TW202241700A - Adhesive sheet for jig fixation, composite sheet for protective film formation, and method for producing chip provided with protective film - Google Patents

Abstract

An adhesive sheet for jig fixation (1) to be used in a composite sheet for protective film formation equipped with a protective film-forming film, wherein the adhesive sheet for jig fixation is configured by laminating a first adhesive agent layer (161), a core material film (162), and a second adhesive agent layer (163), in that order, in the thickness direction thereof, and the adhesive sheet for jig fixation (1) has a ratio (Ah/Bh) of the breaking strength (Ah) determined from a tensile test of a test piece after heating for two hours at 130 DEG C and the 180 DEG adhesive peel strength (Bh) to SUS304 of a test piece after heating for two hours at 130 DEG C of 1.25 or more.

Description

Adhesive sheet for jig fixing, composite sheet for forming protective film, and wafer with protective film

The present invention relates to an adhesive sheet for fixing a jig, a composite sheet for forming a protective film having an adhesive layer for a jig formed using the adhesive sheet for fixing a jig, and a method for manufacturing a wafer with a protective film. This case claims priority based on Japanese Patent Application No. 2021-047594 filed in Japan on March 22, 2021, and the content of the application is incorporated herein.

In recent years, semiconductor devices have been manufactured using a packaging method called a so-called face-down method. In the face-down method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the inner surface on the side opposite to the circuit surface of the semiconductor wafer may be exposed.

On the inner surface of the bare semiconductor wafer, after the dicing step or packaging, in order to prevent cracks in the semiconductor wafer, sometimes a resin film containing an organic material is formed, and it is incorporated as a semiconductor wafer with a protective film device. A composite sheet for protective film formation combining a protective film forming film and a dicing tape is used for the production and processing of a semiconductor wafer with a protective film (for example, Patent Document 1).

For example, the composite sheet 101 for forming a protective film as shown in FIG. The jig adhesive layer 16 fixed to the fixing jig such as the ring frame. The release film 15 may be laminated on the protective film forming film 13 and the adhesive layer 16 for jigs. In addition, the jig adhesive layer 16 may have a multilayer structure in which the first adhesive layer 161 , the core material film 162 , and the second adhesive layer 163 are sequentially laminated in the thickness direction thereof. The core film 162 is often made of polyvinyl chloride (for example, Patent Document 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2016-15456.

[Problem to be Solved by the Invention]

When using a protective film forming composite sheet equipped with a protective film forming film to manufacture a wafer with a protective film, for example, first, as shown in FIGS. The adhesive layer 16 is attached to the jig 18 for fixing, and the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the inner surface 9b of the workpiece 9 such as a semiconductor wafer, thereby making the supporting sheet 10 There is a first laminated composite sheet 501 formed by laminating the protective film forming film 13 and the workpiece 9 sequentially in the thickness direction.

For example, if the protective film-forming film 13 is thermosetting, the peripheral edge of the first laminated composite sheet 501 is attached to the jig 18 for fixing through the adhesive layer 16 for the jig, and the first laminated composite sheet is composited. Sheet 501 is heated (FIG. 5C). In this way, the protective film 13' is formed by thermally curing the protective film forming film 13. As shown in FIG. The second laminated composite sheet 502 .

Then, the second laminated composite sheet 502 is cooled, and then, as shown in FIG. 5E , the workpiece 9 in the second laminated composite sheet 502 is divided on the support sheet 10, and the protective film 13' is cut. Through the above method, the third laminated composite sheet 503 in which the plurality of wafers 901 with protective films are fixed on the supporting sheet 10 is manufactured.

Then, as shown in FIG. 5F , pick-up is performed by tearing off the wafer 901 with a protective film in the third laminated composite sheet 503 from the supporting sheet 10 . After picking up the wafers 901 with the protective film for all the wafers 901 with the protective film of the target, the fourth laminated composite sheet 504 remaining after tearing off the wafers 901 with the protective film from the third laminated composite sheet 503 is as shown in FIG. 5G As shown, the state of being attached to the jig 18 for fixing is maintained by the adhesive layer 16 for the jig. As shown in FIG. 5H , by peeling the fourth laminated composite sheet 504 from the fixing jig 18 , the fixing jig 18 is returned to FIG. 5A and used again.

When the protective film forming film is thermally cured using a conventional protective film forming composite sheet provided with a thermosetting protective film forming film, the adhesive force between the jig adhesive layer 16 and the fixing jig 18 becomes stronger. , when the fourth laminated composite sheet 504 is peeled off from the jig 18 for fixing, since strong tension is applied, as shown in FIG. The adhesive agent layer 16 for jigs peeled to the side of the 4th laminated composite sheet 504 may break|break the adhesive agent layer 16 for jigs.

Even when the protective film forming film is not thermosetting, when the protective film wafer is manufactured, since the first laminated composite sheet 501 is stored for a long time or heat-treated, the adhesive layer 16 for the jig and the fixed The adhesive force between the jigs 18 becomes stronger, and when the fourth laminated composite sheet 504 is peeled off from the fixing jig 18, the adhesive layer 16 for the jig may break due to strong tension. If the jig adhesive layer 16 breaks, as shown in FIG. Layer 16 with adhesive. In order to reuse the fixing jig 18 , it is necessary to peel off the jig adhesive layer 16 remaining on the side of the fixing jig 18 , which becomes an unnecessary load.

The object of the present invention is to provide an adhesive sheet for fixing a jig, a composite sheet for forming a protective film having an adhesive layer for a jig formed using the adhesive sheet for fixing a jig, and a method for manufacturing a wafer with a protective film; The aforementioned adhesive sheet for jig fixing has a core material film, and the aforementioned adhesive sheet for jig fixing is used to form a composite sheet for forming a protective film having an adhesive layer for jig, and when used to manufacture a wafer with a protective film, the jig The adhesive layer can be easily peeled off from the fixing jig without breaking. [Means to solve the problem]

The present invention provides the following adhesive sheet for fixing a jig, a composite sheet for forming a protective film, and a method for manufacturing a wafer with a protective film.

[1] An adhesive sheet for fixing a jig, which is used for a protective film forming composite sheet provided with a protective film forming film; the first adhesive layer, the core material film, and the second adhesive layer are sequentially arranged in the thickness direction of these It is composed of laminated layers; the breaking strength (Ah) obtained by the tensile test of the test piece after the above-mentioned fixture fixing adhesive sheet is heated at 130°C for 2 hours is relative to the 180° of the test piece after heating at 130°C for 2 hours to SUS304 The ratio (Ah/Bh) of the pull-off adhesive force (Bh) is 1.25 or more. [2] The adhesive sheet for fixture fixing as described in [1], wherein the 180° tear-off adhesive force (Bh) is 2.0N/10mm to 12N/10mm. [3] The adhesive sheet for fixing a jig according to [1] or [2], wherein the breaking strength (Ah) is 6 N/10 mm or more. [4] The adhesive sheet for fixing a jig according to any one of [1] to [3], wherein the first adhesive layer and the second adhesive layer are composed of an adhesive for a jig containing an acrylic resin The weight average molecular weight of the aforesaid acrylic resin is more than 700,000. [5] The adhesive sheet for fixing a jig according to any one of [1] to [4], wherein the acrylic resin does not have a structural unit derived from (meth)acrylic acid.

[6] The adhesive sheet for fixing a jig as described in any one of [1] to [5], wherein the constituent material of the core film is linear low-density polyethylene, non-stretched polypropylene, or polyvinyl chloride . [7] The adhesive sheet for fixing a jig as described in any one of [1] to [6], wherein the above-mentioned adhesive sheet for fixing a jig is obtained by a tensile test on a test piece after heating at 130°C for 2 hours The elongation at break (Xh) is above 100%. [8] The adhesive sheet for fixing a jig as described in any one of [1] to [7], wherein the above-mentioned adhesive sheet for fixing a jig is obtained by a tensile test on a test piece after heating at 130°C for 2 hours The ratio (Xh/X0) of the elongation at break (Xh) to the elongation at break (X0) obtained by the tensile test of the test piece before heating is 0.10 to 1.50.

[9] A composite sheet for forming a protective film, comprising: a support sheet, a protective film forming film provided on one side of the support sheet, and a film provided on the one side of the support sheet or on The adhesive layer for jigs near the periphery of the first surface on the opposite side to the support sheet in the protective film forming film; the adhesive layer for jigs uses any one of [1] to [8]. The jig fixing described in item is formed by the adhesive sheet. [10] The composite sheet for forming a protective film according to [9], wherein the protective film forming film is thermosetting.

[11] A method of manufacturing a wafer with a protective film, wherein the aforementioned wafer with a protective film comprises: a wafer, and a protective film disposed on the inner surface of the aforementioned wafer; and, the manufacturing method of the aforementioned wafer with a protective film has the following steps: The above steps: attach the adhesive layer for the jig in the composite sheet for forming the protective film to the jig for fixing, and attach the composite sheet for forming the protective film as described in [9] or [10] on the inner surface of the workpiece. The protective film forming film in the sheet, whereby the step of making the first laminated composite sheet formed by laminating the protective film forming film and the aforementioned workpieces sequentially in the thickness direction on the aforementioned support sheet; The aforementioned workpiece is divided, and the aforementioned protective film forming film or the protective film obtained by hardening the aforementioned protective film forming film is cut to produce a plurality of wafers with protective film forming film or wafers with protective film are fixed The step of placing the third laminated composite sheet on the aforementioned support sheet; and, tearing the aforementioned wafer with protective film forming film or the aforementioned wafer with protective film in the aforementioned third laminated composite sheet from the aforementioned support sheet, thereby performing Pick up steps.

