first pressure-sensitive adhesive composition (I-2) having a solid content concentration of 30% by mass as the first pressure-sensitive adhesive composition. In addition, all the compounding parts in this "manufacture of the 1st adhesive composition" are solid content conversion values.
- the first pressure-sensitive adhesive composition obtained above is applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment.
- the first pressure-sensitive adhesive layer having a thickness of 60 ⁇ m was formed by heating and drying at 120 ° C. for 2 minutes.
- a polyolefin film (thickness 25 ⁇ m), an adhesive layer (thickness 2.5 ⁇ m), a polyethylene terephthalate film (thickness 50 ⁇ m), an adhesive layer
- a first support sheet was obtained by laminating a laminated film having a thickness of 105 ⁇ m in which a (thickness of 2.5 ⁇ m) and a polyolefin film (thickness of 25 ⁇ m) were laminated in this order.
- thermosetting resin composition obtained above is applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. And it was made to dry at 100 degreeC for 2 minute (s), and the 40-micrometer-thick thermosetting resin film was produced.
- SP-PET 381031 manufactured by Lintec Co., Ltd., thickness 38 ⁇ m
- the release film is removed from the first pressure-sensitive adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin film obtained above is bonded to the exposed surface of the first pressure-sensitive adhesive layer.
- the 1st base material, the 1st adhesive layer, the thermosetting resin film, and the peeling film obtained the 1st sheet
- thermosetting resin film (second protective film-forming film) having a thickness of 40 ⁇ m.
- the release film is removed from the first adhesive layer of the second support sheet, and the exposed surface of the first adhesive layer is The exposed surfaces of the second protective film-forming film obtained in step 1 are bonded together, and the first base material, the first pressure-sensitive adhesive layer, the second protective film-forming film, and the release film are laminated in this order in the thickness direction.
- second protective film forming sheet was obtained.
- thermosetting resin film and second protective film forming film Using the thermosetting resin composition obtained above, the thermosetting property having a thickness of 50 ⁇ m is the same as that for manufacturing the first protective film-forming sheet described above except that the coating amount is different. A resin film was prepared and laminated with 10 layers to prepare a thermosetting resin film having a thickness of 500 ⁇ m. Similarly, using the composition for forming a second protective film forming film obtained above, except that the coating amount is different, the same method as that for producing the second protective film forming film described above is used. A second protective film-forming film made of a thermosetting resin having a thickness of 50 ⁇ m was prepared, and this was laminated with 10 layers to prepare a second protective film-forming film having a thickness of 500 ⁇ m.
- thermosetting resin film was produced from this thermosetting resin film, and the exothermic peak temperature was measured using a conventionally known differential scanning calorimetry (DSC) apparatus.
- DSC differential scanning calorimetry
- a sample for evaluation was prepared from a thermosetting resin film, and the coefficient of thermal expansion (CTE ⁇ 1) was measured using a conventionally known thermomechanical analysis (TMA) apparatus under conditions based on JIS K7197. The measurement results from these tests are shown in Table 3 below.
- Example 1 As shown in Table 3 below, in Example 1, it was confirmed that the exothermic peak temperature was 185 ° C. within the range specified by the present invention for both the thermosetting resin film and the second protective film forming film.
- the linear expansion coefficient of the thermosetting resin film is 47 ( ⁇ 10 ⁇ 6 / ° C.)
- the linear expansion coefficient of the second protective film forming film is 50 ( ⁇ 10 ⁇ 6 / ° C.). It was confirmed that it was within the range defined by the present invention.
- thermosetting resin film obtained above a kit of thermosetting resin film and second protective film forming film
- the first protective film is formed on the bump forming surface of the semiconductor wafer, and the second is formed on the back surface.
- a protective film was formed. That is, first, a second protective film forming film is attached to the back surface side of a semiconductor wafer having a plurality of bumps on the front surface, and a first protective film forming sheet is attached to the front surface side. Then, a laminated body in which a semiconductor wafer and a first protective film forming sheet (thermosetting resin film) were sequentially laminated was produced. At this time, as the second protective film forming film, a film in which a dicing tape was attached to the surface opposite to the surface attached to the back surface of the semiconductor wafer was used.
- the dicing tape is attached to the ring frame for wafer dicing to fix the laminate (semiconductor wafer) on the ring frame,
- the support sheet was peeled from the first protective film forming sheet.
- thermosetting resin film on the semiconductor wafer fixed to the ring frame for wafer dicing using a pressure heat curing apparatus (“RAD-9100” manufactured by Lintec Corporation). While heating at a set temperature of 180 ° C. for 1 hour to soften the thermosetting resin film, it was cured to form a first protective film. At the same time, the second protective film-forming film was softened and then cured to form a second protective film.
- RAD-9100 manufactured by Lintec Corporation
- the semiconductor wafer having the first protective film and the second protective film formed on each surface is cut into chips by a dicing process, and then the semiconductor wafer divided into chips is removed from the ring frame while removing the dicing tape. And peeled off.
- Example 1 in which the first protective film was formed on the bump forming surface of the semiconductor wafer (the second protective film was formed on the back surface) using the film kit having the configuration according to the present invention. It was confirmed that no warping occurred after the thermosetting resin film was cured to form the first protective film.
- Example 2 and 3 The films of Examples 2 and 3, including the first protective film-forming sheet and the second protective film-forming film, as in Example 1, except that the thermosetting resin composition was as shown in Table 1 below. Kits were manufactured and evaluated in the same manner as described above, and the results are shown in Table 3 below.
- thermosetting resin film and the second protective film-forming film had an exothermic peak temperature of 185 ° C. or 195 ° C. It was confirmed that it was within the range specified by the invention.
- the linear expansion coefficient of the thermosetting resin film is 47 ( ⁇ 10 ⁇ 6 / ° C.)
- the linear expansion coefficient of the second protective film forming film is 50 ( ⁇ 10 ⁇ 6 / ° C.).
- the linear expansion coefficient of the thermosetting resin film is 80 ( ⁇ 10 ⁇ 6 / ° C.)
- the linear expansion coefficient of the second protective film forming film is 50 ( ⁇ 10 ⁇ 6 / ° C.). It was confirmed that it was within the range defined by the present invention.
- Example 2 in which the first protective film was formed on the bump forming surface of the semiconductor wafer (the second protective film was formed on the back surface) using the film kit having the configuration according to the present invention. 3, as in Example 1, it was confirmed that no warpage occurred after the thermosetting resin film was cured to form the first protective film.
- thermosetting resin film exceeds the upper limit defined in claims 2 and 4 of the present invention, and the thermosetting resin film and The difference in thermal expansion coefficient with the second protective film forming film also exceeds the upper limit value. For this reason, in Comparative Example 1, the warp occurred so that the end portion of the semiconductor wafer was directed to the bump forming surface side (first protective film forming surface side).
- the heat generation peak temperature of the thermosetting resin film exceeds the upper limit defined in the present invention, and heat generation between the thermosetting resin film and the second protective film forming film The difference in peak temperature also exceeds the upper limit. For this reason, in Comparative Example 2, the warp occurred so that the end portion of the semiconductor wafer was directed to the bump forming surface side (first protective film forming surface side).
- the heat generation start temperature and heat generation between the thermosetting resin film attached to the front surface of the semiconductor wafer and the second protective film forming film attached to the back surface are defined. It is clear that by optimizing the relationship between the peak temperatures, it is possible to suppress the warpage of the semiconductor wafer and to manufacture a highly reliable semiconductor package.
- the present invention can be used for manufacturing a semiconductor chip or the like having bumps in connection pad portions used in a flip chip mounting method.
- thermosetting resin film and second protective film formation film 50 ... laminate, 51 ... bump, 51a ... surface (bump surface) ), 60... Dicing tape, 60a... Upper surface (dicing tape).
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Abstract
Description
本出願は、2015年11月4日に日本に出願された特願2015-217097号に基づき、優先権を主張し、その内容をここに援用する。 The present invention relates to a kit of a thermosetting resin film and a second protective film forming film, a thermosetting resin film, a first protective film forming sheet provided with the thermosetting resin film, and a first protection for a semiconductor wafer. The present invention relates to a film forming method.
This application claims priority based on Japanese Patent Application No. 2015-217097 filed in Japan on November 4, 2015, the contents of which are incorporated herein by reference.
以下に、本発明の熱硬化性樹脂フィルムと第2保護膜形成フィルムのキット10、熱硬化性樹脂フィルム1及び第1保護膜形成用シート1Aの構成について、順次詳述する。 That is, the
Below, the structure of the thermosetting resin film of this invention and the
図1A及び図1Bに例示するような、本発明に係るフィルムキット10は、上述したように、半導体ウエハ5における複数のバンプ5を保護する第1保護膜1a(図1C及び図1D参照)を形成するためのものである。 << Kit of thermosetting resin film and second protective film forming film (film kit) >>
As described above, the
第1保護膜1aは、本発明の熱硬化性樹脂フィルム1を用いて形成されたものであり、半導体ウエハ5の表面5aを被覆し、さらに、バンプ51のうち、頂上とその近傍以外の表面51aを被覆している。このように、第1保護膜1aは、バンプ51の表面51aのうち、バンプ51の頂上とその近傍以外の領域に密着するとともに、半導体ウエハ5の表面(回路面)5aにも密着して、バンプ51を埋め込んでいる。なお、図1A及び図1Bに示す例においては、バンプとして、上記のような、ほぼ球状の形状(球の一部が平面によって切り取られた形状)のものを示しているが、本発明に係る硬化性樹脂フィルム1から形成される第1保護膜1aによって保護できるバンプの形状は、これには限定されない。例えば、図1A及び図1B中に示すような、ほぼ球状の形状のバンプを、高さ方向(図1A及び図1B中において半導体ウエハ5の表面5aに対して直交する方向)に引き伸ばしてなる形状、即ち、ほぼ長球状である回転楕円体の形状(長球状である回転楕円体の長軸方向の一端を含む部位が平面によって切り取られた形状)のバンプや、上記のような、ほぼ球状の形状を、高さ方向に押し潰してなる形状、即ち、ほぼ扁球状である回転楕円体の形状(扁球状である回転楕円体の短軸方向の一端を含む部位が平面によって切り取られた形状)のバンプも、好ましい形状のバンプとして挙げられる。また、本発明に係る硬化性樹脂フィルム1によって形成される第1保護膜1aは、その他の如何なる形状のバンプに対しても適用可能であるが、特に、バンプの形状が、上記のような球状又は楕円等を含む球状である場合おいて、半導体ウエハの表面及びバンプを保護する効果が顕著に得られる。 A plurality of
The first
また、フィルムキット10は、熱硬化性樹脂フィルム1及び第2保護膜形成フィルム2の示差走査熱量分析法によって測定される発熱ピーク温度が、それぞれ100~200℃であり、熱硬化性樹脂フィルム1と第2保護膜形成フィルム2との発熱ピーク温度の差が35℃未満である構成とされている。さらに、フィルムキット10は、熱硬化性樹脂フィルム1の線膨張係数が5~80(×10-6/℃)であり、且つ、第2保護膜形成フィルム2の線膨張係数との差が35(×10-6/℃)未満である構成とすることができる。 And the
In addition, the
本発明のフィルムキット10によれば、上述のような、半導体ウエハ5に付与される応力の矯正作用により、半導体ウエハ5を含む積層体に反りが生じるのを抑制することができるので、信頼性に優れた半導体パッケージを製造することが可能となる。 Moreover, in this invention, after making the relationship of the heat generation start temperature and heat generation peak temperature between the
According to the
一方、本発明においては、上記のような発熱開始温度、発熱ピーク温度及び線膨張係数の関係を採用することで、半導体ウエハ5の加熱時、熱硬化性樹脂フィルム1の硬化よりも、第2保護膜形成フィルム2の硬化の方が早く開始される。これにより、半導体ウエハ5には、熱硬化性樹脂フィルム1の加熱硬化による応力F1が付与される前段階から、半導体ウエハ5の端部5cが図1C中の下方に向かう方向、即ち、第2保護膜形成フィルム2側に引っ張られる方向の応力F2が付与される。このように、半導体ウエハ5に対して応力F1が付与される前に、この応力F1とは反対方向の応力2が付与されることで、これら応力F1,F2のバランスがとれた相殺(矯正)関係となるので、半導体ウエハ5に反りが発生するのを抑制することが可能となる。 More specifically, as shown in FIG. 1C, due to shrinkage or the like when the
On the other hand, in the present invention, by adopting the relationship between the heat generation start temperature, the heat generation peak temperature, and the linear expansion coefficient as described above, when the
これに対し、本発明に係るフィルムキット10によれば、上述したように、熱硬化性樹脂フィルム1と第2保護膜形成フィルム2との間の発熱開始温度及び発熱ピーク温度の関係を最適化することで、半導体ウエハ5に付与される応力の矯正作用が得られ、半導体ウエハ5に反りが生じるのを抑制できるというものである。 As shown in FIG. 6, when the
On the other hand, according to the
本発明に係る半導体ウエハ用第1保護膜の形成方法は、図1A~図1Dに示すように、半導体ウエハ5における複数のバンプ51を有する表面5aに、これら複数のバンプ51を保護するための第1保護膜1aを形成する方法である。本発明の半導体ウエハ用第1保護膜の形成方法は、例えば、上記構成を有する本発明のフィルムキット10、熱硬化性樹脂フィルム1、又は第1保護膜形成用シート1Aを用いて、半導体ウエハ5の表面5aに第1保護膜1aを形成する。本発明の半導体ウエハ用第1保護膜の形成方法は、第2保護膜形成フィルム2、半導体ウエハ5及び熱硬化性樹脂フィルム1が順次積層された積層体50を形成する積層ステップと、半導体ウエハ5の表面5aに第1保護膜1aを形成する硬化ステップとを備えて概略構成される。 << Method for Forming First Protective Film for Semiconductor Wafer >>
As shown in FIGS. 1A to 1D, a method for forming a first protective film for a semiconductor wafer according to the present invention is for protecting a plurality of
上記構成を有する本発明のフィルムキット10においては、熱硬化性樹脂フィルム1が、第1支持シート11の一方の表面11a上に備えられる第1保護膜形成用シート1Aとして、フィルムキット10に含まれる構成を採用することができる。
以下に、第1保護膜形成用シート1A、及び、それに含まれる熱硬化性樹脂フィルム1の各構成について詳述する。 << First protective film forming sheet >>
In the
Below, each structure of 1 A of 1st sheets for protective film formation, and the
第1保護膜形成用シート1Aに備えられる第1支持シート11は、1層(単層)からなるものでもよいし、2層以上の複数層からなるものでもよい。第1支持シート11が複数層からなる場合、これら複数層の構成材料及び厚さは、互いに同一でも異なっていてもよく、これら複数層の組み合わせは、本発明の効果を損なわない限り、特に限定されない。 <First support sheet>
The
図2は、本発明の第1保護膜形成用シートの一例を模式的に示す断面図である。図2に示す第1保護膜形成用シート1Aは、第1支持シート11として、第1基材12上に第1粘着剤層13が積層されてなるものを用いたものである。即ち、第1保護膜形成用シート1Aは、第1基材12上に第1粘着剤層13を備え、第1粘着剤層13上に熱硬化性成分を含む熱硬化性樹脂フィルム1を備えて構成されている。第1支持シート11は、第1基材12及び第1粘着剤層13の積層体であり、第1支持シート11の一方の表面11a上、即ち、第1粘着剤層13の一方の表面13a上に熱硬化性樹脂フィルム1が設けられている。
第1保護膜形成用シート1Aにおいて、熱硬化性樹脂フィルム1は、上述の様に、半導体ウエハのバンプ形成面に貼着して用いられ、半導体ウエハの裏面に貼付する第2保護膜形成フィルムとの間で、発熱開始温度及び発熱ピーク温度、さらには線膨張係数の関係が最適化されてなるものである。 An example of the first protective film-forming sheet according to the present invention will be described for each kind of the first support sheet with reference to FIGS.