[12] A method of manufacturing a wafer with a protective film, wherein the aforementioned wafer with a protective film comprises: a wafer, and a protective film disposed on the inner surface of the aforementioned wafer; and, the manufacturing method of the aforementioned wafer with a protective film has the following steps: The above steps: attach the adhesive layer for the jig in the composite sheet for forming the protective film to the jig for fixing, and attach the protective layer of the composite sheet for forming the protective film as described in [10] on the inner surface of the workpiece. Film forming film, whereby the step of producing the first laminated composite sheet formed by laminating the protective film forming film and the aforementioned workpieces sequentially in the thickness direction on the aforementioned support sheet; at the peripheral portion of the first laminated composite sheet In the state attached to the aforementioned fixing jig, the aforementioned first laminated composite sheet is heated to harden the aforementioned protective film forming film to form the aforementioned protective film, thereby fabricating the aforementioned protective film and the aforementioned workpiece on the aforementioned supporting sheet. The step of laminating and forming the second laminated composite sheet in the thickness direction of these: by dividing the aforementioned workpiece in the aforementioned second laminated composite sheet on the aforementioned support sheet, and cutting the aforementioned protective film to produce a plurality of A step in which the wafer with a protective film is fixed on the third laminated composite sheet on the aforementioned support sheet; and, the step of pulling the aforementioned wafer with a protective film in the aforementioned third laminated composite sheet from the aforementioned support sheet, thereby performing a step of picking up . [Efficacy of the invention]

According to the present invention, there can be provided an adhesive sheet for fixing a jig, a composite sheet for forming a protective film having an adhesive layer for a jig formed using the adhesive sheet for fixing a jig, and a method for manufacturing a wafer with a protective film; The aforementioned adhesive sheet for jig fixing has a core material film, and the aforementioned adhesive sheet for jig fixing is used to form a composite sheet for forming a protective film having an adhesive layer for jig, and when used to manufacture a wafer with a protective film, the jig The adhesive layer can be easily peeled off from the fixing jig without breaking.

[Adhesive sheet for jig fixing] An adhesive sheet for fixing a jig according to an embodiment of the present invention is an adhesive sheet for fixing a jig used for a composite sheet for forming a protective film having a protective film forming film, and consists of a first adhesive layer, a core material film, and a second adhesive layer. The two adhesive layers are sequentially laminated in the thickness direction of these layers.

Hereinafter, an example of the adhesive sheet for fixing a jig according to this embodiment will be described with reference to the drawings.

Fig. 1 is a cross-sectional view schematically showing an example of an adhesive sheet for jig fixing according to this embodiment. In addition, in the drawings used in the following description, in order to easily understand the features of the present invention, the main parts may be enlarged for convenience, and the dimensional ratio of each component may not necessarily be the same as the actual one.

The adhesive sheet 1 for fixture fixing shown in FIG. 1 is composed of a first release film 151, a first adhesive layer 161, a core material film 162, a second adhesive layer 163, and a second release film 152 in sequence. It is formed by laminating layers in the thickness direction.

The adhesive sheet for jig fixing shown in FIG. 1 can be dug out into a ring shape as described later to form an adhesive layer for jigs composed of a first adhesive layer 161, a core material film 162, and a second adhesive layer 163. 16. It can be used in the composite sheet for forming a protective film 101 , the composite sheet for forming a protective film 102 , and the composite sheet for forming a protective film 104 as shown in FIGS. 2 to 4 .

The first adhesive layer, the core material film, and the second adhesive layer are sequentially laminated in the thickness direction of these adhesive sheets for jig fixing. The test piece is obtained by tensile test after heating at 130°C for 2 hours. The ratio (Ah/Bh) of the breaking strength (Ah) [N/10mm] to the 180° tear-off adhesion (Bh) [N/10mm] of the test piece to SUS304 after heating at 130°C for 2 hours is more than 1.25.

The adhesive sheet for jig fixing of this embodiment has a ratio (Ah/Bh) of 1.25 or more, and the above-mentioned adhesive sheet for jig fixing can be used to form a composite sheet for forming a protective film having an adhesive layer for jigs, and can be used in use. When manufacturing a wafer with a protective film, the adhesive layer for the jig can be easily peeled off from the jig for fixing without breaking.

The adhesive sheet for jig fixing is preferably at least 1.40, more preferably at least 1.55, still more preferably at least 1.65, and most preferably at least 1.75.

The upper limit of the ratio (Ah/Bh) is not limited, but is preferably 6.5 or less, more preferably 5.5 or less, still more preferably 4.5 or less from the viewpoint of good handleability of the jig fixing adhesive sheet.

The 180° tear-off adhesion (Bh) of the test piece to SUS304 after heating the above-mentioned fixture fixing adhesive sheet at 130°C for 2 hours is preferably 2.0N/10mm to 12N/10mm. The aforementioned 180° pull-off adhesion (Bh) is preferably at least 2.0 N/10 mm, more preferably at least 2.4 N/10 mm, and still more preferably at least 2.8 N/10 mm. By making the tear-off adhesive force (Bh) more than the aforementioned lower limit value, a composite sheet for forming a protective film having an adhesive layer for a jig is formed using an adhesive sheet for fixing a jig and used for manufacturing a wafer with a protective film When it is used, it can reduce the risk of floating from the fixing jig during the heating process or after the heating process.

The aforementioned adhesive sheet for jig fixing is preferably such that the aforementioned 180° tear-off adhesive force (Bh) is 12 N/10 mm or less, more preferably 10 N/10 mm or less, particularly preferably 9.2 N/10 mm or less. By making the peeling adhesive force (Bh) below the above-mentioned upper limit, a composite sheet for forming a protective film having an adhesive layer for a jig is formed using an adhesive sheet for fixing a jig and used for manufacturing a wafer with a protective film When it is used, it is not easy to produce residual glue on the side of the fixing jig and can be easily peeled off from the fixing jig.

The aforementioned adhesive sheet for jig fixing is preferably 6 N/10mm or higher, more preferably 8 N/10 mm or higher, and still more preferably 10 N/10 mm or higher in the test piece after heating at 130° C. for 2 hours. When the breaking strength (Ah) is set to be more than the above-mentioned lower limit value, when a protective film-forming composite sheet having a jig adhesive layer is formed using an adhesive sheet for jig fixing and used to manufacture a wafer with a protective film, The adhesive layer for jigs can be more easily peeled off from the jig for fixation without breaking.

The breaking strength (Ah) is preferably at most 100 N/10 mm, more preferably at most 60 N/10 mm, and still more preferably at most 40 N/10 mm. By making breaking strength (Ah) below the said upper limit, the adhesive sheet for jig fixing can be made easy to handle.

The above-mentioned adhesive sheet for fixture fixing is preferably a test piece heated at 130°C for 2 hours, and the elongation at break (Xh) obtained by the tensile test is 100% or more, more preferably 200% or more, and more preferably More than 300%, preferably more than 400%. When the elongation at break (Xh) is set to be more than the aforementioned lower limit value, and a composite sheet for forming a protective film having an adhesive layer for a jig is formed using an adhesive sheet for fixing a jig and used to manufacture a wafer with a protective film , the adhesive layer for the jig can be easily peeled off from the jig for fixing without breaking.

The above-mentioned adhesive sheet for fixture fixing is preferably a test piece before heating and has an elongation at break (X0) obtained by a tensile test of 100% or more, more preferably 200% or more, and more preferably 300% or more. When the elongation at break (X0) is set to be more than the above-mentioned lower limit value, and a composite sheet for forming a protective film having an adhesive layer for a jig is formed using an adhesive sheet for fixing a jig and used to manufacture a wafer with a protective film When the workpiece attached to the composite sheet for protective film formation has a defect, even if the workpiece is peeled off to make the workpiece reusable (rework), the adhesive layer for the jig can still be removed. Fractured and easily peeled off from the fixing jig.

The elongation at break (Xh) obtained by the tensile test of the test piece after heating the above-mentioned fixture-fixing adhesive sheet at 130°C for 2 hours is relative to the elongation at break (Xh) obtained by the tensile test of the test piece before heating ( The ratio (Xh/X0) of X0) is preferably from 0.10 to 1.50, more preferably from 0.30 to 1.30. By setting the elongation at break (Xh) within the above numerical range, it is easy to form a composite sheet for forming a protective film having an adhesive layer for a jig using an adhesive sheet for fixing a jig and to manufacture a wafer with a protective film. It is also used for both heating process and non-heating process. For example, when you want to use the same device to peel off the adhesive sheet for fixing the jig from the jig for fixing, you can not change the conditions intentionally, even in the process of reproducing (that is, before heating), or manufacturing a protective film. After the wafer (that is, after heating), it can still be easily peeled off under the same condition setting.

(Measuring method of breaking strength (Ah) after heating and elongation at break (Xh) after heating) Cut the adhesive sheet for jig fixing into strips with a width of 10mm and a length of 80mm, heat at 130°C for 2 hours, and let it cool. When the adhesive sheet for jig fixing is composed of the first release film 151, the first adhesive layer 161, the core material film 162, the second adhesive layer 163, and the second release film 152, which are sequentially laminated in the thickness direction of these , the second peeling film 152 is peeled off from the second adhesive layer 163 , and further, the first peeling film 151 is peeled off from the first adhesive layer 161 . Regarding the test piece of the jig fixing adhesive sheet composed of the first adhesive layer 161, the core material film 162, and the second adhesive layer 163 laminated sequentially in the thickness direction, at 23°C, the distance between chucks The tensile test was carried out under the conditions of 50mm and tensile speed of 200mm/min, and the breaking strength (Ah) [N/10mm] and the breaking elongation (Xh) [%] were obtained.