FIG. 2 is a cross-sectional view schematically showing an example of the first protective film-forming sheet of the present invention. A first protective film-forming
In the first protective
図3に示す第1保護膜形成用シート1Bは、第1支持シートとして、第1基材上に第1中間層が積層され、第1中間層上に第1粘着剤層が積層されてなるものを用いている。即ち、第1保護膜形成用シート1Bは、第1基材12上に第1中間層14を備え、第1中間層14上に第1粘着剤層13を備え、第1粘着剤層13上に熱硬化性樹脂フィルム1を備えて構成されている。第1支持シート11Aは、第1基材12、第1中間層14及び第1粘着剤層13がこの順に積層されてなる積層体であり、第1支持シート11Aの一方の表面11a上、即ち、第1粘着剤層13の一方の表面13a上に熱硬化性樹脂フィルム1が設けられている。
第1保護膜形成用シート1Bは、換言すると、図2に示す第1保護膜形成用シート1Aにおいて、第1基材12と第1粘着剤層13との間に、さらに第1中間層14を備えたものである。
第1保護膜形成用シート1Bにおいて、熱硬化性樹脂フィルム1は、上述の様に、半導体ウエハのバンプ形成面に貼着して用いられ、半導体ウエハの裏面に貼付する第2保護膜形成フィルムとの間で、発熱開始温度及び発熱ピーク温度、さらには線膨張係数の関係が最適化されてなるものである。 FIG. 3 is a cross-sectional view schematically showing another example of the first protective film-forming sheet of the present invention. 3, the same components as those shown in FIG. 2 are denoted by the same reference numerals as those in FIG. 2, detailed description thereof is omitted, and the same applies to FIG. 4.
A first protective film-forming
In other words, in the first protective
In the first protective
図4に示す第1保護膜形成用シート1Cは、第1支持シートとして、第1基材のみからなるものを用いている。即ち、第1保護膜形成用シート1Cは、第1基材12上に熱硬化性樹脂フィルム1を備えて構成されている。第1支持シート11Bは、第1基材12のみから構成され、第1支持シート11Bの一方の表面11a上、即ち、第1基材12の一方の表面12a上に熱硬化性樹脂フィルム1が直接接触して設けられている。
第1保護膜形成用シート1Cは、換言すると、図2に示す第1保護膜形成用シート1Aにおいて、第1粘着剤層13が除かれてなるものである。
第1保護膜形成用シート1Cにおいて、熱硬化性樹脂フィルム1は、上述の様に、半導体ウエハのバンプ形成面に貼着して用いられ、半導体ウエハの裏面に貼付する第2保護膜形成フィルム2との間で、発熱開始温度及び発熱ピーク温度、さらには線膨張係数の関係が最適化されてなるものである。
以下に、第1支持シートの各構成について詳述する。 FIG. 4 is a cross-sectional view schematically showing still another example of the first protective film-forming sheet of the present invention.
In the first protective film-forming
In other words, the first protective
In the first protective
Below, each structure of a 1st support sheet is explained in full detail.
第1支持シートに備えられる第1基材は、シート状又はフィルム状のものであり、その構成材料としては、例えば、以下の各種樹脂が挙げられる。
第1基材を構成する樹脂としては、例えば、低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(LLDPE)、高密度ポリエチレン(HDPE)等のポリエチレン;ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ノルボルネン樹脂等のポリエチレン以外のポリオレフィン;エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸エステル共重合体、エチレン-ノルボルネン共重合体等のエチレン系共重合体(モノマーとしてエチレンを用いて得られた共重合体);ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂(モノマーとして塩化ビニルを用いて得られた樹脂);ポリスチレン;ポリシクロオレフィン;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン-2,6-ナフタレンジカルボキシレート、すべての構成単位が芳香族環式基を有する全芳香族ポリエステル等のポリエステル;2種以上の前記ポリエステルの共重合体;ポリ(メタ)アクリル酸エステル;ポリウレタン;ポリウレタンアクリレート;ポリイミド;ポリアミド;ポリカーボネート;フッ素樹脂;ポリアセタール;変性ポリフェニレンオキシド;ポリフェニレンスルフィド;ポリスルホン;ポリエーテルケトン等が挙げられる。
また、前記樹脂としては、例えば、前記ポリエステルとそれ以外の樹脂との混合物等のポリマーアロイも挙げられる。前記ポリエステルとそれ以外の樹脂とのポリマーアロイは、ポリエステル以外の樹脂の量が比較的少量であるものが好ましい。
また、前記樹脂としては、例えば、ここまでに例示した前記樹脂の1種又は2種以上が架橋した架橋樹脂;ここまでに例示した前記樹脂の1種又は2種以上を用いたアイオノマー等の変性樹脂も挙げられる。 [First base material]
The 1st base material with which a 1st support sheet is provided is a sheet form or a film form, and the following various resin is mentioned as the constituent material, for example.
Examples of the resin constituting the first substrate include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene. Polyolefins other than polyethylene, such as resins; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer Polymer (copolymer obtained using ethylene as monomer); Vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as monomer); Polystyrene; Polycyclo Olefin; polyethylene terephthalate, poly Polyesters such as tylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all the structural units have aromatic cyclic groups; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.
ここで、「第1基材の厚さ」とは、第1基材全体の厚さを意味し、例えば、複数層からなる第1基材の厚さとは、第1基材を構成するすべての層の合計の厚さを意味する。 The thickness of the first base material is preferably 5 to 1000 μm, more preferably 10 to 500 μm, further preferably 15 to 300 μm, and particularly preferably 20 to 150 μm.
Here, the “thickness of the first base material” means the thickness of the entire first base material. For example, the thickness of the first base material composed of a plurality of layers means all of the first base material. Means the total thickness of the layers.
また、後述する第1粘着剤層又は硬化性樹脂層がエネルギー線硬化性を有する場合、第1基材はエネルギー線を透過させるものであることが好ましい。 The first substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
Moreover, when the 1st adhesive layer or curable resin layer mentioned later has energy-beam sclerosis | hardenability, it is preferable that a 1st base material is a thing which permeate | transmits an energy beam.
第1粘着剤層は、シート状又はフィルム状であり、粘着剤を含有する。
前記粘着剤としては、例えば、アクリル系樹脂((メタ)アクリロイル基を有する樹脂からなる粘着剤)、ウレタン系樹脂(ウレタン結合を有する樹脂からなる粘着剤)、ゴム系樹脂(ゴム構造を有する樹脂からなる粘着剤)、シリコーン系樹脂(シロキサン結合を有する樹脂からなる粘着剤)、エポキシ系樹脂(エポキシ基を有する樹脂からなる粘着剤)、ポリビニルエーテル、ポリカーボネート等の粘着性樹脂が挙げられ、アクリル系樹脂が好ましい。 [First adhesive layer]
A 1st adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the pressure-sensitive adhesive include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber resin (a resin having a rubber structure). ), Silicone resins (adhesives composed of resins having a siloxane bond), epoxy resins (adhesives composed of resins having an epoxy group), polyvinyl ether, polycarbonate, and other adhesive resins. Based resins are preferred.
ここで、「第1粘着剤層の厚さ」とは、第1粘着剤層全体の厚さを意味し、例えば、複数層からなる第1粘着剤層の厚さとは、第1粘着剤層を構成するすべての層の合計の厚さを意味する。 The thickness of the first pressure-sensitive adhesive layer is preferably 1 to 1000 μm, more preferably 5 to 500 μm, and particularly preferably 10 to 100 μm.
Here, the “thickness of the first pressure-sensitive adhesive layer” means the thickness of the entire first pressure-sensitive adhesive layer. For example, the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers means the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.
本発明において、「エネルギー線」とは、電磁波又は荷電粒子線の中でエネルギー量子を有するものを意味し、その例として、紫外線、電子線等が挙げられる。
紫外線は、例えば、紫外線源として高圧水銀ランプ、ヒュージョンHランプ、キセノンランプ、又はLED等を用いることで照射できる。電子線は、電子線加速器等によって発生させたものを照射できる。
本発明において、「エネルギー線硬化性」とは、エネルギー線を照射することにより硬化する性質を意味し、「非エネルギー線硬化性」とは、エネルギー線を照射しても硬化しない性質を意味する。 The first pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive. The first pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
In the present invention, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or an LED as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present invention, “energy ray curable” means the property of being cured by irradiation with energy rays, and “non-energy ray curable” means the property of not being cured even when irradiated with energy rays. .
第1粘着剤層は、粘着剤を含有する第1粘着剤組成物を用いて形成できる。例えば、第1粘着剤層の形成対象面に第1粘着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に第1粘着剤層を形成できる。第1粘着剤層のより具体的な形成方法は、他の層の形成方法とともに、後ほど詳細に説明する。第1粘着剤組成物中の、常温で気化しない成分同士の含有量の比率は、通常、第1粘着剤層の前記成分同士の含有量の比率と同じとなる。なお、本実施形態において、「常温」とは、特に冷やしたり、熱したりしない温度、即ち平常の温度を意味し、例えば、15~25℃の温度等が挙げられる。 {{First adhesive composition}}
A 1st adhesive layer can be formed using the 1st adhesive composition containing an adhesive. For example, a 1st adhesive layer can be formed in the target site | part by applying a 1st adhesive composition to the formation object surface of a 1st adhesive layer, and making it dry as needed. A more specific method for forming the first pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers. In the first pressure-sensitive adhesive composition, the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the first pressure-sensitive adhesive layer. In the present embodiment, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
第1粘着剤組成物(I-1)は、上述の様に、非エネルギー線硬化性の粘着性樹脂(I-1a)と、エネルギー線硬化性化合物と、を含有する。 {First adhesive composition (I-1)}
As described above, the first pressure-sensitive adhesive composition (I-1) contains the non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and the energy ray-curable compound.
前記粘着性樹脂(I-1a)は、アクリル系樹脂であることが好ましい。
前記アクリル系樹脂としては、例えば、少なくとも(メタ)アクリル酸アルキルエステル由来の構成単位を有するアクリル系重合体が挙げられる。
前記アクリル系樹脂が有する構成単位は、1種のみでもよいし、2種以上でもよい。前記アクリル系樹脂が有する構成単位が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Adhesive resin (I-1a))
The adhesive resin (I-1a) is preferably an acrylic resin.
As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
The acrylic resin may have only one type of structural unit, or two or more types of structural units. When the acrylic resin has two or more structural units, the combination and ratio thereof can be arbitrarily selected.
(メタ)アクリル酸アルキルエステルとして、より具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル((メタ)アクリル酸ラウリル)、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル((メタ)アクリル酸ミリスチル)、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル((メタ)アクリル酸パルミチル)、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル((メタ)アクリル酸ステアリル)、(メタ)アクリル酸ノナデシル、及び(メタ)アクリル酸イコシル等が挙げられる。 Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred.