(Measurement method of 180° peel-off adhesion (Bh) after heating) Cut the jig-fixing adhesive sheet into strips with a width of 10 mm and a length of 250 mm, so that the first adhesive layer 161 attached to the side of the fixing jig is exposed, and the exposed jig-fixing adhesive sheet The first adhesive layer 161 was attached to the ♯1200HL-polished surface of the ♯1200HL (Hair Line)-polished SUS304 board by making a 2kg roller back and forth once. Heat at 130°C for 2 hours, let it cool, and measure the 180° peel-off adhesion (Bh) at a speed of 300mm/min at 23°C and 50%RH in accordance with JISZ0237.

The 180° tear-off adhesive force of the adhesive sheet for fixing the fixture can also expose the first adhesive layer 161 of the adhesive sheet for fixing the fixture, and measure the side of the first adhesive layer 161 of the adhesive sheet for fixing the fixture. 180° peel-off adhesive force; the second adhesive layer 163 can also be exposed, and the 180° peel-off adhesive force of the side of the second adhesive layer 163 of the adhesive sheet for fixture fixing can be measured. Either of the 180° peel-off adhesive force on the side of the first adhesive layer 161 or the 180° peel-off adhesive force on the side of the second adhesive layer 163 of the adhesive sheet for jig fixing should be within the above-mentioned range, Preferably, both the 180° peel-off adhesive force on the side of the first adhesive layer 161 and the 180° peel-off adhesive force on the side of the second adhesive layer 163 of the adhesive sheet for jig fixing are within the above-mentioned ranges.

(Calculation method of ratio (Ah/Bh)) Ratio (Ah) of the breaking strength (Ah) of the test piece heated at 130°C for 2 hours to the 180° peel-off adhesion (Bh) of the test piece to SUS304 after heating at 130°C for 2 hours /Bh) can be calculated by dividing the aforementioned breaking strength (Ah) by the aforementioned 180° tear-off adhesion (Bh).

(Measuring method of elongation at break (X0) before heating) Cut the jig fixing adhesive sheet into strips with a width of 10 mm and a length of 80 mm. When the adhesive sheet for jig fixing is composed of the first release film 151, the first adhesive layer 161, the core material film 162, the second adhesive layer 163, and the second release film 152, which are sequentially laminated in the thickness direction of these , the second peeling film 152 is peeled off from the second adhesive layer 163 , and further, the first peeling film 151 is peeled off from the first adhesive layer 161 . Regarding the test piece of the jig fixing adhesive sheet composed of the first adhesive layer 161, the core material film 162, and the second adhesive layer 163 laminated sequentially in the thickness direction, at 23°C, the distance between chucks Under the conditions of 50mm and tensile speed of 200mm/min, the tensile test was carried out, and the elongation at break (X0) [%] before heating was obtained.

(Calculation method of ratio (Xh/X0)) The ratio of the elongation at break (Xh) obtained by the tensile test of the test piece after heating at 130°C for 2 hours to the elongation at break (X0) obtained by the tensile test of the test piece before heating (Xh/ X0) can be calculated by dividing the aforementioned elongation at break (Xh) by the aforementioned elongation at break (X0).

Hereinafter, each layer constituting the adhesive sheet for jig fixing will be described in detail.

[core film] Various resins can be mentioned as a constituent material of the said core material film. Examples of the aforementioned resins include polyethylenes such as low-density polyethylene (LDPE; low density polyethylene), linear low-density polyethylene (LLDPE; linear low density polyethylene), and high-density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; polyolefin-based thermoplastic elastomers such as ethylene-propylene rubber, and ethylene-vinyl acetate copolymer , ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norbornene copolymer and other ethylene-based copolymers (copolymers obtained by using ethylene as a monomer); polystyrene ; Polycycloolefin; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Polyethylene isophthalate, Poly-2,6-naphthalene dicarboxylic acid Ethylene glycol esters, polyesters such as wholly aromatic polyesters whose constituent units are all aromatic ring groups; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes ; Polyacrylate urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Wait.

From the point of view that the above-mentioned elongation at break (X0), strength at break (Ah) and elongation at break (Xh) of the aforementioned adhesive sheet for jig fixing can be adjusted more easily to the above-mentioned numerical range, the constituent material of the aforementioned core material film Among them, it is preferable to contain polyolefin or polyvinyl chloride. In addition, it is more preferable to contain linear low-density polyethylene, non-extended polypropylene, or polyvinyl chloride.

The resin constituting the core material film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these resins can be selected arbitrarily.

The core material film may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the core film may also be 5 μm to 140 μm, preferably 16 μm to 100 μm, more preferably 20 μm to 80 μm, and more preferably 40 μm to 60 μm. When the thickness of the core film is in this range, the flexibility of the jig fixing adhesive sheet can be increased, and wrinkles can be prevented from being generated in the protective film forming composite sheet using the jig fixing adhesive sheet.

However, in order to adjust the aforementioned breaking strength (Ah), the thickness of the core film should not be excessively thickened. In particular, by making the thickness of the core film below the aforementioned upper limit, due to the relationship between the height of the core film, it is possible to prevent the pressing of the lamination roller of the tape sticking machine from being concentrated only on the ring-shaped frame and cause the sticking of the tape sticking machine. Poor adhesion prevents tunneling when the composite sheet for forming a protective film is stored in a roll form, and also prevents a decrease in cuttability during press processing.

Here, the "thickness of the core film" means the thickness of the entire core film, for example, the thickness of the core film composed of multiple layers means the total thickness of all the layers constituting the core film. The core film may contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the above-mentioned resins.

The core material film is preferably transparent, but may be colored as necessary, and other layers may be vapor-deposited.

In order to adjust the first adhesive layer on both sides of the core film and the adhesiveness relative to the first adhesive layer, the surface of the core film can also be subjected to the following treatments: sandblasting, solvent treatment, etc., embossing treatment; corona Discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other acidification treatments; lipophilic treatment; hydrophilic treatment, etc. In addition, the surface of the core film can also be treated with primer.

The core material film can also have adhesiveness on at least one side surface by containing a specific range of components (such as resin, etc.).

○Manufacturing method of core film The core film can be produced by a known method. For example, the resin-containing core film can be produced by molding the above-mentioned resin composition containing the core film.

[First adhesive layer and second adhesive layer] The first adhesive layer and the second adhesive layer satisfy the aforementioned conditions of peel-off adhesive force, and may be non-energy ray curable or energy ray curable, preferably non-energy ray curable. In this specification, "non-energy ray curability" means the property of not being cured even when irradiated with energy ray. Conversely, the property of hardening by irradiation of energy rays is called "energy ray hardening". In this specification, the so-called "energy line" means an energy line having energy quanta in electromagnetic waves or charged particle beams. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED (Light Emitting Diode, Light Emitting Diode) lamp as an ultraviolet source. Electron beams may be irradiated to those generated by an electron beam accelerator or the like.

The thicknesses of the first adhesive layer and the second adhesive layer are preferably 2 μm to 15 μm, more preferably 3 μm to 12 μm, and especially preferably 4 μm from the aspect of appropriately adjusting the aforementioned 180° peel-off adhesive force. to 10 μm.

The total thickness of the first adhesive layer, the core material film and the second adhesive layer is preferably 10 μm to 170 μm, more preferably 20 μm to 100 μm, still more preferably 30 μm to 70 μm, especially preferably 35 μm to 60 μm. The aforementioned 180° peel-off adhesive force can be appropriately adjusted by setting the total thickness above the aforementioned lower limit, and the flexibility of the jig fixing adhesive sheet can be improved by setting the total thickness below the aforementioned upper limit. , to prevent wrinkles from occurring in the protective film forming composite sheet using the aforementioned jig fixing adhesive sheet.

The aforementioned first adhesive layer and second adhesive layer system can be formed using an adhesive composition for a jig containing an adhesive. For example, the first adhesive layer can be formed on the target site by applying the adhesive composition for a jig on the surface to be formed of the first adhesive layer and drying it as necessary. The adhesive composition for a jig can be applied to the surface to be formed of the second adhesive layer, and dried as necessary to form the second adhesive layer on the target site. More specific methods for forming the first adhesive layer and the second adhesive layer are described in detail below together with the methods for forming other layers. The content ratio of the components that do not vaporize at room temperature in the adhesive composition for jigs is usually the same as the content ratio of the above-mentioned components in the adhesive layer.

The coating of the adhesive composition for jigs may be performed by a known method, for example, an air knife coater, a knife coater, a rod coater, a gravure coater, a roll coater, Roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coater, etc. Methods of using various coaters.

The drying conditions of the adhesive composition for jigs are not particularly limited, but if the adhesive composition for jigs contains the solvent described later, it is preferable to perform heat drying. In this case, for example, it is preferable to use 70 ℃ to 130 ℃ and 10 seconds to 5 minutes for drying.

Examples of the jig adhesive composition for forming the first adhesive layer and the second adhesive layer include a non-energy ray-curable adhesive composition, or an energy-ray-curable adhesive composition described later. It is preferably a non-energy ray curable adhesive composition.

Here, examples of the non-energy ray-curable adhesive composition include those containing the following resins: acrylic resins (resins containing constituent units derived from (meth)acrylates), urethane resins (resin with urethane bond), rubber-based resin (resin with rubber structure), silicone-based resin (resin with siloxane bond), epoxy-based resin (resin with epoxy group) , polyvinyl ether, or an adhesive resin such as polycarbonate (hereinafter referred to as "adhesive resin (i)").

(adhesive resin (i)) Among the above-mentioned adhesive resins (i), acrylic resin is preferable, because it has high adhesion to the fixing jig 18 such as a ring frame, and can effectively prevent self-fixation of the composite sheet for protective film formation in the cutting step, etc. Use jig 18 to peel off. As said acrylic resin in adhesive resin (i), the acrylic polymer which has the structural unit derived from an alkyl (meth)acrylate at least is mentioned, for example. The structural unit which the said acrylic resin has may be only one type, and may be two or more types, and when there are two or more types, the combination and ratio of these structural units can be arbitrarily selected.

Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the aforementioned alkyl group is preferably linear or branched. shape. As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, third-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-(meth)acrylate Nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Decadecyl (meth)acrylate Hexadecyl (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth) Nonadecyl acrylate, eicosyl (meth)acrylate, etc.

From the viewpoint of improving the adhesive force of the first adhesive layer and the second adhesive layer, the acrylic polymer is preferably derived from an alkyl (meth)acrylate having the aforementioned alkyl group having 4 or more carbon atoms. the constituent unit. And, from the point of view that the adhesive force of the adhesive layer can be further improved, the carbon number of the aforementioned alkyl group is preferably 4-12, more preferably 4-8. In addition, the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably an alkyl acrylate.

The aforementioned acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. Examples of the above-mentioned functional group-containing monomer include: the starting point of cross-linking by reacting the above-mentioned functional group with a cross-linking agent described later; A monomer that introduces unsaturated groups into the side chains of acrylic polymers by reacting functional groups such as glycidyl groups and glycidyl groups.

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxyl group, an amino group, an epoxy group etc. are mentioned, for example. That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

Examples of the aforementioned hydroxyl-containing monomers include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryl skeleton) such as allyl alcohol, and the like. From the point of view that the crosslinking reaction becomes easy, it is preferably 4-hydroxybutyl acrylate or 2-hydroxyethyl (meth)acrylate, more preferably 4-hydroxybutyl acrylate or 2-hydroxybutyl acrylate. Hydroxyethyl esters, especially 4-hydroxybutyl acrylate.

As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylenically unsaturated dicarboxylic acids such as maleic acid and citraconic acid (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. base) carboxyalkyl acrylate, etc.

The functional group-containing monomer is preferably a hydroxyl-containing monomer or a carboxyl-containing monomer, more preferably a hydroxyl-containing monomer.

The aforementioned acrylic resin as the adhesive resin (i) is preferably an acrylic polymer having a constituent unit derived from an alkyl (meth)acrylate and a constituent unit derived from a hydroxyl group-containing monomer, and may have a constituent unit derived from An acrylic polymer derived from a constituent unit of an alkyl (meth)acrylate, a constituent unit derived from a hydroxyl group-containing monomer, and a constituent unit derived from a carboxyl group-containing monomer. The aforementioned acrylic resin preferably does not have a structural unit derived from (meth)acrylic acid.

The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these functional group-containing monomers can be selected arbitrarily.

In the aforementioned acrylic polymer, the content of the constituent units derived from the functional group-containing monomer is preferably 0.5% by mass to 12% by mass, more preferably 0.8% by mass to 10% by mass, relative to the total amount of the constituent units, More preferably, it is 1.0 mass % to 5.0 mass %.

The said acrylic polymer may further have the structural unit derived from another monomer other than the structural unit derived from the alkyl (meth)acrylate and the functional group containing monomer. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with an alkyl (meth)acrylate or the like. Examples of the other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

The aforementioned other monomer constituting the aforementioned acrylic polymer may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these other monomers may be selected arbitrarily.

The weight average molecular weight (Mw) of the said acrylic resin in adhesive resin (i) becomes like this. Preferably it is 700,000 or more, More preferably, it is 800,000 or more. By making the weight average molecular weight (Mw) of the acrylic resin more than the aforementioned lower limit, the aforementioned 180° peel-off adhesive force (Bh) of the aforementioned jig fixing adhesive sheet can be adjusted more easily to the aforementioned numerical range.

The weight average molecular weight of the acrylic resin in the adhesive resin (i) is preferably at most 10 million, more preferably at most 5 million, and even more preferably at most 2 million. By setting the weight-average molecular weight of the acrylic resin to be equal to or less than the upper limit, the breaking strength (Ah) and the 180° peel-off adhesive force (Bh) of the jig-fixing adhesive sheet can be adjusted more easily to the above-mentioned range of values.

In addition, in this specification, unless otherwise specified, weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC; Gel Permeation Chromatography) method.

The glass transition temperature (Tg) of the acrylic resin in the adhesive resin (i) is preferably -70°C to 30°C, more preferably -65°C to -5°C, still more preferably -60°C to -20°C, Especially preferably -55°C to -40°C. By making the Tg of the acrylic resin within the aforementioned range, when used in the manufacture of a wafer with a protective film, it is difficult to generate floating from the fixing jig after heating, and the residue generated on the side of the fixing jig Less glue makes it easier to obtain adhesive sheets for jig fixing.

The glass transition temperature (Tg) of an acrylic resin can be calculated using the Fox's formula shown below. 1/Tg=(W1/Tg1)+(W2/Tg2)+...+(Wm/Tgm) (where, Tg is the glass transition temperature of acrylic resin, Tg1, Tg2,...Tgm are the raw materials of acrylic resin The glass transition temperature of the homopolymer of the monomer, W1, W2, ... Wm is the mass fraction of each monomer. Among them, W1 + W2 + ... + Wm = 1.) The glass transition temperature of the homopolymer of each monomer in the aforementioned Fox's formula can use the value recorded in the polymer data/handbook, adhesive handbook, or Polymer Handbook. For example, the Tg of methyl acrylate homopolymer is 10°C, the Tg of 2-hydroxyethyl acrylate homopolymer is -15°C, the Tg of n-butyl acrylate homopolymer is -54°C, and the Tg of ethyl acrylate homopolymer Tg of -24°C, Tg of 4-hydroxybutyl acrylate homopolymer is -32°C, Tg of N,N-dimethylacrylamide homopolymer is 119°C, acryloylmorpholine homopolymer The Tg of the product was 145°C, and the Tg of the glycidyl methacrylate homopolymer was 41°C.

Adhesive resins (i) other than the aforementioned acrylic polymer preferably have a structural unit derived from a functional group-containing monomer, similarly to the aforementioned acrylic polymer.

The adhesive resin (i) contained in the adhesive composition for jigs may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these adhesive resins (i) may be arbitrary. to choose.

In the adhesive composition for jigs, the ratio of the content of the adhesive resin (i) to the total content of the components other than the solvent (that is, the content of the adhesive resin (i) in the adhesive layer) is preferably 60 % by mass to 99% by mass, more preferably 70% by mass to 98% by mass, especially preferably 80% by mass to 96% by mass. By setting the aforementioned ratio of the content of the adhesive resin (i) in such a range, the aforementioned 180° peel-off adhesive force (Bh) of the aforementioned jig fixing adhesive sheet can be adjusted more easily to the aforementioned numerical range.

(crosslinking agent (ii)) The adhesive composition for jigs preferably contains a crosslinking agent (ii). The crosslinking agent (ii) reacts with the said functional group, for example, and crosslinks adhesive resin (i) mutually. Examples of the crosslinking agent (ii) include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of these diisocyanates. Epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents with glycidyl groups); Hexa[1-(2-methyl)-aziridinyl]triphosphine triazine and other aziridine-based cross-linking agents Cross-linking agent (cross-linking agent with aziridine group); metal chelate cross-linking agent such as aluminum chelate (cross-linking agent with metal chelate structure); isocyanurate-based cross-linking agent (Crosslinking agent with isocyanuric acid skeleton), etc. In terms of improving the cohesive force of the adhesive and making it easy to adjust the aforementioned 180° tear-off adhesive force (Bh) of the aforementioned jig-fixing adhesive sheet to the aforementioned numerical range, and from the aspect of being easy to obtain, the crosslinking agent (ii) Preferably, it is an isocyanate-based crosslinking agent.

The crosslinking agent (ii) contained in the adhesive composition for jigs may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these crosslinking agents (ii) can be arbitrary. to choose.

When the adhesive composition for jigs contains the cross-linking agent (ii), the content of the cross-linking agent (ii) relative to the content of 100 parts by mass of the adhesive resin (i) in the adhesive composition for jigs is It is preferably 0.02 to 4.0 parts by mass, more preferably 0.03 to 2.0 parts by mass, more preferably 0.04 to 1.0 parts by mass, especially preferably 0.04 to 0.3 parts by mass. By making the said content of a crosslinking agent (ii) more than the said lower limit, the effect by using a crosslinking agent (ii) can be acquired more notably. Moreover, by making the said content of a crosslinking agent (ii) into the said range, the said 180 degree peeling adhesive force (Bh) of the said jig fixing adhesive sheet can be adjusted more easily to the said numerical range.

(other additives) The adhesive composition for jigs may also contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the efficacy of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, Reaction delay agent, crosslinking accelerator (catalyst) and other known additives. In addition, the reaction delaying agent is, for example, a component that suppresses an unintended crosslinking reaction in the jig adhesive composition being stored due to the action of a catalyst mixed in the jig adhesive composition. As a reaction retarder, for example, a compound that forms a chelate complex by chelating a catalyst, more specifically, a molecule having two or more carbonyl groups (-C(=O)- ) compounds.

The other additives contained in the jig adhesive composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio of these other additives may be selected arbitrarily.

In the adhesive composition for jigs, the content of other additives is not particularly limited, and can be appropriately selected according to the types of additives.

(solvent) The adhesive composition for jigs may also contain a solvent. The adhesive composition for jigs improves the applicability to the surface to be coated by containing a solvent.

The aforementioned solvent is preferably an organic solvent, and examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.

As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (i) may not be removed from the adhesive resin (i), but may be directly used in the adhesive composition for jigs, and may also be used in jigs. When the adhesive composition is produced, the solvent used in the production of the adhesive resin (i) is additionally added, which is the same or a different type of solvent.

The solvent contained in the jig adhesive composition may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio of these solvents can be selected arbitrarily.

In the adhesive composition for jigs, the content of the solvent is not particularly limited, as long as it is properly adjusted.