More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meta) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, and icosyl (meth) acrylate.
前記官能基含有モノマーとしては、例えば、前記官能基が後述する架橋剤と反応することで架橋の起点となったり、前記官能基が不飽和基含有化合物中の不飽和基と反応することで、アクリル系重合体の側鎖に不飽和基の導入を可能とするものが挙げられる。 The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group reacts with a crosslinking agent to be described later to become a starting point of crosslinking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound, The thing which enables introduction | transduction of an unsaturated group to the side chain of an acrylic polymer is mentioned.
即ち、官能基含有モノマーとしては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、及びエポキシ基含有モノマー等が挙げられる。 Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
前記他のモノマーは、(メタ)アクリル酸アルキルエステル等と共重合可能なものであれば特に限定されない。
前記他のモノマーとしては、例えば、スチレン、α-メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、及びアクリルアミド等が挙げられる。 In addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer, the acrylic polymer may further have a structural unit derived from another monomer.
The other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
一方、前記アクリル系重合体中の官能基に、エネルギー線重合性不飽和基(エネルギー線重合性基)を有する不飽和基含有化合物を反応させたものは、上述のエネルギー線硬化性の粘着性樹脂(I-2a)として使用できる。
なお、本発明において、「エネルギー線重合性」とは、エネルギー線を照射することにより重合する性質を意味する。 The acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
On the other hand, the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).
In the present invention, “energy beam polymerizability” means a property of polymerizing by irradiation with energy rays.
第1粘着剤組成物(I-1)が含有する前記エネルギー線硬化性化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー又はオリゴマーが挙げられる。
エネルギー線硬化性化合物のうち、モノマーとしては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトール(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-へキサンジオール(メタ)アクリレート等の多価(メタ)アクリレート;ウレタン(メタ)アクリレート;ポリエステル(メタ)アクリレート;ポリエーテル(メタ)アクリレート;エポキシ(メタ)アクリレート等が挙げられる。
エネルギー線硬化性化合物のうち、オリゴマーとしては、例えば、上記で例示したモノマーが重合してなるオリゴマー等が挙げられる。
エネルギー線硬化性化合物は、分子量が比較的大きく、第1粘着剤層の貯蔵弾性率を低下させにくいという点では、ウレタン(メタ)アクリレート、ウレタン(メタ)アクリレートオリゴマーが好ましい。 (Energy ray curable compound)
Examples of the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4. Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the first pressure-sensitive adhesive layer is difficult to be lowered.
粘着性樹脂(I-1a)として、(メタ)アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、第1粘着剤組成物(I-1)は、さらに架橋剤を含有することが好ましい。 (Crosslinking agent)
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), the first pressure-sensitive adhesive composition The product (I-1) preferably further contains a crosslinking agent.
架橋剤としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、これらジイソシアネートのアダクト体等のイソシアネート系架橋剤(イソシアネート基を有する架橋剤);エチレングリコールグリシジルエーテル等のエポキシ系架橋剤(グリシジル基を有する架橋剤);ヘキサ[1-(2-メチル)-アジリジニル]トリフオスファトリアジン等のアジリジン系架橋剤(アジリジニル基を有する架橋剤);アルミニウムキレート等の金属キレート系架橋剤(金属キレート構造を有する架橋剤);イソシアヌレート系架橋剤(イソシアヌル酸骨格を有する架橋剤)等が挙げられる。
粘着剤の凝集力を向上させて第1粘着剤層の粘着力を向上させる点、及び入手が容易である等の点から、架橋剤はイソシアネート系架橋剤であることが好ましい。 For example, the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
As a crosslinking agent, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( Cross-linking agent having a glycidyl group); Aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanuric acid skeleton) and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and improving the adhesive strength of the first pressure-sensitive adhesive layer, and being easily available.
第1粘着剤組成物(I-1)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する第1粘着剤組成物(I-1)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 (Photopolymerization initiator)
The first pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The first pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
また、前記光重合開始剤としては、例えば、1-クロロアントラキノン等のキノン化合物;アミン等の光増感剤等を用いることもできる。 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, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc. Α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; , Dibenzyl, benzophenone, 2,4-diethylthioxanthone, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.
第1粘着剤組成物(I-1)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、例えば、帯電防止剤、酸化防止剤、軟化剤(可塑剤)、充填剤(フィラー)、防錆剤、着色剤(顔料、染料)、増感剤、粘着付与剤、反応遅延剤、架橋促進剤(触媒)等の公知の添加剤が挙げられる。
なお、反応遅延剤とは、例えば、第1粘着剤組成物(I-1)中に混入している触媒の作用によって、保存中の第1粘着剤組成物(I-1)において、目的としない架橋反応が進行するのを抑制するものである。反応遅延剤としては、例えば、触媒に対するキレートによってキレート錯体を形成するものが挙げられ、より具体的には、1分子中にカルボニル基(-C(=O)-)を2個以上有するものが挙げられる。 (Other additives)
The first pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
Note that the reaction retarding agent means, for example, the purpose of the first pressure-sensitive adhesive composition (I-1) during storage due to the action of the catalyst mixed in the first pressure-sensitive adhesive composition (I-1). It suppresses that the crosslinking reaction which does not progress. Examples of the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C (═O) —) in one molecule. Can be mentioned.
第1粘着剤組成物(I-1)は、溶媒を含有していてもよい。第1粘着剤組成物(I-1)は、溶媒を含有していることで、塗工対象面への塗工適性が向上する。 (solvent)
The first pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the first pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
第1粘着剤組成物(I-2)は、上述の様に、非エネルギー線硬化性の粘着性樹脂(I-1a)の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂(I-2a)を含有する。 {First adhesive composition (I-2)}
As described above, the first pressure-sensitive adhesive composition (I-2) is an energy ray-curable pressure-sensitive adhesive having an unsaturated group introduced in the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). Resin (I-2a) is contained.
前記粘着性樹脂(I-2a)は、例えば、粘着性樹脂(I-1a)中の官能基に、エネルギー線重合性不飽和基を有する不飽和基含有化合物を反応させることで得られる。 (Adhesive resin (I-2a))
The adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
前記エネルギー線重合性不飽和基としては、例えば、(メタ)アクリロイル基、ビニル基(エテニル基)、及びアリル基(2-プロペニル基)等が挙げられ、(メタ)アクリロイル基が好ましい。
粘着性樹脂(I-1a)中の官能基と結合可能な基としては、例えば、水酸基又はアミノ基と結合可能なイソシアネート基及びグリシジル基、並びにカルボキシ基又はエポキシ基と結合可能な水酸基及びアミノ基等が挙げられる。 The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group. A compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, 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 carboxy group or an epoxy group. Etc.
粘着性樹脂(I-2a)として、例えば、粘着性樹脂(I-1a)におけるものと同様な、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、第1粘着剤組成物(I-2)は、さらに架橋剤を含有していてもよい。 (Crosslinking agent)
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, the first adhesive composition The product (I-2) may further contain a crosslinking agent.
第1粘着剤組成物(I-2)が含有する架橋剤は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-2)が含有する架橋剤が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 Examples of the crosslinking agent in the first pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the first pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type or two or more types. When the first pressure-sensitive adhesive composition (I-2) contains two or more crosslinking agents, the combination and ratio thereof can be arbitrarily selected.
第1粘着剤組成物(I-2)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する第1粘着剤組成物(I-2)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 (Photopolymerization initiator)
The first pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The first pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
第1粘着剤組成物(I-2)が含有する光重合開始剤は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-2)が含有する光重合開始剤が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the first pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-2) may be one kind or two or more kinds. When the first pressure-sensitive adhesive composition (I-2) contains two or more photopolymerization initiators, their combination and ratio can be arbitrarily selected.
第1粘着剤組成物(I-2)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
第1粘着剤組成物(I-2)における前記その他の添加剤としては、第1粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
第1粘着剤組成物(I-2)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-2)が含有するその他の添加剤が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Other additives)
The first pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additive in the first pressure-sensitive adhesive composition (I-2) include the same additives as those in the first pressure-sensitive adhesive composition (I-1).
The other additive contained in the first pressure-sensitive adhesive composition (I-2) may be one kind or two or more kinds. When there are two or more other additives contained in the first pressure-sensitive adhesive composition (I-2), their combination and ratio can be arbitrarily selected.
第1粘着剤組成物(I-2)は、第1粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
第1粘着剤組成物(I-2)における前記溶媒としては、第1粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
第1粘着剤組成物(I-2)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-2)において、溶媒の含有量は特に限定されず、適宜調節すればよい。 (solvent)
The first pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the first pressure-sensitive adhesive composition (I-2) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
The solvent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
In the first pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted as appropriate.
第1粘着剤組成物(I-3)は、上述の様に、前記粘着性樹脂(I-2a)と、エネルギー線硬化性低分子化合物と、を含有する。 {First adhesive composition (I-3)}
As described above, the first pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound.
第1粘着剤組成物(I-3)が含有する前記エネルギー線硬化性低分子化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー及びオリゴマーが挙げられ、第1粘着剤組成物(I-1)が含有するエネルギー線硬化性化合物と同じものが挙げられる。
第1粘着剤組成物(I-3)が含有する前記エネルギー線硬化性低分子化合物は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-3)が含有する前記エネルギー線硬化性低分子化合物が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Energy ray curable low molecular weight compound)
Examples of the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) include monomers and oligomers that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays. And the same energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1).
The energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. When the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) is two or more kinds, the combination and ratio thereof can be arbitrarily selected.
第1粘着剤組成物(I-3)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する第1粘着剤組成物(I-3)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 (Photopolymerization initiator)
The first pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The first pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
第1粘着剤組成物(I-3)が含有する光重合開始剤は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-3)における前記光重合開始剤が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators as those in the first pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. When there are two or more photopolymerization initiators in the first pressure-sensitive adhesive composition (I-3), their combination and ratio can be arbitrarily selected.
第1粘着剤組成物(I-3)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、第1粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
第1粘着剤組成物(I-3)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-3)が含有するその他の添加剤が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Other additives)
The first pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range that does not impair the effects of the present invention.
Examples of the other additives include the same additives as the other additives in the first pressure-sensitive adhesive composition (I-1).
The other additive contained in the first pressure-sensitive adhesive composition (I-3) may be only one kind or two or more kinds. When there are two or more other additives contained in the first pressure-sensitive adhesive composition (I-3), the combination and ratio thereof can be arbitrarily selected.
第1粘着剤組成物(I-3)は、第1粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
第1粘着剤組成物(I-3)における前記溶媒としては、第1粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
第1粘着剤組成物(I-3)が含有する溶媒は、1種のみでもよいし、2種以上でもよい。第1粘着剤組成物(I-3)が含有する溶媒が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-3)において、溶媒の含有量は特に限定されず、適宜調節すればよい。 (solvent)
The first pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the first pressure-sensitive adhesive composition (I-3) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
The solvent contained in the first pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. In the case where the first pressure-sensitive adhesive composition (I-3) contains two or more solvents, the combination and ratio thereof can be arbitrarily selected.
In the first pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited and may be appropriately adjusted.
ここまでは、第1粘着剤組成物(I-1)、第1粘着剤組成物(I-2)及び第1粘着剤組成物(I-3)について主に説明したが、これらの含有成分として説明したものは、これら3種の第1粘着剤組成物以外の全般的な第1粘着剤組成物(本実施形態においては、「第1粘着剤組成物(I-1)~(I-3)以外の第1粘着剤組成物」と称する)でも、同様に用いることができる。 {First pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3)}
So far, the first pressure-sensitive adhesive composition (I-1), the first pressure-sensitive adhesive composition (I-2), and the first pressure-sensitive adhesive composition (I-3) have been mainly described. The first pressure-sensitive adhesive composition other than these three types of the first pressure-sensitive adhesive compositions (in this embodiment, “first pressure-sensitive adhesive compositions (I-1) to (I- It is also possible to use the same in the first pressure-sensitive adhesive composition other than 3).
非エネルギー線硬化性の第1粘着剤組成物としては、例えば、アクリル系樹脂((メタ)アクリロイル基を有する樹脂)、ウレタン系樹脂(ウレタン結合を有する樹脂)、ゴム系樹脂(ゴム構造を有する樹脂)、シリコーン系樹脂(シロキサン結合を有する樹脂)、エポキシ系樹脂(エポキシ基を有する樹脂)、ポリビニルエーテル、又はポリカーボネート等の粘着性樹脂を含有するものが挙げられ、アクリル系樹脂を含有するものが好ましい。 As the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable first pressure-sensitive adhesive composition, the first non-energy ray-curable first composition is used. An adhesive composition is also mentioned.
Examples of the non-energy ray curable first pressure-sensitive adhesive composition include acrylic resins (resins having a (meth) acryloyl group), urethane resins (resins having a urethane bond), and rubber resins (having a rubber structure). Resins), silicone resins (resins having a siloxane bond), epoxy resins (resins having an epoxy group), polyvinyl ethers, or those containing adhesive resins such as polycarbonates, and those containing acrylic resins Is preferred.
第1粘着剤組成物(I-1)~(I-3)等の前記第1粘着剤組成物は、前記粘着剤と、必要に応じて前記粘着剤以外の成分等の、第1粘着剤組成物を構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。 <The manufacturing method of a 1st adhesive composition>
The first pressure-sensitive adhesive composition such as the first pressure-sensitive adhesive compositions (I-1) to (I-3) includes the first pressure-sensitive adhesive, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive as necessary. It is obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
前記第1中間層は、シート状又はフィルム状であり、その構成材料は目的に応じて適宜選択すればよく、特に限定されない。
例えば、半導体表面を覆う第1保護膜に、半導体表面に存在するバンプの形状が反映されることによって、第1保護膜が変形してしまうことの抑制を目的とする場合、前記第1中間層の好ましい構成材料としては、第1中間層の貼付性がより向上する点から、ウレタン(メタ)アクリレート等が挙げられる。 [First intermediate layer]
The first intermediate layer is in the form of a sheet or film, and the constituent material may be appropriately selected according to the purpose, and is not particularly limited.
For example, when the first protective film covering the semiconductor surface reflects the shape of the bumps existing on the semiconductor surface and is intended to prevent the first protective film from being deformed, the first intermediate layer Examples of preferable constituent materials include urethane (meth) acrylate and the like from the viewpoint that the adhesiveness of the first intermediate layer is further improved.
ここで、「第1中間層の厚さ」とは、第1中間層全体の厚さを意味し、例えば、複数層からなる第1中間層の厚さとは、第1中間層を構成するすべての層の合計の厚さを意味する。 The thickness of the first intermediate layer can be adjusted as appropriate according to the height of the bump on the surface of the semiconductor to be protected. However, the thickness of the first intermediate layer is 50 to 600 μm because the influence of the relatively high bump can be easily absorbed. It is preferably 70 to 500 μm, more preferably 80 to 400 μm.
Here, the “thickness of the first intermediate layer” means the thickness of the entire first intermediate layer. For example, the thickness of the first intermediate layer composed of a plurality of layers means all of the first intermediate layer. Means the total thickness of the layers.
第1中間層は、その構成材料を含有する第1中間層形成用組成物を用いて形成できる。
例えば、第1中間層の形成対象面に第1中間層形成用組成物を塗工し、必要に応じて乾燥させたり、エネルギー線の照射によって硬化させることで、目的とする部位に第1中間層を形成できる。第1中間層のより具体的な形成方法は、他の層の形成方法とともに、後ほど詳細に説明する。第1中間層形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、第1中間層の前記成分同士の含有量の比率と同じとなる。ここで、「常温」とは、先に説明したとおりである。 {{First intermediate layer forming composition}}
A 1st intermediate | middle layer can be formed using the composition for 1st intermediate | middle layer formation containing the constituent material.
For example, the first intermediate layer-forming composition is applied to the surface of the first intermediate layer and dried as necessary, or cured by irradiation with energy rays, so that the first intermediate layer is formed on the target site. Layers can be formed. A more specific method for forming the first intermediate layer will be described in detail later along with methods for forming other layers. The ratio of the content of components that do not vaporize at room temperature in the first intermediate layer forming composition is usually the same as the content ratio of the components of the first intermediate layer. Here, “normal temperature” is as described above.
第1中間層形成用組成物は、エネルギー線硬化性を有する場合、乾燥後に、さらにエネルギー線の照射により硬化させることが好ましい。 The drying conditions for the first intermediate layer forming composition are not particularly limited, but when the first intermediate layer forming composition contains a solvent to be described later, it is preferably heat-dried. Drying is preferably performed at 70 to 130 ° C. for 10 seconds to 5 minutes.
When the composition for forming the first intermediate layer has energy ray curability, it is preferably cured by irradiation with energy rays after drying.
第1中間層形成用組成物(II-1)は、上述の様に、ウレタン(メタ)アクリレートを含有する。 {First intermediate layer forming composition (II-1)}
As described above, the first intermediate layer forming composition (II-1) contains urethane (meth) acrylate.
ウレタン(メタ)アクリレートは、1分子中に少なくとも(メタ)アクリロイル基及びウレタン結合を有する化合物であり、エネルギー線重合性を有する。
ウレタン(メタ)アクリレートは、単官能のもの(1分子中に(メタ)アクリロイル基を1個のみ有するもの)であってもよいし、二官能以上のもの(1分子中に(メタ)アクリロイル基を2個以上有するもの)、即ち多官能のものであってもよいが、少なくとも単官能のものを用いることが好ましい。 (Urethane (meth) acrylate)
Urethane (meth) acrylate is a compound having at least a (meth) acryloyl group and a urethane bond in one molecule, and has energy ray polymerizability.
The urethane (meth) acrylate may be monofunctional (having only one (meth) acryloyl group in one molecule) or bifunctional or more ((meth) acryloyl group in one molecule). Having two or more), i.e., polyfunctional, it is preferable to use at least monofunctional.
前記ポリオール化合物は、1分子中に水酸基を2個以上有する化合物であれば、特に限定されない。
前記ポリオール化合物は、1種を単独で用いてもよいし、2種以上を併用してもよい。前記ポリオール化合物として2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 (A) Polyol compound The polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.
The said polyol compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as said polyol compound, those combinations and ratios can be selected arbitrarily.
前記ポリオール化合物は、2官能のジオール、3官能のトリオール、4官能以上のポリオール等のいずれであってもよいが、入手が容易であり、汎用性及び反応性等に優れる点では、ジオールが好ましい。 Examples of the polyol compound include alkylene diol, polyether type polyol, polyester type polyol, and polycarbonate type polyol.
The polyol compound may be any of a bifunctional diol, a trifunctional triol, a tetrafunctional or higher polyol, etc., but a diol is preferable in terms of easy availability and excellent versatility and reactivity. .
前記ポリエーテル型ポリオールは、特に限定されないが、ポリエーテル型ジオールであることが好ましく、前記ポリエーテル型ジオールとしては、例えば、下記一般式(1)で表される化合物が挙げられる。 -Polyether type polyol The polyether type polyol is not particularly limited, but is preferably a polyether type diol, and examples of the polyether type diol include compounds represented by the following general formula (1). It is done.
(但し、上記(1)式中、nは2以上の整数であり;Rは2価の炭化水素基であり、複数個のRは互いに同一であっても異なっていてもよい。)
(However, in said (1) Formula, n is an integer greater than or equal to 2; R is a bivalent hydrocarbon group, and several R may mutually be same or different.)
前記ポリエステル型ポリオールは、特に限定されないが、例えば、多塩基酸又はその誘導体を用いて、エステル化反応を行うことで得られたもの等が挙げられる。なお、本実施形態において「誘導体」とは、特に断りのない限り、元の化合物の1個以上の基がそれ以外の基(置換基)で置換されてなるものを意味する。ここで、「基」とは、複数個の原子が結合してなる原子団だけでなく、1個の原子も包含するものとする。 -Polyester type polyol Although the said polyester type polyol is not specifically limited, For example, what was obtained by performing esterification reaction using a polybasic acid or its derivative (s), etc. are mentioned. In the present embodiment, the “derivative” means one obtained by substituting one or more groups of the original compound with other groups (substituents) unless otherwise specified. Here, the “group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.
前記多塩基酸としては、例えば、飽和脂肪族多塩基酸、不飽和脂肪族多塩基酸、芳香族多塩基酸等が挙げられ、これらのいずれかに該当するダイマー酸を用いてもよい。 As said polybasic acid and its derivative (s), the polybasic acid normally used as a manufacturing raw material of polyester and its derivative (s) are mentioned.
Examples of the polybasic acid include saturated aliphatic polybasic acids, unsaturated aliphatic polybasic acids, aromatic polybasic acids, and the like, and dimer acids corresponding to any of these may be used.
前記不飽和脂肪族多塩基酸としては、例えば、マレイン酸、フマル酸等の不飽和脂肪族二塩基酸等が挙げられる。
前記芳香族多塩基酸としては、例えば、フタル酸、イソフタル酸、テレフタル酸、2,6-ナフタレンジカルボン酸等の芳香族二塩基酸;トリメリット酸等の芳香族三塩基酸;ピロメリット酸等の芳香族四塩基酸等が挙げられる。 Examples of the saturated aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and saturated aliphatic dibasic acids such as sebacic acid. It is done.
Examples of the unsaturated aliphatic polybasic acid include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.
Examples of the aromatic polybasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid; aromatic tribasic acids such as trimellitic acid; pyromellitic acid and the like And aromatic tetrabasic acids.
前記触媒としては、例えば、ジブチルスズオキサイド、オクチル酸第一スズ等のスズ化合物;テトラブチルチタネート、テトラプロピルチタネート等のアルコキシチタン等が挙げられる。 In the esterification reaction for obtaining the polyester type polyol, a known catalyst may be used as necessary.
Examples of the catalyst include tin compounds such as dibutyltin oxide and stannous octylate; alkoxy titanium such as tetrabutyl titanate and tetrapropyl titanate.
ポリカーボネート型ポリオールは、特に限定されないが、例えば、上記(1)式で表される化合物と同様のグリコールと、アルキレンカーボネートと、を反応させて得られたもの等が挙げられる。
ここで、グリコール及びアルキレンカーボネートは、いずれも1種を単独で用いてもよいし、2種以上を併用してもよい。グリコール及びアルキレンカーボネートとして2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 Polycarbonate-type polyol The polycarbonate-type polyol is not particularly limited, and examples thereof include those obtained by reacting the same glycol as the compound represented by the above formula (1) with an alkylene carbonate.
Here, each of glycol and alkylene carbonate may be used alone or in combination of two or more. When using 2 or more types together as glycol and alkylene carbonate, those combinations and ratios can be arbitrarily selected.
ポリオール化合物の水酸基価から算出した前記数平均分子量とは、下記式から算出された値である。
[ポリオール化合物の数平均分子量]=[ポリオール化合物の官能基数]×56.11×1000/[ポリオール化合物の水酸基価(単位:mgKOH/g)] The number average molecular weight calculated from the hydroxyl value of the polyol compound is preferably 1000 to 10,000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000. When the number average molecular weight is 1000 or more, excessive generation of urethane bonds is suppressed, and control of the viscoelastic characteristics of the first intermediate layer becomes easier. Moreover, the excessive softening of a 1st intermediate | middle layer is suppressed because the said number average molecular weight is 10,000 or less.
The number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.
[Number average molecular weight of polyol compound] = [Number of functional groups of polyol compound] × 56.11 × 1000 / [Hydroxyl value of polyol compound (unit: mgKOH / g)]
ポリオール化合物と反応させる前記多価イソシアネート化合物は、イソシアネート基を2個以上有するものであれば、特に限定されない。
多価イソシアネート化合物は、1種を単独で用いてもよいし、2種以上を併用してもよい。多価イソシアネート化合物として2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 (I) Polyvalent isocyanate compound The polyvalent isocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.
A polyvalent isocyanate compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as a polyvalent isocyanate compound, those combinations and ratios can be selected arbitrarily.
これらの中でも、多価イソシアネート化合物は、取り扱い性の点から、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート又はキシリレンジイソシアネートであることが好ましい。 Examples of the polyvalent isocyanate compound include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2. Cycloaliphatic diisocyanates such as 4,4′-diisocyanate, ω, ω′-diisocyanate dimethylcyclohexane, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1, And aromatic diisocyanates such as 5-diisocyanate.
Among these, the polyvalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylylene diisocyanate from the viewpoint of handleability.
前記末端イソシアネートウレタンプレポリマーと反応させる、前記(メタ)アクリル系化合物は、1分子中に少なくとも水酸基及び(メタ)アクリロイル基を有する化合物であれば、特に限定されない。
前記(メタ)アクリル系化合物は、1種を単独で用いてもよいし、2種以上を併用してもよい。前記(メタ)アクリル系化合物として2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 (U) (Meth) acrylic compound The (meth) acrylic compound to be reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in one molecule. .
The said (meth) acrylic-type compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as said (meth) acrylic-type compound, those combinations and ratios can be selected arbitrarily.
これらの中でも、前記(メタ)アクリル系化合物は、水酸基含有(メタ)アクリル酸エステルであることが好ましく、水酸基含有(メタ)アクリル酸アルキルエステルであることがより好ましく、(メタ)アクリル酸2-ヒドロキシエチルであることが特に好ましい。 Examples of the (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyl-3-phenyloxypropyl, hydroxyl group-containing (meth) acrylate such as pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; N-methylol (meth) acrylamid Hydroxyl group-containing (meth) acrylamide and the like; vinyl alcohol, vinyl phenol or bisphenol A diglycidyl ether (meth) reaction products obtained by reacting acrylic acid.
Among these, the (meth) acrylic compound is preferably a hydroxyl group-containing (meth) acrylic ester, more preferably a hydroxyl group-containing (meth) acrylic acid alkyl ester, and (meth) acrylic acid 2- Particularly preferred is hydroxyethyl.
例えば、前記ウレタン(メタ)アクリレートの重量平均分子量は、1000~100000であることが好ましく、3000~80000であることがより好ましく、5000~65000であることが特に好ましい。前記重量平均分子量が1000以上であることで、ウレタン(メタ)アクリレートと後述する重合性モノマーとの重合物において、ウレタン(メタ)アクリレート由来の構造同士の分子間力に起因して、第1中間層の硬さの最適化が容易となる。
なお、本実施形態において、重量平均分子量とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値である。 The urethane (meth) acrylate may be an oligomer, a polymer, or a mixture of an oligomer and a polymer, but is preferably an oligomer.