[Manufacturing method of adhesive composition for jig] The adhesive composition for jigs is obtained by preparing the components used to constitute the composition. The order of addition of each component is not particularly limited, and two or more components may be added at the same time. When using a solvent, the solvent may be mixed with any formulation components other than the solvent and the formulation components may be diluted beforehand, or the solvent may be mixed with these formulation components without pre-diluting any formulation components other than the solvent. Mix to use.

The method of mixing the ingredients is not particularly limited, as long as it is properly selected from known methods such as the following methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; A method of mixing by applying ultrasonic waves. The temperature and time during the addition and mixing of each component are not particularly limited as long as the ingredients are not deteriorated, as long as they are properly adjusted, the temperature is preferably 15°C to 30°C.

[First release film and second release film] The adhesive sheet for jig fixing can be supplied in a form in which a first release film and a second release film are layered on both surfaces of the first adhesive layer and the second adhesive layer.

The first release film and the second release film are not particularly limited, and commercially available release films can be used, for example: polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, etc. Polyethylene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film , ethylene-vinyl acetate copolymer film, ionomer resin film, ethylene-(meth)acrylic acid copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, poly An imide film, a fluororesin film, etc., preferably a polyethylene terephthalate film. In addition, crosslinked films of these films can also be used. Furthermore, laminated films of these films can also be used.

The surface tension of the surface of the first release film contacting the first adhesive layer and the surface of the second release film contacting the second adhesive layer is preferably 40 mN/m or less, more preferably 37 mN/m or less, especially preferably Below 35mN/m. The lower limit of surface tension is usually around 25mN/m. Such a release film with a relatively low surface tension can be obtained by appropriately selecting a material, or can be obtained by coating a release agent on the surface of the release film and applying a release treatment. The surface tension of the surface contacting the first adhesive layer in the first release film and the surface contacting the second adhesive layer in the second release film may be the same or different. The surface of the agent layer becomes the heavy peeling surface so that the surface tension of the two is different.

As the release agent used for peeling treatment, alkyd, polysiloxane, fluorine, unsaturated polyester, polyolefin, wax, rubber, etc. are used, especially alkyd and polysiloxane , Fluorine-based stripping agents are heat-resistant and preferred.

In order to use the above-mentioned release agent to release the surface of the film that becomes the base of the first release film and the second release film, etc., the release agent is directly in a solvent-free state, or is diluted with a solvent or emulsified. Gravure coater, wire-wound bar coater, air knife coater, roll coater, etc., supply the release film coated with release agent at room temperature or under heating, or What is necessary is just to form a release agent layer by hardening with an electron beam.

The surface roughness (Ra) of the surface contacting the first adhesive layer in the first release film and the surface contacting the second adhesive layer in the second release film is preferably from 10nm to 100nm, preferably from 15nm to 60nm, preferably from 15nm to 60nm. Preferably, it is 20nm to 50nm. The surface roughness (Ra) of the surface contacting the first adhesive layer of the first release film and the surface contacting the second adhesive layer of the second release film may be the same or different.

[Manufacturing method of adhesive sheet for jig fixing] The adhesive sheet for jig fixing can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

For example, the first adhesive layer is formed on the release-treated surface of the first release film by applying the adhesive composition for jigs of the first adhesive layer on the release-treated surface of the first release film. The exposed surface of the first adhesive layer is pasted on the first surface of one side of the core material film. The adhesive composition for jigs of the second adhesive layer is coated on the release-treated surface of the second release film, and the second adhesive layer is formed on the release-treated surface of the second release film. By sticking the exposed surface of the second adhesive layer on the second surface of the other side of the core film, it can be used to manufacture the first adhesive layer, the core film, and the second adhesive layer in order of these thicknesses Adhesive sheets for jig fixing formed by laminating layers in one direction.

[Composite sheet for protective film formation] A composite sheet for forming a protective film according to an embodiment of the present invention includes: a support sheet, a protective film forming film provided on one side of the support sheet, and a protective film formed on the one side of the support sheet or The adhesive layer for jigs provided near the peripheral portion of the first surface on the opposite side to the support sheet in the protective film forming film; The jig is fixed with an adhesive sheet. Hereinafter, an example of the composite sheet for protective film formation of this embodiment is demonstrated, referring drawings.

Fig. 2 is a cross-sectional view schematically showing an example of the composite sheet for forming a protective film according to this embodiment. In addition, in FIG. 2 and subsequent figures, the same reference numerals as in the case of the already-described figures are assigned to the same constituent elements as those shown in the already-described figures, and detailed description thereof will be omitted.

The protective film-forming composite sheet 101 shown here includes a support sheet 10 and a protective film-forming film provided on a surface (sometimes referred to as "first surface" in this specification) 10a of the support sheet 10. 13 constitute. The support sheet 10 is composed of a base material 11 and an adhesive layer 12 provided on one surface (first surface) 11 a of the base material 11 . In the composite sheet 101 for protective film formation, the adhesive layer 12 is arrange|positioned between the base material 11 and the protective film formation film 13. That is, the composite sheet 101 for forming a protective film is provided with a support sheet 10 composed of a base material 11 and an adhesive layer 12, a protective film forming film 13 provided on the surface of the adhesive layer 12 of the support sheet 10, and The protective film forms the jig adhesive layer 16 provided near the periphery of the first surface of the film 13 on the opposite side to the support sheet 10 . The first surface 10 a of the support sheet 10 is the same as the surface (sometimes referred to as “first surface” in this specification) 12 a on the side opposite to the substrate 11 side of the adhesive layer 12 .

The composite sheet 101 for protective film formation is further equipped with the adhesive agent layer 16 for jigs, and the peeling film 15 on the protective film formation film 13. In the protective film forming composite sheet 101, the protective film forming film 13 is laminated on the entire or substantially entire surface of the first surface 12a of the adhesive layer 12, and the protective film forming film 13 is on the opposite side to the adhesive layer 12 side. Adhesive layer 16 for jigs is laminated on a part of surface (sometimes referred to as "first surface" in this specification) 13a, that is, a region near the peripheral edge. Furthermore, among the first surface 13a of the protective film forming film 13, the area where the adhesive layer 16 for jigs is not laminated, and the surface of the adhesive layer 16 for jigs that is on the opposite side to the side of the protective film forming film 13 ( The peeling film 15 is laminated|stacked on 16a sometimes called a "1st surface" in this specification. The support sheet 10 is provided on the surface (sometimes referred to as a "second surface" in this specification) opposite to the first surface 13a of the protective film forming film 13 .

Not limited to the case of the composite sheet 101 for forming a protective film, in the composite sheet for forming a protective film of this embodiment, the release film may have any configuration, and the composite sheet for forming a protective film of this embodiment may or may not be provided with a release film. .

The protective film forming composite sheet 101 is attached to the inner surface of the workpiece on the first surface 13a of the protective film forming film 13 in the state where the peeling film 15 is removed, and then the first surface of the jig adhesive layer 16 is attached to the inner surface of the workpiece. The surface 16a is attached to a fixing jig 18 such as a ring frame and used.

Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to this embodiment. In the protective film forming composite sheet 102 shown here, except that the shape and size of the protective film forming film are different, and the adhesive for jigs is laminated on the first surface of the adhesive layer instead of the first surface of the protective film forming film. Other than that, it is the same as the protective film forming composite sheet 101 shown in FIG. 2 .

More specifically, in the protective film forming composite sheet 102, the protective film forming film 23 is laminated on a part of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12 (Fig. 3 in the left and right directions) on the central side of the area. Furthermore, in the region where the protective film forming film 23 is not laminated on the first surface 12a of the adhesive layer 12, the adhesive for the jig is laminated so as to surround the protective film forming film 23 from the outside in the width direction without contact. Agent layer 16. Furthermore, in the protective film forming film 23, the surface opposite to the adhesive layer 12 side (sometimes referred to as "first surface" in this specification) 23a, and the first surface 16a of the jig adhesive layer 16 A release film 15 is laminated. The support sheet 10 is provided on the surface (sometimes referred to as a "second surface" in this specification) opposite to the first surface 23a of the protective film forming film 23 .

Fig. 4 is a cross-sectional view schematically showing still another example of the composite sheet for forming a protective film according to this embodiment. The composite sheet 104 for protective film formation shown here is the same as the composite sheet 101 for protective film formation shown in FIG.

The supporting sheet 20 is only composed of the base material 11 . That is, the composite sheet 104 for protective film formation is comprised by laminating|stacking the base material 11 and the protective film forming film 13 in the thickness direction of these. The composite sheet 104 for forming a protective film includes: a support sheet 20 composed only of the base material 11 , a protective film forming film 13 provided on one side of the support sheet 20 , and a surface on the aforementioned side of the support sheet 10 Adhesive layer 16 for jigs provided near the upper peripheral edge. The surface (first surface) 20 a of the support sheet 20 on the protective film forming film 13 side is the same as the first surface 11 a of the base material 11 .

The composite sheet for forming a protective film in this embodiment is not limited to the composite sheet for forming a protective film shown in FIGS. Some configurations of the composite sheet for protective film formation are changed or deleted, or other configurations are further added to the composite sheet for protective film formation described so far.

Next, each layer which comprises the composite sheet for protective film formation is demonstrated in more detail.

○Support piece The above-mentioned supporting sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these layers may be the same or different from each other, and the combination of these layers is not particularly limited within the range that does not impair the effects of the present invention.

The support sheet is preferably transparent, and can be colored as needed. When the protective film forming film has energy ray curability, it is preferable that the support sheet allows energy ray to penetrate.

As a support sheet, the support sheet provided with the base material and the adhesive layer provided on one side of the said base material, the support sheet which consists only of a base material, etc. are mentioned, for example. When the support sheet has an adhesive layer, in the composite sheet for protective film formation, an adhesive layer is arrange|positioned between a base material and a protective film forming film.