For example, the urethane (meth) acrylate has a weight average molecular weight of preferably from 1,000 to 100,000, more preferably from 3000 to 80,000, and particularly preferably from 5,000 to 65,000. Due to the intermolecular force between the structures derived from urethane (meth) acrylate in the polymer of urethane (meth) acrylate and a polymerizable monomer described later, the weight average molecular weight is 1000 or more. Optimization of layer hardness is facilitated.
In the present embodiment, the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
第1中間層形成用組成物(II-1)は、製膜性をより向上させる点から、前記ウレタン(メタ)アクリレート以外に、重合性モノマーを含有していてもよい。
前記重合性モノマーは、エネルギー線重合性を有し、重量平均分子量が1000以上であるオリゴマー及びポリマーを除くものであって、1分子中に少なくとも1個の(メタ)アクリロイル基を有する化合物であることが好ましい。 (Polymerizable monomer)
The first intermediate layer forming composition (II-1) may contain a polymerizable monomer in addition to the urethane (meth) acrylate, from the viewpoint of further improving the film forming property.
The polymerizable monomer is a compound having energy ray polymerizability and excluding oligomers and polymers having a weight average molecular weight of 1000 or more and having at least one (meth) acryloyl group in one molecule. It is preferable.
「1置換アミノ基」及び「2置換アミノ基」における、水素原子が置換される水素原子以外の基(即ち、置換基)としては、例えば、アルキル基等が挙げられる。 Here, “amino group-containing (meth) acrylic acid ester” means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with an amino group (—NH 2 ). . Similarly, “monosubstituted amino group-containing (meth) acrylic acid ester” means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a monosubstituted amino group, “Disubstituted amino group-containing (meth) acrylic acid ester” means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a disubstituted amino group.
Examples of the group other than the hydrogen atom in which the hydrogen atom is substituted in the “monosubstituted amino group” and the “disubstituted amino group” (that is, a substituent) include an alkyl group.
前記複素環式基を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリロイルモルホリン等が挙げられる。 The heterocyclic group in the (meth) acrylic acid ester having a heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group.
Examples of the (meth) acrylic acid ester having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryloylmorpholine.
第1中間層形成用組成物(II-1)は、前記ウレタン(メタ)アクリレート及び重合性モノマー以外に、光重合開始剤を含有していてもよい。光重合開始剤を含有する第1中間層形成用組成物(II-1)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 (Photopolymerization initiator)
The first intermediate layer forming composition (II-1) may contain a photopolymerization initiator in addition to the urethane (meth) acrylate and the polymerizable monomer. The first intermediate layer-forming composition (II-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
第1中間層形成用組成物(II-1)は、本発明の効果を損なわない範囲内において、前記ウレタン(メタ)アクリレート以外の樹脂成分を含有していてもよい。
前記樹脂成分の種類と、その第1中間層形成用組成物(II-1)における含有量は、目的に応じて適宜選択すればよく、特に限定されない。 (Resin components other than urethane (meth) acrylate)
The first intermediate layer forming composition (II-1) may contain a resin component other than the urethane (meth) acrylate as long as the effects of the present invention are not impaired.
The kind of the resin component and the content in the first intermediate layer forming composition (II-1) may be appropriately selected according to the purpose, and are not particularly limited.
第1中間層形成用組成物(II-1)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、例えば、架橋剤、帯電防止剤、酸化防止剤、連鎖移動剤、軟化剤(可塑剤)、充填剤、防錆剤、着色剤(顔料、染料)等の公知の添加剤が挙げられる。
例えば、前記連鎖移動剤としては、1分子中に少なくとも1個のチオール基(メルカプト基)を有するチオール化合物が挙げられる。 (Other additives)
The first intermediate layer forming composition (II-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additives include known crosslinking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), and the like. An additive is mentioned.
For example, the chain transfer agent includes a thiol compound having at least one thiol group (mercapto group) in one molecule.
第1中間層形成用組成物(II-1)は、溶媒を含有していてもよい。第1中間層形成用組成物(II-1)は、溶媒を含有していることで、塗工対象面への塗工適性が向上する。 (solvent)
The first intermediate layer forming composition (II-1) may contain a solvent. Since the first intermediate layer forming composition (II-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
第1中間層形成用組成物(II-1)等の第1中間層形成用組成物は、これを構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。 {{Method for producing first intermediate layer forming composition}}
The first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) can be obtained by blending the components for constituting the first intermediate layer forming composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
本発明の熱硬化性樹脂フィルム1は、熱硬化性樹脂組成物からなり、上述したように、半導体ウエハ5の表面(回路面)5a、及び、この表面5a状に設けられた複数のバンプ51を保護するためのフィルムであり、熱硬化により第1保護膜1aを形成する。本発明の熱硬化性樹脂フィルム1を用いて第1保護膜1aを形成することで、半導体ウエハ5の表面(回路面)5aと、バンプ51の表面5a近傍の部位、すなわち基部とが、第1保護膜1aで十分に保護される。 <Thermosetting resin film>
The
またさらに、熱硬化性樹脂フィルム1は、線膨張係数が5~80(×10-6/℃)であり、且つ、第2保護膜形成フィルム2の線膨張係数との差が35(×10-6/℃)未満となるように構成することができる。 As described above, in the
Furthermore, the
従って、熱硬化性樹脂フィルム1の、示差走査熱量分析法によって測定される発熱開始温度、発熱ピーク温度及び線膨張係数は、熱硬化性樹脂組成物の含有成分の種類及び量のいずれか一方又は両方を調節することで調節できる。
熱硬化性樹脂組成物及びその製造方法については、追って詳しく説明する。 The
Therefore, the heat generation starting temperature, the heat generation peak temperature, and the linear expansion coefficient measured by the differential scanning calorimetry of the
The thermosetting resin composition and the manufacturing method thereof will be described in detail later.
熱硬化性樹脂フィルム1が複数層である場合には、熱硬化性樹脂フィルム1を構成する全ての層が、上述の発熱開始温度及び発熱ピーク温度の条件を満たせばよい。 The
When the
ここで、「熱硬化性樹脂フィルムの厚さ」とは、熱硬化性樹脂フィルム1全体の厚さを意味し、例えば、複数層からなる熱硬化性樹脂フィルム1の厚さとは、熱硬化性樹脂フィルム1を構成するすべての層の合計の厚さを意味する。 The thickness of the
Here, the “thickness of the thermosetting resin film” means the thickness of the entire
熱硬化性樹脂フィルム1は、その構成材料を含有する熱硬化性樹脂組成物、即ち、少なくとも熱硬化性成分を含む熱硬化性樹脂組成物を用いて形成できる。例えば、熱硬化性樹脂フィルム1の形成対象面に熱硬化性樹脂組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に熱硬化性樹脂フィルム1を形成できる。熱硬化性樹脂組成物中の、常温で気化しない成分同士の含有量の比率は、通常、熱硬化性樹脂フィルム1の前記成分同士の含有量の比率と同じとなる。ここで、「常温」とは、先に説明したとおりである。 [Thermosetting resin composition]
The
熱硬化性樹脂組成物としては、例えば、重合体成分(A)及び熱硬化性成分(B)を含有する熱硬化性樹脂組成物(III-1)等が挙げられる。 {Thermosetting resin composition (III-1)}
Examples of the thermosetting resin composition include a thermosetting resin composition (III-1) containing a polymer component (A) and a thermosetting component (B).
重合体成分(A)は、熱硬化性樹脂フィルム1に造膜性や可撓性等を付与するための重合体化合物である。
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1が含有する重合体成分(A)は、1種のみでもよいし、2種以上でもよい。熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1が含有する重合体成分(A)が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Polymer component (A))
The polymer component (A) is a polymer compound for imparting film forming property, flexibility, and the like to the
The polymer component (A) contained in the thermosetting resin composition (III-1) and the
アクリル系樹脂の重量平均分子量(Mw)は、10000~2000000であることが好ましく、100000~1500000であることがより好ましい。アクリル系樹脂の重量平均分子量が上記の下限値以上であることで、熱硬化性樹脂フィルム1の形状安定性(保管時の経時安定性)が向上する。また、アクリル系樹脂の重量平均分子量が上記の上限値以下であることで、被着体の凹凸面へ熱硬化性樹脂フィルム1が追従し易くなり、例えば、被着体と熱硬化性樹脂フィルム1との間でボイド等の発生がより抑制される効果が得られる。 As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the above lower limit, the shape stability (time stability during storage) of the
(メタ)アクリル酸イソボルニル、(メタ)アクリル酸ジシクロペンタニル等の(メタ)アクリル酸シクロアルキルエステル;
(メタ)アクリル酸ベンジル等の(メタ)アクリル酸アラルキルエステル;
(メタ)アクリル酸ジシクロペンテニルエステル等の(メタ)アクリル酸シクロアルケニルエステル;
(メタ)アクリル酸ジシクロペンテニルオキシエチルエステル等の(メタ)アクリル酸シクロアルケニルオキシアルキルエステル;
(メタ)アクリル酸イミド;
(メタ)アクリル酸グリシジル等のグリシジル基含有(メタ)アクリル酸エステル;
(メタ)アクリル酸ヒドロキシメチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシブチル、(メタ)アクリル酸4-ヒドロキシブチル等の水酸基含有(メタ)アクリル酸エステル;
(メタ)アクリル酸N-メチルアミノエチル等の置換アミノ基含有(メタ)アクリル酸エステル等が挙げられる。ここで、「置換アミノ基」とは、アミノ基の1個又は2個の水素原子が水素原子以外の基で置換されてなる基を意味する。 Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 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 ((meth) acrylic acid (Uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as heptadecyl acrylate and octadecyl (meth) acrylate (stearyl (meth) acrylate), is a chain structure having 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) Hydroxyl group-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylate. Here, the “substituted amino group” means a group formed by replacing one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.
熱硬化性成分(B)は、熱硬化性樹脂フィルム1を硬化させて、硬質の第1保護膜1aを形成するための成分である。
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1が含有する熱硬化性成分(B)は、1種のみでもよいし、2種以上でもよい。熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1が含有する熱硬化性成分(B)が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Thermosetting component (B))
The thermosetting component (B) is a component for curing the
The thermosetting component (B) contained in the thermosetting resin composition (III-1) and the
エポキシ系熱硬化性樹脂は、エポキシ樹脂(B1)及び熱硬化剤(B2)からなる。
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1が含有するエポキシ系熱硬化性樹脂は、1種のみでもよいし、2種以上でもよい。熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1が含有するエポキシ系熱硬化性樹脂が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (A) Epoxy thermosetting resin The epoxy thermosetting resin comprises an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the thermosetting resin composition (III-1) and the
エポキシ樹脂(B1)としては、公知のものが挙げられ、例えば、多官能系エポキシ樹脂、ビフェニル化合物、ビスフェノールAジグリシジルエーテル及びその水添物、オルソクレゾールノボラックエポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、及びフェニレン骨格型エポキシ樹脂等、2官能以上のエポキシ化合物が挙げられる。 ・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Examples thereof include bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.
また、不飽和炭化水素基を有するエポキシ樹脂としては、例えば、エポキシ樹脂を構成する芳香環等に、不飽和炭化水素基を有する基が直接結合した化合物等が挙げられる。
不飽和炭化水素基は、重合性を有する不飽和基であり、その具体的な例としては、エテニル基(ビニル基)、2-プロペニル基(アリル基)、(メタ)アクリロイル基、(メタ)アクリルアミド基等が挙げられ、アクリロイル基が好ましい。 Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin 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 to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.
エポキシ樹脂(B1)のエポキシ当量は、100~1000g/eqであることが好ましく、300~800g/eqであることがより好ましい。なお、エポキシ樹脂(B1)のエポキシ当量は、JIS K7236:2001に準拠した方法で測定することが可能である。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30000 in view of curability of the
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq. In addition, the epoxy equivalent of an epoxy resin (B1) can be measured by the method based on JISK7236: 2001.
熱硬化剤(B2)は、エポキシ樹脂(B1)に対する硬化剤として機能する。
熱硬化剤(B2)としては、例えば、1分子中にエポキシ基と反応し得る官能基を2個以上有する化合物が挙げられる。前記官能基としては、例えば、フェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシ基、酸基が無水物化された基等が挙げられ、フェノール性水酸基、アミノ基、又は酸基が無水物化された基であることが好ましく、フェノール性水酸基又はアミノ基であることがより好ましい。 ・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
As a thermosetting agent (B2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
熱硬化剤(B2)のうち、アミノ基を有するアミン系硬化剤としては、例えば、ジシアンジアミド(以下、「DICY」と略記することがある)等が挙げられる。 Among the thermosetting agents (B2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins. .
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
不飽和炭化水素基を有する熱硬化剤(B2)としては、例えば、フェノール樹脂の水酸基の一部が、不飽和炭化水素基を有する基で置換されてなる化合物、フェノール樹脂の芳香環に、不飽和炭化水素基を有する基が直接結合してなる化合物等が挙げられる。
熱硬化剤(B2)における前記不飽和炭化水素基は、上述の不飽和炭化水素基を有するエポキシ樹脂における不飽和炭化水素基と同様のものである。 The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.
熱硬化剤(B2)のうち、例えば、ビフェノール、ジシアンジアミド等の非樹脂成分の分子量は、特に限定されないが、例えば、60~500であることが好ましい。 Of the thermosetting agent (B2), for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000. The number average molecular weight can also be measured by a conventionally known gel permeation chromatography (GPC) method (styrene standard).
Among the thermosetting agents (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1は、硬化促進剤(C)を含有していてもよい。硬化促進剤(C)は、熱硬化性樹脂組成物(III-1)の硬化速度を調整するための成分である。
好ましい硬化促進剤(C)としては、例えば、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の第3級アミン;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等のイミダゾール類(1個以上の水素原子が水素原子以外の基で置換されたイミダゾール);トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等の有機ホスフィン類(1個以上の水素原子が有機基で置換されたホスフィン);テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート等のテトラフェニルボロン塩等が挙げられる。 (Curing accelerator (C))
The thermosetting resin composition (III-1) and the
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms) An imidazole substituted with a group of; an organic phosphine such as tributylphosphine, diphenylphosphine, triphenylphosphine (a phosphine having one or more hydrogen atoms substituted with an organic group); tetraphenylphosphonium tetraphenylborate Tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1は、充填材(D)を含有していてもよい。熱硬化性樹脂フィルム1が充填材(D)を含有することにより、熱硬化性樹脂フィルム1を硬化して得られた第1保護膜1aは、熱膨張係数を上記範囲に調整することが容易となり、この熱膨張係数を第1保護膜1aの形成対象物に対して最適化することで、熱硬化性樹脂フィルムを用いて得られたパッケージの信頼性がより向上する。また、熱硬化性樹脂フィルム1が充填材(D)を含有することにより、第1保護膜1aの吸湿率を低減したり、放熱性を向上させたりすることもできる。 (Filler (D))
The thermosetting resin composition (III-1) and the
好ましい無機充填材としては、例えば、シリカ、アルミナ、タルク、炭酸カルシウム、チタンホワイト、ベンガラ、炭化ケイ素、窒化ホウ素等の粉末;これら無機充填材を球形化したビーズ;これら無機充填材の表面改質品;これら無機充填材の単結晶繊維;ガラス繊維等が挙げられる。
これらの中でも、無機充填材は、シリカ又はアルミナであることが好ましい。 The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1は、カップリング剤(E)を含有していてもよい。カップリング剤(E)として、無機化合物又は有機化合物と反応可能な官能基を有するものを用いることにより、熱硬化性樹脂フィルム1の被着体に対する接着性及び密着性を向上させることができる。また、カップリング剤(E)を用いることで、熱硬化性樹脂フィルム1を硬化して得られた第1保護膜1aは、耐熱性を損なうことなく、耐水性が向上する。 (Coupling agent (E))
The thermosetting resin composition (III-1) and the
好ましい前記シランカップリング剤としては、例えば、3-グリシジルオキシプロピルトリメトキシシラン、3-グリシジルオキシプロピルメチルジエトキシシラン、3-グリシジルオキシプロピルトリエトキシシラン、3-グリシジルオキシメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-(2-アミノエチルアミノ)プロピルトリメトキシシラン、3-(2-アミノエチルアミノ)プロピルメチルジエトキシシラン、3-(フェニルアミノ)プロピルトリメトキシシラン、3-アニリノプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、ビス(3-トリエトキシシリルプロピル)テトラスルファン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、及びイミダゾールシラン等が挙げられる。 The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred.
Preferred examples of the 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-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. Can be mentioned.
重合体成分(A)として、上述のアクリル系樹脂等の、他の化合物と結合可能なビニル基、(メタ)アクリロイル基、アミノ基、水酸基、カルボキシ基、イソシアネート基等の官能基を有するものを用いる場合、熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1は、前記官能基を他の化合物と結合させて架橋するための架橋剤(F)を含有していてもよい。架橋剤(F)を用いて架橋することにより、熱硬化性樹脂フィルム1の初期接着力及び凝集力を調節できる。 (Crosslinking agent (F))
As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin. When used, the thermosetting resin composition (III-1) and the
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1は、本発明の効果を損なわない範囲内において、汎用添加剤(I)を含有していてもよい。
汎用添加剤(I)は、公知のものでよく、目的に応じて任意に選択でき、特に限定されないが、好ましいものとしては、例えば、可塑剤、帯電防止剤、酸化防止剤、着色剤(染料、顔料)、ゲッタリング剤等が挙げられる。 (General-purpose additive (I))
The thermosetting resin composition (III-1) and the
The general-purpose additive (I) may be a known one, and can be arbitrarily selected according to the purpose. The general-purpose additive (I) is not particularly limited, but preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye Pigments), gettering agents and the like.
熱硬化性樹脂組成物(III-1)及び熱硬化性樹脂フィルム1の汎用添加剤(I)の含有量は、特に限定されず、目的に応じて適宜選択すればよい。 The general-purpose additive (I) contained in the thermosetting resin composition (III-1) and the
The contents of the general-purpose additive (I) in the thermosetting resin composition (III-1) and the
熱硬化性樹脂組成物(III-1)は、さらに溶媒を含有することが好ましい。溶媒を含有する熱硬化性樹脂組成物(III-1)は、取り扱い性が良好となる。
前記溶媒は特に限定されないが、好ましいものとしては、例えば、トルエン、キシレン等の炭化水素;メタノール、エタノール、2-プロパノール、イソブチルアルコール(2-メチルプロパン-1-オール)、1-ブタノール等のアルコール;酢酸エチル等のエステル;アセトン、メチルエチルケトン等のケトン;テトラヒドロフラン等のエーテル;ジメチルホルムアミド、N-メチルピロリドン等のアミド(アミド結合を有する化合物)等が挙げられる。
熱硬化性樹脂組成物(III-1)が含有する溶媒は、1種のみでもよいし、2種以上でもよい。熱硬化性樹脂組成物(III-1)が含有する溶媒が2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (solvent)
The thermosetting resin composition (III-1) preferably further contains a solvent. The thermosetting resin composition (III-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-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 thermosetting resin composition (III-1) may be only one type or two or more types. When the thermosetting resin composition (III-1) contains two or more solvents, the combination and ratio thereof can be arbitrarily selected.
熱硬化性樹脂組成物(III-1)等の熱硬化性樹脂組成物は、これを構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。 {{Method for producing thermosetting resin composition}}
A thermosetting resin composition such as the thermosetting resin composition (III-1) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
第1保護膜形成用シート1Aは、上述の各層を対応する位置関係となるように順次積層することで製造できる。各層の形成方法は、先に説明したとおりである。
例えば、第1支持シート11を製造するときに、第1基材上に第1粘着剤層又は第1中間層を積層する場合には、第1基材上に上述の第1粘着剤組成物又は第1中間層形成用組成物を塗工し、必要に応じて乾燥させるか、又はエネルギー線を照射することで、第1粘着剤層又は第1中間層を積層できる。 <The manufacturing method of the sheet | seat for 1st protective film formation>
The first protective
For example, when manufacturing the
また、例えば、第1基材上に第1中間層が積層され、前記第1中間層上に第1粘着剤層が積層されてなる第1支持シート11を製造する場合には、まず、第1基材上に第1中間層形成用組成物を塗工し、必要に応じて乾燥させるか、又はエネルギー線を照射することで、第1基材上に第1中間層を積層しておく。また、別途、剥離フィルム上に第1粘着剤組成物を塗工し、必要に応じて乾燥させることで、剥離フィルム上に第1粘着剤層を形成しておく。そして、この第1粘着剤層の露出面を、第1基材上に積層済みの第1中間層の露出面と貼り合わせて、第1粘着剤層を第1中間層上に積層することで、第1支持シート11が得られる。この場合、例えば、さらに別途、剥離フィルム上に熱硬化性樹脂組成物又はエネルギー線硬化性保護膜形成用組成物を塗工し、必要に応じて乾燥させることで、剥離フィルム上に熱硬化性成分を含む熱硬化性樹脂フィルム1を形成しておく。そして、この熱硬化性樹脂フィルム1の露出面を、第1中間層上に積層済みの第1粘着剤層の露出面と貼り合わせて、熱硬化性樹脂フィルム1を第1粘着剤層上に積層することで、第1保護膜形成用シート1Aが得られる。 For example, a first protective film-forming sheet (a
For example, when manufacturing the
いずれの方法においても、剥離フィルムは目的とする積層構造を形成後の任意のタイミングで取り除けばよい。 In addition, when laminating | stacking a 1st adhesive layer or a 1st intermediate | middle layer on a 1st base material, as above-mentioned, a 1st adhesive composition or a composition for 1st intermediate | middle layer formation on a 1st base material Instead of the method of applying the product, the first pressure-sensitive adhesive composition or the first intermediate layer-forming composition is applied on the release film, and is dried or irradiated with energy rays as necessary. The first pressure-sensitive adhesive layer or the first intermediate layer is formed on the release film, and the exposed surface of these layers is bonded to one surface of the first base material, whereby the first pressure-sensitive adhesive layer or the first intermediate layer is bonded. An intermediate layer may be laminated on the substrate.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.
本発明においては、上記の第1保護膜形成用シート1Aに加え、図5に示すように、さらに、第2保護膜形成フィルム2が、第2支持シート21の一方の表面21a上に備えられる第2保護膜形成用シート2Aとして、フィルムキット10(図1A等を参照)に含まれる構成を採用することができる。 <Second protective film forming film and second protective film forming sheet>
In the present invention, in addition to the first protective
このような着色剤としては、有機又は無機の顔料及び染料を用いることができる。
染料としては、例えば、酸性染料、反応染料、直接染料、分散染料、カチオン染料等の、何れの染料であっても用いることが可能である。
また、顔料としては、特に制限されず、公知の顔料から適宜選択して用いることができる。
これらの中でも、電磁波や赤外線の遮蔽性が良好で、且つ、レーザーマーキング法による識別性をより向上できる観点から、黒色顔料を用いることが好ましい。
黒色顔料としては、例えば、カーボンブラック、酸化鉄、二酸化マンガン、アニリンブラック、活性炭等が挙げられるが、半導体チップの信頼性が高められる観点から、カーボンブラックが好ましい。
なお、これらの着色剤は、単独又は2種以上を組み合わせて用いてもよい。 Moreover, as the 2nd protective
As such a colorant, organic or inorganic pigments and dyes can be used.
As the dye, for example, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used.
Moreover, it does not restrict | limit especially as a pigment, It can select from a well-known pigment suitably and can be used.
Among these, it is preferable to use a black pigment from the viewpoints of good shielding properties against electromagnetic waves and infrared rays and further improving the discriminability by the laser marking method.
Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like. From the viewpoint of improving the reliability of the semiconductor chip, carbon black is preferable.
In addition, you may use these colorants individually or in combination of 2 or more types.
以上説明したように、本発明に係る熱硬化性樹脂フィルムと第2保護膜形成フィルムのキット、熱硬化性樹脂フィルム、この熱硬化性樹脂フィルムを備えた第1保護膜形成用シートによれば、半導体ウエハの表面に貼付する熱硬化性樹脂フィルムと、裏面に貼付する第2保護膜形成フィルムとの間の、発熱開始温度及び発熱ピーク温度の関係を最適化することにより、熱硬化性樹脂フィルムが加熱硬化する際の収縮等によって半導体ウエハに付与される応力が、第2保護膜形成フィルムが加熱硬化する際の応力によって矯正される。これにより、半導体ウエハに反りが発生するのを抑制することができ、信頼性に優れた半導体パッケージを製造することが可能となる。 << Action and effect >>
As explained above, according to the kit of the thermosetting resin film and the second protective film forming film, the thermosetting resin film, and the first protective film forming sheet provided with the thermosetting resin film according to the present invention. The thermosetting resin is optimized by optimizing the relationship between the heat generation start temperature and the heat generation peak temperature between the thermosetting resin film attached to the surface of the semiconductor wafer and the second protective film forming film attached to the back surface. The stress applied to the semiconductor wafer due to shrinkage or the like when the film is heat-cured is corrected by the stress when the second protective film forming film is heat-cured. Thereby, it is possible to suppress the warpage of the semiconductor wafer, and it is possible to manufacture a highly reliable semiconductor package.
即ち、本発明に係る熱硬化性樹脂フィルムと第2保護膜形成フィルムのキットは、熱硬化性樹脂フィルム1の示差走査熱量分析(DSC)法によって測定される発熱開始温度が、示差走査熱量分析法によって測定される第2保護膜形成フィルム2の示差走査熱量分析法によって測定される発熱開始温度以上であり、さらに、示差走査熱量分析法によって測定される熱硬化性樹脂フィルム1及び第2保護膜形成フィルム2の示差走査熱量分析法によって測定される発熱ピーク温度が、それぞれ、185~200℃であり、熱硬化性樹脂フィルム1と第2保護膜形成フィルム2との発熱ピーク温度の差が0~10℃の範囲である構成とすることができる。
また、本発明に係る熱硬化性樹脂フィルム1と第2保護膜形成フィルム2のキットにおいては、熱硬化性樹脂フィルム1の線膨張係数が47~80(×10-6/℃)の範囲であり、且つ、第2保護膜形成フィルム2の線膨張係数との差が3~30(×10-6/℃)の範囲である構成を採用することができる。 In addition, in the kit of the thermosetting resin film and the second protective film forming film according to the present invention, for example, the following configuration can be adopted.