When using the support sheet provided with a base material and an adhesive layer, in the composite sheet for protective film formation, the adhesiveness and peelability of a support sheet and a protective film forming film can be adjusted easily. When using the support sheet which consists only of a base material, the composite sheet for protective film formation can be manufactured at low cost.

○Substrate The aforementioned base material is in the form of a sheet or a film, and examples of the constituent material of the base material include various resins. Examples of the aforementioned resins include polyethylenes such as low-density polyethylene (LDPE; low density polyethylene), linear low-density polyethylene (LLDPE; linear low density polyethylene), and high-density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- Ethylene-based copolymers (copolymers obtained by using ethylene as a monomer) such as (meth)acrylate copolymers and ethylene-norbornene copolymers; polystyrene; polycycloolefins; polyethylene terephthalate , Polyethylene naphthalate, Polybutylene terephthalate, Polyethylene isophthalate, Polyethylene-2,6-naphthalene dicarboxylate, all constituent units have aromatic ring formula Polyesters such as wholly aromatic polyesters; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes; polyacrylic urethanes; polyimides; Polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide;

The constituent material of the aforementioned substrate is preferably polyolefin-containing resin, among which polyolefin other than polyethylene is preferred, and polypropylene is more preferred.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than this polyester, are also mentioned, for example. The polymer alloy of the aforementioned polyester and a resin other than the polyester preferably has a relatively small amount of the resin other than the polyester. In addition, examples of the aforementioned resins include: crosslinked resins obtained by crosslinking one or more types of the aforementioned resins exemplified so far; Modified resins such as polymers.

The resin constituting the base material may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these resins can be selected arbitrarily.

The base material may also be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the substrate is preferably from 50 μm to 300 μm, more preferably from 60 μm to 100 μm. When the thickness of the base material is within such a range, the flexibility of the support sheet and the composite sheet for forming a protective film, and the adhesion property to workpieces such as semiconductor wafers are further improved. Here, the "thickness of the substrate" refers to the thickness of the entire substrate, for example, the thickness of a substrate composed of multiple layers refers to the total thickness of all the layers constituting the substrate.

The base material may contain various well-known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the aforementioned resins.

The base material is preferably transparent, and may be colored as necessary, and another layer may be vapor-deposited.

For the base material, in order to adjust the adhesiveness of the adhesive layer or protective film formed on the base material, the following treatments may be performed on the surface: roughening treatment such as sandblasting treatment, solvent treatment, etc.; Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other acidification treatments; lipophilic treatment; hydrophilic treatment, etc. In addition, the surface of the substrate can also be treated with primer.

The substrate can also have adhesiveness on at least one side by containing a specific range of ingredients (such as resin, etc.).

○Adhesive layer The aforementioned adhesive layer is sheet-like or film-like and contains an adhesive. Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins.

In this specification, "adhesive resin" includes both an adhesive resin and an adhesive resin. For example, the above-mentioned adhesive resins include not only resins that have adhesiveness by themselves, but also resins that express adhesiveness by using in combination with other ingredients such as additives, or that express adhesiveness by the presence of triggers such as heat or water. resin etc.

The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the adhesive layer is not particularly limited, preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and most preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, for example, the thickness of the adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.

The adhesive layer is preferably transparent, and may be colored as necessary. When the protective film forming film has energy ray curability, it is preferable that the pressure-sensitive adhesive layer penetrates energy ray.

The adhesive layer may be either energy ray curable or non-energy ray curable. The energy ray hardening adhesive layer can adjust the physical properties before and after hardening. For example, the wafer with a protective film can be picked up more easily by hardening the energy ray-curable adhesive layer before picking up a wafer with a protective film described later.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer can be formed on the target site by applying the adhesive composition on the surface to be formed of the adhesive layer and drying it as necessary. In the adhesive composition, the content ratio of the components that do not vaporize at normal temperature is usually the same as the content ratio of the aforementioned components of the adhesive layer.

The application and drying of the adhesive composition can be performed, for example, in the same manner as the above-mentioned application and drying of the adhesive composition for jigs.

When the adhesive layer is energy ray curable, the energy ray curable adhesive composition includes, for example, an acrylic resin (I-1a) containing a hydroxyl group and non-energy ray curable adhesive (hereinafter Sometimes abbreviated as "adhesive resin (I-1a)"), and an adhesive composition (I-1) of an energy ray-curable compound; containing the above-mentioned adhesive resin (I-1a) that is non-energy ray-curable Adhesive composition (I-2) of an energy-ray-curable adhesive resin (I-2a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)") having an unsaturated group introduced into its side chain; Adhesive composition (I-3) and the like containing the aforementioned adhesive resin (I-2a) and an energy ray-curable compound.

When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include an adhesive composition containing the aforementioned non-energy ray-curable adhesive resin (I-1a) ( I-4) etc.

[Non-energy ray-curable adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is an acrylic resin having a hydroxyl group. As said acrylic resin, the acrylic polymer which has the structural unit derived from the monomer containing a hydroxyl group, and the structural unit derived from an alkyl (meth)acrylate is mentioned, for example. Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the aforementioned alkyl group is preferably linear or branched. shape.

The aforementioned acrylic polymer may have units derived from functional groups other than the hydroxyl-containing monomer in addition to the constituent units derived from the hydroxyl-containing monomer and the constituent units derived from the alkyl (meth)acrylate. The constituent units of the body. Examples of functional group-containing monomers including hydroxyl-containing monomers include: starting point of crosslinking by reacting the aforementioned functional group with a cross-linking agent described later; The reaction of functional groups such as isocyanate group and glycidyl group in the unsaturated group compound can introduce unsaturated group monomer into the side chain of the acrylic polymer.

Examples of the functional group-containing monomer include carboxyl group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers, in addition to hydroxyl group-containing monomers.

The said acrylic polymer may further have the structural unit derived from another monomer other than the structural unit derived from the alkyl (meth)acrylate and the functional group containing monomer. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with an alkyl (meth)acrylate or the like. Examples of the other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

In the aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter including these adhesive compositions, Abbreviated as "adhesive composition (I-1) to adhesive composition (I-4)"), the structural units of the aforementioned acrylic resin such as the aforementioned acrylic polymer may be only one type, or may be two or more types , when there are two or more of them, the combination and ratio of these constituent units can be selected arbitrarily.

In the aforementioned acrylic polymer, the ratio of the amount of the structural unit derived from the functional group-containing monomer to the total amount of the structural unit is preferably 1% by mass to 35% by mass.

Adhesive resin (I-1a) contained in adhesive composition (I-1) or adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, The combination and ratio of these adhesive resins (I-1a) can be selected arbitrarily.

In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-4), the content ratio of the adhesive resin (I-1a) relative to the total mass of the aforementioned adhesive layer It is preferably 5% by mass to 99% by mass, and may be, for example, any one of 25% by mass to 98% by mass, 45% by mass to 97% by mass, and 65% by mass to 96% by mass.

[Energy Ray Curing Adhesive Resin (I-2a)] The aforementioned adhesive resin (I-2a) can be obtained, for example, by reacting an unsaturated group-containing compound having an energy ray polymerizable unsaturated group with a functional group in the aforementioned adhesive resin (I-1a). get.

The aforementioned unsaturated group-containing compound is a group having a group that reacts not only with the aforementioned energy ray polymerizable unsaturated group, but also with the functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a). Resin (I-1a)-bonded compound. Examples of the aforementioned energy ray polymerizable unsaturated group include (meth)acryl, vinyl (ethenyl; ethylene), allyl (2-propenyl), and the like, preferably (methyl) Acryl. Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amine groups, and carboxyl groups that can be bonded to epoxy groups. hydroxyl and amine groups.

Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl isocyanate, and glycidyl (meth)acrylate.

Adhesive resin (I-2a) contained in adhesive composition (I-2) or adhesive composition (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, The combination and ratio of these adhesive resins (I-2a) can be selected arbitrarily.

In the adhesive layer formed by the adhesive composition (I-2) or the adhesive composition (I-3), the content ratio of the adhesive resin (I-2a) relative to the total mass of the aforementioned adhesive layer Preferably it is 5% by mass to 99% by mass.

[Energy Beam Curing Compound] Examples of the aforementioned energy ray-curable compound contained in the aforementioned adhesive composition (I-1) or adhesive agent composition (I-3) include, for example, compounds having an energy-ray-polymerizable unsaturated group that can be irradiated with energy rays. And hardened monomer or oligomer.

Among the energy ray curable compounds, examples of monomers include: trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate Poly(meth)acrylates such as (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; (meth)acrylic acid amine Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc. Among the energy ray-curable compounds, examples of the oligomers include oligomers of polymers of the monomers exemplified above, and the like.

The aforementioned energy ray-curing compound contained in the adhesive composition (I-1) or adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, the energy The combination and ratio of the line-curing compounds can be selected arbitrarily.

In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-3), the ratio of the content of the energy ray-curable compound to the total mass of the adhesive layer is preferable 1% by mass to 50% by mass.

[Crosslinking agent] Adhesive composition (I-1) to adhesive composition (I-4) may further contain an isocyanate crosslinking agent.

The crosslinking agent reacts with the hydroxyl group to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a).

In the aforementioned adhesive composition (I-1) to adhesive composition (I-4), with respect to the content of adhesive resin (I-1a) or adhesive resin (I-2a) of 100 mass parts, crosslinking The content of the agent is preferably 0.01 to 50 parts by mass, for example, may be any of 1 to 40 parts by mass, 5 to 35 parts by mass, and 10 to 30 parts by mass.

[Photopolymerization Initiator] Adhesive composition (I-1), adhesive composition (I-2), and adhesive composition (I-3) (these adhesive compositions are included below, and sometimes abbreviated as "adhesive composition (I- 1) to the adhesive composition (I-3)") may further contain a photopolymerization initiator. Adhesive composition (I-1) to adhesive composition (I-3) containing a photopolymerization initiator can sufficiently undergo hardening reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, Benzoin dimethyl ketal, 2,4-diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile , benzoyl, dibenzoyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide and β-chloroanthraquinone, etc.