That is, in the kit of the thermosetting resin film and the second protective film forming film according to the present invention, the heat generation starting temperature of the
In the kit of the
・重合体成分
重合体成分(A)-1:アクリル酸ブチル(以下、「BA」と略記する)(55質量部)、アクリル酸メチル(以下、「MA」と略記する)(10質量部)、メタクリル酸グリシジル(以下、「GMA」と略記する)(20質量部)及びアクリル酸-2-ヒドロキシエチル(以下、「HEA」と略記する)(15質量部)を共重合してなるアクリル系樹脂(重量平均分子量800000、ガラス転移温度-28℃)。各成分の配合比を下記表1に示す。
・エポキシ樹脂
エポキシ樹脂(B1)-1:液状ビスフェノールF型エポキシ樹脂(三菱化学社製「YL983U」)
エポキシ樹脂(B1)-2:多官能芳香族型エポキシ樹脂(日本化薬社製「EPPN-502H」)
エポキシ樹脂(B1)-3:ジシクロペンタジエン型エポキシ樹脂(DIC社製「EPICLON HP-7200」)
・熱硬化剤
熱硬化剤(B2)-1:ノボラック型フェノール樹脂(昭和電工社製「BRG-556」)
・硬化促進剤
硬化促進剤(C)-1:2-フェニル-4,5-ジヒドロキシメチルイミダゾール(四国化成工業社製「キュアゾール2PHZ-PW」)
・充填材
充填材(D)-1:エポキシ基で修飾された球状シリカ(アドマテックス社製「アドマナノ YA050C-MKK」、平均粒径0.05μm)
・顔料
黒色顔料(L)-1:東洋インキ社製「マルチラックA-903 ブラック」 The component used for manufacture of a thermosetting resin composition is shown below.
Polymer component Polymer component (A) -1: butyl acrylate (hereinafter abbreviated as “BA”) (55 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) (10 parts by mass) Acrylic copolymer obtained by copolymerizing glycidyl methacrylate (hereinafter abbreviated as “GMA”) (20 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass). Resin (weight average molecular weight 800,000, glass transition temperature -28 ° C.). The compounding ratio of each component is shown in Table 1 below.
-Epoxy resin Epoxy resin (B1) -1: Liquid bisphenol F type epoxy resin ("YL983U" manufactured by Mitsubishi Chemical Corporation)
Epoxy resin (B1) -2: Multifunctional aromatic epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin (B1) -3: Dicyclopentadiene type epoxy resin (“EPICLON HP-7200” manufactured by DIC)
・ Thermosetting agent Thermosetting agent (B2) -1: Novolac-type phenolic resin (“BRG-556” manufactured by Showa Denko KK)
Curing accelerator Curing accelerator (C) -1: 2-Phenyl-4,5-dihydroxymethylimidazole (Curesol 2PHZ-PW, manufactured by Shikoku Chemicals)
Filler Filler (D) -1: Spherical silica modified with an epoxy group (“Admanano YA050C-MKK” manufactured by Admatechs, average particle size 0.05 μm)
・ Pigment Black Pigment (L) -1: “Multirack A-903 Black” manufactured by Toyo Ink Co., Ltd.
<第1保護膜形成用シート(熱硬化性樹脂フィルム)の製造>
(熱硬化性樹脂組成物の製造)
重合体成分(A)-1、エポキシ樹脂(B1)-1、エポキシ樹脂(B1)-2、エポキシ樹脂(B1)-3、熱硬化剤(B2)-1、硬化促進剤(C)-1、及び充填材(D)-1を、溶媒以外の全ての成分の総含有量に対する含有量の割合が下記表1に示す値(表1中において「含有量の割合」と記載している)となるようにメチルエチルケトンに溶解又は分散させて、23℃で撹拌することで、熱硬化性樹脂組成物として、固形分濃度が55質量%である熱硬化性樹脂組成物(III-1)を得た。なお、下記表1中の含有成分の欄の「-」との記載は、熱硬化性樹脂組成物がその成分を含有していないことを意味する。 [Example 1]
<Manufacture of first protective film forming sheet (thermosetting resin film)>
(Manufacture of thermosetting resin composition)
Polymer component (A) -1, epoxy resin (B1) -1, epoxy resin (B1) -2, epoxy resin (B1) -3, thermosetting agent (B2) -1, curing accelerator (C) -1 , And the filler (D) -1 is the value shown in the following Table 1 with respect to the total content of all components other than the solvent (described as “content ratio” in Table 1) By dissolving or dispersing in methyl ethyl ketone and stirring at 23 ° C., a thermosetting resin composition (III-1) having a solid content concentration of 55% by mass is obtained as a thermosetting resin composition. It was. In addition, the description of “-” in the column of the contained component in Table 1 below means that the thermosetting resin composition does not contain the component.
アクリル酸-2-エチルヘキシル(以下、「2EHA」と略記する)(80質量部)、HEA(20質量部)を共重合体の原料として、重合反応を行うことで、アクリル系重合体を得た。
このアクリル系重合体に、2-メタクリロイルオキシエチルイソシアネート(以下、「MOI」と略記する)(22質量部、HEAに対して約80モル%)を加え、空気気流中において50℃で48時間付加反応を行うことで、目的とする粘着性樹脂(I-2a)を得た。 (Production of adhesive resin (I-2a))
An acrylic polymer was obtained by conducting a polymerization reaction using 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (80 parts by mass) and HEA (20 parts by mass) as raw materials for the copolymer. .
To this acrylic polymer, 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as “MOI”) (22 parts by mass, about 80 mol% with respect to HEA) was added and added at 50 ° C. for 48 hours in an air stream. By carrying out the reaction, the intended adhesive resin (I-2a) was obtained.
上記で得られた粘着性樹脂(I-2a)(100質量部)に対して、イソシアネート系架橋剤として、トリメチロールプロパンのトリレンジイソシアネート三量体付加物(東ソー社製「コロネートL」)(0.5質量部)を加えて23℃で撹拌することで、第1粘着剤組成物として、固形分濃度が30質量%である第1粘着剤組成物(I-2)を得た。なお、この「第1粘着剤組成物の製造」における配合部数は、すべて固形分換算値である。 (Production of first pressure-sensitive adhesive composition)
For the adhesive resin (I-2a) (100 parts by mass) obtained above, a tolylene diisocyanate trimer adduct of trimethylolpropane (“Coronate L” manufactured by Tosoh Corporation) (as an isocyanate crosslinking agent) ( 0.5 parts by mass) was added and stirred at 23 ° C. to obtain a first pressure-sensitive adhesive composition (I-2) having a solid content concentration of 30% by mass as the first pressure-sensitive adhesive composition. In addition, all the compounding parts in this "manufacture of the 1st adhesive composition" are solid content conversion values.
ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の前記剥離処理面に、上記で得られた第1粘着剤組成物を塗工し、120℃で2分間加熱乾燥させることにより、厚さ60μmの第1粘着剤層を形成した。
次いで、この第1粘着剤層の露出面に、第1基材として、ポリオレフィンフィルム(厚さ25μm)、接着剤層(厚さ2.5μm)、ポリエチレンテレフタレートフィルム(厚さ50μm)、接着剤層(厚さ2.5μm)及びポリオレフィンフィルム(厚さ25μm)がこの順に積層されてなる、厚さ105μmの積層フィルムを貼り合せることにより、第1支持シートを得た。 (Manufacture of sheet for forming first protective film)
The first pressure-sensitive adhesive composition obtained above is applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. The first pressure-sensitive adhesive layer having a thickness of 60 μm was formed by heating and drying at 120 ° C. for 2 minutes.
Next, on the exposed surface of the first pressure-sensitive adhesive layer, as a first substrate, a polyolefin film (thickness 25 μm), an adhesive layer (thickness 2.5 μm), a polyethylene terephthalate film (
上記と同様の剥離フィルム(リンテック社製「SP-PET381031」)用い、この剥離処理面に、上記で得られた熱硬化性樹脂組成物と同様にして得られた、下記表2に示す組成の第2保護膜形成フィルム形成用組成物を塗工した後、100℃で2分間乾燥させることにより、厚さ40μmの熱硬化性樹脂フィルム(第2保護膜形成フィルム)を作製した。 (Production of second protective film-forming film)
Using a release film similar to the above ("SP-PET 381031" manufactured by Lintec Corporation), the release treatment surface of the composition shown in Table 2 below was obtained in the same manner as the thermosetting resin composition obtained above. After coating the composition for forming a second protective film-forming film, it was dried at 100 ° C. for 2 minutes to produce a thermosetting resin film (second protective film-forming film) having a thickness of 40 μm.
(各フィルムの発熱ピーク温度並びに線膨張係数の測定)
上記で得られた熱硬化性樹脂組成物を用いて、その塗工量が異なる点以外は、上述の第1保護膜形成用シートの製造時と同様の方法で、厚さ50μmの熱硬化性樹脂フィルムを作製し、これを10層で積層させて、厚さ500μmの熱硬化性樹脂フィルムを作製した。
また、同様に、上記で得られた第2保護膜形成フィルム形成用組成物を用いて、その塗工量が異なる点以外は、上述の第2保護膜形成フィルムの製造時と同様の方法で、厚さ50μmの熱硬化性樹脂からなる第2保護膜形成フィルムを作製し、これを10層で積層させて、厚さ500μmの第2保護膜形成フィルムを作製した。 <Evaluation of thermosetting resin film and second protective film forming film>
(Measurement of exothermic peak temperature and linear expansion coefficient of each film)
Using the thermosetting resin composition obtained above, the thermosetting property having a thickness of 50 μm is the same as that for manufacturing the first protective film-forming sheet described above except that the coating amount is different. A resin film was prepared and laminated with 10 layers to prepare a thermosetting resin film having a thickness of 500 μm.
Similarly, using the composition for forming a second protective film forming film obtained above, except that the coating amount is different, the same method as that for producing the second protective film forming film described above is used. A second protective film-forming film made of a thermosetting resin having a thickness of 50 μm was prepared, and this was laminated with 10 layers to prepare a second protective film-forming film having a thickness of 500 μm.
同様に、熱硬化性樹脂フィルムから評価用試料を作製し、JIS K 7197に準拠した条件で、従来公知の熱機械分析(TMA)装置を用いて熱膨張係数(CTE α1)を測定した。
これら各試験による測定結果を下記表3に示す。 Next, a sample for evaluation was produced from this thermosetting resin film, and the exothermic peak temperature was measured using a conventionally known differential scanning calorimetry (DSC) apparatus.
Similarly, a sample for evaluation was prepared from a thermosetting resin film, and the coefficient of thermal expansion (CTE α1) was measured using a conventionally known thermomechanical analysis (TMA) apparatus under conditions based on JIS K7197.
The measurement results from these tests are shown in Table 3 below.
(熱硬化性樹脂フィルムが硬化して第1保護膜を形成した後の反りの確認)
上記で得られた熱硬化性樹脂フィルム(熱硬化性樹脂フィルムと第2保護膜形成フィルムのキット)を用いて、半導体ウエハのバンプ形成面に第1保護膜を形成するとともに、裏面に第2保護膜を形成した。
即ち、まず、表面に複数のバンプを備える半導体ウエハの裏面側に第2保護膜形成フィルムを貼着するとともに、表面側に第1保護膜形成用シートを貼着し、第2保護膜形成フィルム、半導体ウエハ、第1保護膜形成用シート(熱硬化性樹脂フィルム)が順次積層された積層体を作製した。また、この際、第2保護膜形成フィルムとして、半導体ウエハの裏面に貼着される面とは反対側の面に、ダイシングテープが貼着されたものを使用した。 <Evaluation of semiconductor wafer after formation of protective film>
(Confirmation of warpage after the thermosetting resin film is cured to form the first protective film)
Using the thermosetting resin film obtained above (a kit of thermosetting resin film and second protective film forming film), the first protective film is formed on the bump forming surface of the semiconductor wafer, and the second is formed on the back surface. A protective film was formed.
That is, first, a second protective film forming film is attached to the back surface side of a semiconductor wafer having a plurality of bumps on the front surface, and a first protective film forming sheet is attached to the front surface side. Then, a laminated body in which a semiconductor wafer and a first protective film forming sheet (thermosetting resin film) were sequentially laminated was produced. At this time, as the second protective film forming film, a film in which a dicing tape was attached to the surface opposite to the surface attached to the back surface of the semiconductor wafer was used.
熱硬化性樹脂組成物組成を下記表1に示す通りとした点以外は、実施例1と同様に、第1保護膜形成用シート及び第2保護膜形成フィルムを含む実施例2,3のフィルムキットを製造し、上記同様に評価して、その結果を下記表3に示した。 [Examples 2 and 3]
The films of Examples 2 and 3, including the first protective film-forming sheet and the second protective film-forming film, as in Example 1, except that the thermosetting resin composition was as shown in Table 1 below. Kits were manufactured and evaluated in the same manner as described above, and the results are shown in Table 3 below.