The photopolymerization initiator contained in the adhesive composition (I-1) to the adhesive composition (I-3) may be only one kind, or may be two or more kinds. In the case of two or more kinds, these photopolymerization initiators The combination and ratio of starters can be selected arbitrarily.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the aforementioned energy ray-curable compound. In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 20 parts by mass.

[Other additives] Adhesive composition (I-1) to adhesive composition (I-4) may also contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the efficacy of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, Reaction delay agent, crosslinking accelerator (catalyst) and other known additives. In addition, the so-called reaction delaying agent is, for example, the adhesive composition (I- 1) A component that performs an unintended cross-linking reaction in the adhesive composition (I-4). As a reaction retarder, for example, a compound that forms a chelate complex by chelating a catalyst, more specifically, a compound having two or more carbonyl groups (-C(=O)-) in one molecule can be mentioned. compound.

The other additives contained in the adhesive composition (I-1) to the adhesive composition (I-4) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination of these other additives and The ratio can be chosen arbitrarily.

The contents of other additives in the adhesive composition (I-1) to adhesive composition (I-4) are not particularly limited, and can be appropriately selected according to the types of additives.

[solvent] Adhesive composition (I-1) to adhesive composition (I-4) may also contain a solvent. Adhesive composition (I-1) to adhesive composition (I-4) improve the applicability to the surface to be coated by containing a solvent.

The aforementioned solvent is preferably an organic solvent, and examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.

The solvent contained in adhesive composition (I-1) to adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these solvents may be Choose arbitrarily.

The contents of the solvents in the adhesive composition (I-1) to adhesive composition (I-4) are not particularly limited, and may be adjusted appropriately.

○Manufacturing method of adhesive composition Adhesive compositions such as adhesive composition (I-1) to adhesive composition (I-4), the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive can be used to constitute the adhesive composition It is obtained by blending the various components. The order of addition of each component is not particularly limited, and two or more components may be added at the same time. The method of mixing the ingredients is not particularly limited, as long as it is properly selected from known methods such as the following methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; A method of mixing by applying ultrasonic waves. The temperature and time during the addition and mixing of each component are not particularly limited as long as the ingredients are not deteriorated, as long as they are properly adjusted, the temperature is preferably 15°C to 30°C.

◇Manufacturing method of support sheet When providing an adhesive layer on a base material, for example, it is only necessary to apply an adhesive composition on a base material, and to dry it as needed. Furthermore, for example, an adhesive layer may be previously formed on the release film by applying the adhesive composition on the release film and drying it as necessary, and bonding the exposed surface of the adhesive layer to one surface of the substrate. combined, whereby an adhesive layer is laminated on the substrate. The release film in this case may be removed at any timing during the production process or use process of the protective film forming composite sheet.

○Protective film forming film The above-mentioned protective film forming film is used by being attached to the inner surface of workpieces such as semiconductor wafers in the method of manufacturing a wafer with a protective film. The protective film forming film can be used to protect the inner surface of a workpiece or a wafer obtained by dividing the aforementioned workpiece.

By using the above-mentioned composite sheet for forming a protective film, a wafer with a protective film including a wafer and a protective film provided on the inner surface of the wafer can be manufactured by a method of manufacturing a wafer with a protective film described later.

Furthermore, a substrate device can be manufactured by using the aforementioned wafer with a protective film. In this specification, the so-called "substrate device" refers to a device formed by flip-chip connecting protruding electrodes on the circuit surface of the chip with a protective film to connection pads on the circuit substrate. For example, when a semiconductor wafer is used as the workpiece, the substrate device includes, for example, a semiconductor device on which a semiconductor wafer with a protective film is mounted.

The protective film forming film may be curable or non-curable. The protective film forming film is preferably curable. When the protective film forming film is curable, the protective film forming film may be a thermosetting protective film forming film or an energy ray curable protective film forming film. The above-mentioned protective film-forming film is more preferably a thermosetting protective film-forming film. In this specification, the protective film forming film after heating and cooling is formed by heating the protective film forming film at normal temperature to a temperature higher than normal temperature, and then cooling to normal temperature, and the resin film after heating and cooling is formed. When the hardness of the film is compared with the hardness of the resin film-forming film before heating at the same temperature, if the resin film-forming film after heating-cooling is harder, the protective film-forming film is thermosetting.

When the protective film forming film is curable, the protective film forming film becomes a protective film by curing the protective film forming film attached to a workpiece such as a semiconductor wafer or a wafer obtained by dividing the workpiece. When the protective film forming film is non-curable, the protective film forming film is regarded as a formed protective film by picking up a chip obtained by dividing a workpiece such as a semiconductor wafer together with the protective film forming film attached to the wafer.

The thermosetting protective film-forming film can be formed using the thermosetting protective film-forming composition (III-1) described below.

[Protective film forming composition (III-1)] Examples of the composition for forming a thermosetting protective film include: Composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (see It is simply referred to as "protective film forming composition (III-1)") and the like.

[Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to a thermosetting protective film-forming film. The polymer component (A) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds. In the case of two or more kinds, these The combination and ratio of the polymer component (A) can be selected arbitrarily.

Examples of the polymer component (A) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like, preferably acrylic resins.

The said acrylic resin is resin containing the structural unit derived from the (meth)acrylate of a monomer. The term "derived from" here means that the aforementioned monomers are subjected to structural changes necessary for polymerization. In addition, in this specification, "(meth)acrylic acid" means the concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers. The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of an acrylic resin is more than the said lower limit, the shape stability (time-dependent stability at the time of storage) of a thermosetting protective film forming film improves. In addition, when the weight average molecular weight of the acrylic resin is not more than the above-mentioned upper limit, the thermosetting protective film-forming film becomes easy to follow the uneven surface of the adherend, and the formation of a film between the adherend and the thermosetting protective film can be further suppressed. gaps etc.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When Tg of an acrylic resin is more than the said lower limit, the adhesive force of a protective film and a support sheet is suppressed, and the peelability of a support sheet improves. Moreover, when Tg of an acrylic resin is below the said upper limit, the adhesive force of a thermosetting protective film formation film and a protective film with respect to an attachment object improves.

Examples of acrylic resins include: polymers of one or more (meth)acrylates; selected from (meth)acrylates, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, Copolymers of two or more monomers such as styrene and N-methylolacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, third-butyl (meth)acrylate, pentyl (meth)acrylate, (meth) ) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), Tridecyl (meth)acrylate, Myristyl (meth)acrylate (myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Cetyl (meth)acrylate Alkyl esters (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. Alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms; cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. ; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Dicyclopentenyloxy (meth)acrylate Cycloalkenyloxyalkyl (meth)acrylate such as ethyl ester; imine (meth)acrylate; (meth)acrylate containing glycidyl group such as glycidyl (meth)acrylate; (meth)acrylic acid Hydroxymethyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Base) 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; (meth)acrylate N-methylaminoethyl base) acrylate, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms in the amino group are replaced by groups other than hydrogen atoms.

The monomers constituting the acrylic resin may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these monomers can be selected arbitrarily.

The acrylic resin may also have functional groups such as vinyl groups, (meth)acryl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional groups in the acrylic resin may be bonded to other compounds through a crosslinking agent (F) described later, or may be directly bonded to other compounds without passing through a crosslinking agent (F). When the acrylic resin is bonded to other compounds through the functional group, the reliability of the package obtained using the composite sheet for forming a protective film tends to improve.

In the composition (III-1) for forming a protective film, regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, in In the thermosetting protective film forming film, the ratio of the content of the polymer component (A) to the total mass of the thermosetting protective film forming film) is preferably at least 1% by mass and less than 85% by mass, preferably More than 2% by mass to less than 65% by mass, more preferably more than 3% by mass to less than 50% by mass, more preferably more than 4% by mass to less than 40% by mass, especially preferably more than 5% by mass to less than 5% by mass 35% by mass, preferably more than 10% by mass and less than 30% by mass.

The polymer component (A) may also correspond to a thermosetting component (B). In this specification, when the protective film-forming composition (III-1) contains such components corresponding to both the polymer component (A) and the thermosetting component (B), the protective film-forming 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 forming a hard protective film by curing the thermosetting protective film forming film having thermosetting properties. The thermosetting component (B) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, The combination and ratio of these thermosetting components (B) can be selected arbitrarily.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins (thermosetting resins having an epoxy group), thermosetting polyimide resins (thermosetting resins having an imide bond). resin), thermosetting unsaturated polyester resin (thermosetting resin having an ester bond and an unsaturated bond between carbon atoms), etc., preferably an epoxy-based thermosetting resin. In this specification, a thermosetting polyimide resin is a general term for a polyimide precursor and a thermosetting polyimide which form a polyimide resin by thermosetting.

(Epoxy Thermosetting Resin) The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2). The epoxy-based thermosetting resin contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, The combination and ratio of these epoxy-type thermosetting resins can be selected arbitrarily.

・Epoxy resin (B1) The epoxy resin (B1) may also be an epoxy resin having an epoxy group in the molecule, and known epoxy resins may be mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A bisphenol A Glycidyl ether and its hydride, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, Bifunctional or higher epoxy compounds having two or more epoxy groups in the molecule, such as phenylene-skeleton epoxy resins.

An epoxy resin having an unsaturated hydrocarbon group can also be used as the epoxy resin (B1).

One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio of these epoxy resins (B1) can be selected arbitrarily.

・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 two or more functional groups which can react with an epoxy group in one molecule is mentioned, for example. Examples of the aforementioned functional groups include: phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, groups formed by anhydrided acid groups, etc., preferably phenolic hydroxyl groups, amino groups, or groups formed by anhydrided acid groups. group, more preferably a phenolic hydroxyl group or an amine group.