[比較例1,2、参考例1,2]
熱硬化性樹脂組成物組成を表1に示す通りとした点以外は、実施例1と同様に、第1保護膜形成用シート及び第2保護膜形成フィルムを含む比較例1,2のフィルムキットを製造し、上記同様に評価して、その結果を下記表3に示した。
また、本実験においては、第2保護膜形成フィルムを半導体ウエハに貼着せず、熱硬化性樹脂フィルムのみを半導体ウエハに貼着して加熱硬化させ、第1保護膜を形成した参考例1の試料を作製するとともに、熱硬化性樹脂フィルムを用いた第1保護膜の形成を行わず、第2保護膜形成フィルムのみを半導体ウエハに貼着して加熱硬化させ、第2保護膜を形成した参考例2の試料を作製し、実施例と同様に評価して、その結果を下記表3に示した。 <Manufacture and Evaluation of Sheet for Forming First Protective Film>
[Comparative Examples 1 and 2, Reference Examples 1 and 2]
The film kits of Comparative Examples 1 and 2 including the first protective film-forming sheet and the second protective film-forming film, as in Example 1, except that the thermosetting resin composition composition is as shown in Table 1. Were manufactured and evaluated in the same manner as described above, and the results are shown in Table 3 below.
Further, in this experiment, the second protective film forming film was not attached to the semiconductor wafer, but only the thermosetting resin film was attached to the semiconductor wafer and cured by heating to form the first protective film. While producing the sample, without forming the first protective film using the thermosetting resin film, only the second protective film-forming film was attached to the semiconductor wafer and cured by heating to form the second protective film. Samples of Reference Example 2 were prepared and evaluated in the same manner as in the Examples, and the results are shown in Table 3 below.
また、比較例2の試料は、熱硬化性樹脂フィルムの発熱ピーク温度が本発明で規定する上限値を超えており、また、熱硬化性樹脂フィルムと第2保護膜形成フィルムとの間の発熱ピーク温度の差も上限値を超えている。このため、比較例2においては、半導体ウエハの端部がバンプ形成面側(第1保護膜形成面側)に向かうように反りが生じていた。 As shown in Table 3 below, in the sample of Comparative Example 1, the thermal expansion coefficient of the thermosetting resin film exceeds the upper limit defined in
In the sample of Comparative Example 2, the heat generation peak temperature of the thermosetting resin film exceeds the upper limit defined in the present invention, and heat generation between the thermosetting resin film and the second protective film forming film The difference in peak temperature also exceeds the upper limit. For this reason, in Comparative Example 2, the warp occurred so that the end portion of the semiconductor wafer was directed to the bump forming surface side (first protective film forming surface side).
また、第1保護膜の形成を行わず、第2保護膜形成フィルムのみを半導体ウエハに貼着して加熱させ、第2保護膜のみを形成した参考例2の試料は、半導体ウエハの端部が裏面側(第2保護膜形成フィルム側)に向かうように反りが生じていた。 As shown in Table 3 below, in the sample of Reference Example 1 in which only the first protective film was formed without attaching the second protective film forming film to the semiconductor wafer, the end of the semiconductor wafer was on the bump forming surface side. Warping occurred as it headed.
In addition, the sample of Reference Example 2 in which only the second protective film is formed by attaching only the second protective film-forming film to the semiconductor wafer and heating it without forming the first protective film is the edge of the semiconductor wafer. Warp occurred so as to face the back side (second protective film forming film side).
Claims (7)
- 半導体ウエハにおける複数のバンプを保護する第1保護膜を形成するための、熱硬化性樹脂フィルムと第2保護膜形成フィルムのキットであって、
前記熱硬化性樹脂フィルムと第2保護膜形成フィルムのキットは、前記半導体ウエハにおける複数のバンプを有する表面に貼付し、加熱硬化させることによって前記表面に第1保護膜を形成するための熱硬化性樹脂フィルム、及び、半導体ウエハの第2保護膜形成フィルムを含み、
前記熱硬化性樹脂フィルム及び前記第2保護膜形成フィルムは、それぞれ、少なくとも熱硬化性成分を含み、
前記熱硬化性樹脂フィルムは、示差走査熱量分析(DSC)法によって測定される発熱開始温度が、前記第2保護膜形成フィルムの示差走査熱量分析法によって測定される発熱開始温度以上であり、
さらに、前記熱硬化性樹脂フィルム及び前記第2保護膜形成フィルムの示差走査熱量分析法によって測定される発熱ピーク温度が、それぞれ100~200℃であり、前記熱硬化性樹脂フィルムと前記第2保護膜形成フィルムとの前記発熱ピーク温度の差が35℃未満である、半導体ウエハに貼付して用いられる、熱硬化性樹脂フィルムと第2保護膜形成フィルムのキット。 A kit of a thermosetting resin film and a second protective film forming film for forming a first protective film for protecting a plurality of bumps in a semiconductor wafer,
The kit of the thermosetting resin film and the second protective film forming film is applied to the surface of the semiconductor wafer having a plurality of bumps, and is heat-cured to form the first protective film on the surface by heat-curing. And a second protective film forming film of the semiconductor wafer,
The thermosetting resin film and the second protective film forming film each include at least a thermosetting component,
The thermosetting resin film has a heat generation start temperature measured by a differential scanning calorimetry (DSC) method equal to or higher than a heat generation start temperature measured by a differential scanning calorimetry method of the second protective film forming film,
Furthermore, the exothermic peak temperatures measured by differential scanning calorimetry of the thermosetting resin film and the second protective film forming film are 100 to 200 ° C., respectively, and the thermosetting resin film and the second protective film are A kit of a thermosetting resin film and a second protective film forming film, which is used by being attached to a semiconductor wafer, wherein the difference in the exothermic peak temperature from the film forming film is less than 35 ° C. - 前記熱硬化性樹脂フィルムの線膨張係数が5×10-6/℃~80×10-6/℃であり、且つ、前記第2保護膜形成フィルムの線膨張係数との差が35×10-6/℃未満である、請求項1に記載の熱硬化性樹脂フィルムと第2保護膜形成フィルムのキット。 The linear expansion coefficient of the thermosetting resin film is 5 × 10 −6 / ° C. to 80 × 10 −6 / ° C., and the difference from the linear expansion coefficient of the second protective film forming film is 35 × 10 − The kit of the thermosetting resin film and 2nd protective film formation film of Claim 1 which is less than 6 / degreeC.
- 前記熱硬化性樹脂フィルムが、第1支持シートの一方の表面上に備えられる第1保護膜形成用シートとして、前記熱硬化性樹脂フィルムと第2保護膜形成フィルムのキットに含まれるとともに、前記第2保護膜形成フィルムが、第2支持シートの一方の表面上に備えられる第2保護膜形成用シートとして、前記熱硬化性樹脂フィルムと第2保護膜形成フィルムのキットに含まれる、請求項1又は請求項2に記載の熱硬化性樹脂フィルムと第2保護膜形成フィルムのキット。 As the first protective film forming sheet provided on one surface of the first support sheet, the thermosetting resin film is included in the kit of the thermosetting resin film and the second protective film forming film, and The second protective film forming film is included in the kit of the thermosetting resin film and the second protective film forming film as a second protective film forming sheet provided on one surface of the second support sheet. The kit of the thermosetting resin film of Claim 1 or Claim 2, and a 2nd protective film formation film.
- 半導体ウエハにおける複数のバンプを有する表面に貼付し、加熱硬化させることによって前記表面に第1保護膜を形成するために、半導体ウエハの第2保護膜形成フィルムと組み合わせて使用される、熱硬化性樹脂フィルムであって、
前記熱硬化性樹脂フィルム及び前記第2保護膜形成フィルムは、それぞれ、少なくとも熱硬化性成分を含み、
前記熱硬化性樹脂フィルムは、示差走査熱量分析(DSC)法によって測定される発熱開始温度が、前記第2保護膜形成フィルムの示差走査熱量分析法によって測定される発熱開始温度以上であり、
さらに、前記熱硬化性樹脂フィルム及び前記第2保護膜形成フィルムの示差走査熱量分析法によって測定される発熱ピーク温度が、それぞれ100~200℃であり、前記熱硬化性樹脂フィルムと前記第2保護膜形成フィルムとの前記発熱ピーク温度の差が35℃未満である、半導体ウエハに貼付して用いられる、熱硬化性樹脂フィルム。 Thermosetting used in combination with a second protective film forming film of a semiconductor wafer in order to form a first protective film on the surface by sticking to a surface having a plurality of bumps in a semiconductor wafer and curing by heating. A resin film,
The thermosetting resin film and the second protective film forming film each include at least a thermosetting component,
The thermosetting resin film has a heat generation start temperature measured by a differential scanning calorimetry (DSC) method equal to or higher than a heat generation start temperature measured by a differential scanning calorimetry method of the second protective film forming film,
Furthermore, the exothermic peak temperatures measured by differential scanning calorimetry of the thermosetting resin film and the second protective film forming film are 100 to 200 ° C., respectively, and the thermosetting resin film and the second protective film are A thermosetting resin film, which is used by being attached to a semiconductor wafer, wherein the difference in the exothermic peak temperature from the film forming film is less than 35 ° C. - さらに、前記熱硬化性樹脂フィルムの線膨張係数が5×10-6/℃~80×10-6/℃であり、且つ、前記第2保護膜形成フィルムの線膨張係数との差が35×10-6/℃未満として用いられる、請求項4に記載の熱硬化性樹脂フィルム。 Further, the linear expansion coefficient of the thermosetting resin film is 5 × 10 −6 / ° C. to 80 × 10 −6 / ° C., and the difference from the linear expansion coefficient of the second protective film forming film is 35 ×. The thermosetting resin film according to claim 4, wherein the thermosetting resin film is used as less than 10 −6 / ° C.
- 請求項4又は請求項5に記載の熱硬化性樹脂フィルムを、第1支持シートの一方の表面上に備えた、第1保護膜形成用シート。 A sheet for forming a first protective film, comprising the thermosetting resin film according to claim 4 or 5 on one surface of the first support sheet.
- 半導体ウエハにおける回路及び複数のバンプを有する表面に、該複数のバンプを保護する第1保護膜を形成する、半導体ウエハ用第1保護膜の形成方法であって、
裏面側に第2保護膜形成フィルムが貼付された前記半導体ウエハの表面に、前記複数のバンプを覆うように熱硬化性樹脂フィルムを貼付することで、前記第2保護膜形成フィルム、前記半導体ウエハ及び前記熱硬化性樹脂フィルムが順次積層された積層体を形成する積層ステップと、
前記積層体を加熱することで、前記熱硬化性樹脂フィルムに前記複数のバンプを貫通させ、前記複数のバンプの各々の間を埋め込むように前記熱硬化性樹脂フィルムを加熱硬化させることで、前記半導体ウエハの表面に前記第1保護膜を形成する硬化ステップと、を含み、
前記熱硬化性樹脂フィルムは、示差走査熱量分析(DSC)法によって測定される発熱開始温度が、前記第2保護膜形成フィルムの示差走査熱量分析法によって測定される発熱開始温度以上であり、
さらに、前記熱硬化性樹脂フィルム及び前記第2保護膜形成フィルムの示差走査熱量分析法によって測定される発熱ピーク温度が、それぞれ100~200℃であり、前記熱硬化性樹脂フィルムと前記第2保護膜形成フィルムとの前記発熱ピーク温度の差が35℃未満の関係である、半導体ウエハ用第1保護膜の形成方法。 A method for forming a first protective film for a semiconductor wafer, comprising: forming a first protective film for protecting the plurality of bumps on a surface of the semiconductor wafer having a circuit and the plurality of bumps;
The second protective film forming film and the semiconductor wafer are attached to the surface of the semiconductor wafer having the second protective film forming film attached to the back side thereof, so as to cover the plurality of bumps. And a lamination step for forming a laminate in which the thermosetting resin films are sequentially laminated,
By heating the laminate, the thermosetting resin film is allowed to penetrate the plurality of bumps, and the thermosetting resin film is heat-cured so as to be embedded between the plurality of bumps. A curing step of forming the first protective film on the surface of the semiconductor wafer,
The thermosetting resin film has a heat generation start temperature measured by a differential scanning calorimetry (DSC) method equal to or higher than a heat generation start temperature measured by a differential scanning calorimetry method of the second protective film forming film,
Furthermore, the exothermic peak temperatures measured by differential scanning calorimetry of the thermosetting resin film and the second protective film forming film are 100 to 200 ° C., respectively, and the thermosetting resin film and the second protective film are A method for forming a first protective film for a semiconductor wafer, wherein the difference in exothermic peak temperature with the film-forming film is less than 35 ° C.
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JP2019006981A (en) * | 2017-06-26 | 2019-01-17 | 味の素株式会社 | Resin composition layer |
JP7210901B2 (en) | 2017-06-26 | 2023-01-24 | 味の素株式会社 | Resin composition layer |
JP2019172761A (en) * | 2018-03-27 | 2019-10-10 | 日本カーバイド工業株式会社 | Resin composition for infrared laser irradiation and resin film for infrared laser irradiation |
Also Published As
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PH12018500801B1 (en) | 2018-10-29 |
KR102541134B1 (en) | 2023-06-08 |
TW201728640A (en) | 2017-08-16 |
KR20180079307A (en) | 2018-07-10 |
CN108140622A (en) | 2018-06-08 |
JPWO2017078053A1 (en) | 2018-02-01 |
CN108140622B (en) | 2021-03-05 |
TWI638845B (en) | 2018-10-21 |
PH12018500801A1 (en) | 2018-10-29 |
SG11201803007TA (en) | 2018-05-30 |
JP6304852B2 (en) | 2018-04-04 |
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