Among the thermosetting agents (B2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, arane Base type phenolic resin, etc. Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as "DICY") and the like.

The thermosetting agent (B2) may also be a thermosetting agent having an unsaturated hydrocarbon group.

The thermosetting agent (B2) is preferably solid at room temperature, and does not show hardening activity to the epoxy resin (B1), on the other hand, it is melted by heating and shows hardening activity to the epoxy resin (B1). Hardener (hereinafter sometimes referred to as "heat-activated latent epoxy resin hardener"). The aforementioned thermally active latent epoxy resin hardener is stably dispersed in the epoxy resin (B1) in the thermosetting protective film forming film at room temperature, but is miscible with the epoxy resin (B1) by heating, and is compatible with the epoxy resin (B1). The epoxy resin (B1) reacts. The storage stability of the composite sheet for forming a protective film is remarkably improved by using the aforementioned heat-activated latent epoxy resin hardener. For example, migration of the curing agent from the thermosetting protective film forming film to the adjacent support sheet or the adhesive layer for jigs is suppressed, effectively suppressing a decrease in the thermosetting properties of the thermosetting protective film forming film. Furthermore, since the heat curability of the thermosetting protective film forming film becomes high, the pick-up property of the wafer with a protective film mentioned later improves further.

Examples of the thermally active latent epoxy resin curing agent include onium salts, dibasic acid hydrazide, dicyandiamine, and amine adducts of curing agents.

In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, and is preferably 60 to 500, for example.

One kind of thermosetting agent (B2) may be used alone, or two or more kinds may be used in combination, and when using two or more kinds together, the combination and ratio of these thermosetting agents (B2) can be selected arbitrarily.

In the protective film forming composition (III-1) and the thermosetting protective film forming film, the content of the thermosetting agent (B2) is preferably 0.1 parts by mass based on 100 parts by mass of the epoxy resin (B1) 500 parts by mass, more preferably 1 part by mass to 200 parts by mass, more preferably 1 part by mass to 50 parts by mass, especially preferably 1 part by mass to 10 parts by mass. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening|curing of a thermosetting protective film formation film will progress more easily. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption rate of a thermosetting protective film forming film falls, and the reliability of the package obtained using the composite sheet for protective film formation improves further.

In the protective film forming composition (III-1), regardless of the type of the thermosetting component (B), the ratio of the content of the thermosetting component (B) to the total content of all components other than the solvent (also That is, in the thermosetting protective film forming film, the ratio of the content of the thermosetting component (B) to the total mass of the thermosetting protective film forming film) is preferably 1% by mass or more and less than 75% by mass, Preferably at least 2% by mass and less than 60% by mass, more preferably at least 3% by mass and less than 50% by mass, more preferably at least 4% by mass and less than 40% by mass, particularly preferably at least 5% by mass Up to less than 35% by mass, preferably more than 6% by mass and less than 30% by mass.

The thermosetting protective film forming film of the embodiment can exemplarily contain a polymer component (A) and a thermosetting component (B). The aforementioned polymer component (A) is an acrylic resin, and the thermosetting component (B) is made of epoxy resin. An epoxy-based thermosetting resin composed of resin (B1) and thermosetting agent (B2).

[Hardening Accelerator (C)] The protective film forming composition (III-1) and the thermosetting protective film forming film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the protective film forming composition (III-1). As a preferred hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol are listed; 2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxy Imidazoles such as methylimidazole (imidazoles in which more than one hydrogen atom is replaced by a group other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one hydrogen atom is replaced by an organic substituted phosphine); tetraphenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl borate and other tetraphenyl borates.

The curing accelerator (C) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds. In the case of two or more kinds, these The combination and ratio of the hardening accelerator (C) can be selected arbitrarily.

When the curing accelerator (C) is used, in the protective film forming composition (III-1) and the thermosetting protective film forming film, the curing is accelerated with respect to the content of the thermosetting component (B) of 100 parts by mass. The content of the agent (C) is preferably from 0.01 parts by mass to 10 parts by mass, more preferably from 0.1 parts by mass to 5 parts by mass. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) can be acquired more notably. In addition, when the content of the curing accelerator (C) is not more than the above-mentioned upper limit, for example, the movement of the highly polar curing accelerator (C) in the thermosetting protective film forming film under high temperature/high humidity conditions is suppressed. The effect of segregation by the adhesive interface side of the adherend becomes higher, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.

[Filler (D)] The protective film forming composition (III-1) and the thermosetting protective film forming film may contain a filler (D). In the protective film obtained by curing the thermosetting protective film-forming film by containing the filler (D) in the thermosetting protective film-forming film, the adjustment of the coefficient of thermal expansion becomes easy, and by adjusting the thermal expansion coefficient to that of the protective film The object to be formed is optimized, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved. In addition, the filler (D) contained in the film formed by the thermosetting protective film can also reduce the moisture absorption rate of the protective film or improve the heat dissipation.

The filler (D) can be any one of an organic filler and an inorganic filler, and is preferably an inorganic filler. Examples of preferable inorganic fillers include powders such as silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers. ; surface modification of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica or alumina.

The filler (D) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds. In the case of two or more kinds, these fillers The combination and ratio of materials (D) can be selected arbitrarily.

When the filler (D) is used, in the protective film forming composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the thermally cured In the protective film-forming film, the ratio of the content of the filler (D) to the total mass of the thermosetting protective film-forming film) is preferably greater than 5% by mass and less than 85% by mass, preferably greater than 20% by mass % to less than 85% by mass, more preferably greater than 30% by mass to less than 80% by mass, more preferably greater than 45% by mass to less than 80% by mass, especially preferably greater than 46% by mass to less than 75% by mass . When the content of the filler (D) is in such a range, the adjustment of the above-mentioned coefficient of thermal expansion becomes easier.

[Coupling agent (E)] The protective film forming composition (III-1) and the thermosetting protective film forming film may contain a coupling agent (E). By using as a coupling agent (E) what has a functional group which can react with an inorganic compound or an organic compound, the adhesiveness and adhesiveness of a thermosetting protective film forming film with respect to an adherend can be improved. In addition, by using the coupling agent (E), the water resistance of the protective film obtained by curing the thermosetting protective film-forming film can be improved without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group possessed by the polymer component (A) or the thermosetting component (B), more preferably a silane coupling agent. As a preferred aforementioned silane coupling agent, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, Ethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldi Ethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyl Trimethoxysilane, vinyltriacetyloxysilane, imidazole silane, etc.

The coupling agent (E) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds. In the case of two or more kinds, these coupling agents The combination and ratio of the mixture (E) can be selected arbitrarily.

In the case of using the coupling agent (E), in the protective film forming composition (III-1) and the thermosetting protective film forming film, relative to the total of the polymer component (A) and the thermosetting component (B) With a content of 100 parts by mass, the content of the coupling agent (E) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, especially preferably 0.1 to 5 parts by mass. When the above-mentioned content of the coupling agent (E) is more than the above-mentioned lower limit value, the dispersibility of the filler (D) to the resin can be improved more remarkably, or the difference between the thermosetting protective film forming film and the adherend can be obtained more remarkably. Improvement of adhesiveness and other effects achieved by using coupling agent (E). Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgassing is further suppressed.

[Crosslinking agent (F)] When using resins such as the above-mentioned acrylic resins having functional groups such as vinyl groups, (meth)acryl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds as the polymer component (A), The protective film-forming composition (III-1) and the thermosetting protective film-forming film may contain a crosslinking agent (F) for crosslinking the functional group with another compound. The storage elastic modulus E' of the thermosetting protective film-forming film can be easily adjusted to an appropriate range by crosslinking using a crosslinking agent (F).

Examples of the crosslinking agent (F) include: organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents agent (crosslinking agent with aziridine group), etc.

Examples of the above-mentioned organic polyvalent isocyanate compounds include isocyanate-based compounds such as toluene diisocyanate (TDI)-based, hexamethylene diisocyanate (HDI)-based, xylene diisocyanate (XDI)-based, and adducts of these diisocyanates. Linking agent (that is, a cross-linking agent having two or more isocyanate groups).

When using an organic polyvalent isocyanate compound as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction between the crosslinking agent (F) and the polymer component (A) can be easily applied to the thermosetting protective film. Form a film and introduce a cross-linked structure.

The crosslinking agent (F) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds. In the case of two or more kinds, these The combination and ratio of the crosslinking agent (F) can be selected arbitrarily.

In the case of using the crosslinking agent (F), the content of the crosslinking agent (F) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, most preferably 0.5 to 5 parts by mass. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) can be acquired more notably. Moreover, when the said content of a crosslinking agent (F) is below the said upper limit, the adhesive force of a thermosetting protective film forming film with respect to a support sheet, or the thermosetting protective film forming film with respect to a workpiece|work or a wafer can be suppressed. The excessive reduction of the adhesion force.

[Energy Beam Curing Compound (G)] The composition (III-1) for protective film formation may contain an energy ray curable compound (G). A film formed by a thermosetting protective film contains an energy ray-curable compound (G), and its properties can be changed by irradiation of energy ray.

Examples of the energy ray-curable compound (G) of the protective film forming composition (III-1) include the same ones as the energy ray-curable compound in the adhesive composition (I-1).

The energy ray-curable compound (G) contained in the protective film forming composition (III-1) may be only one kind, or may be two or more kinds. In the case of two or more kinds, these energy ray-curable compounds ( The combination and ratio of G) can be selected arbitrarily.

In the case of using the energy ray-curable compound (G), in the protective film-forming composition (III-1), the energy ray-curable compound ( The ratio of the content of G) is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 40% by mass, particularly preferably 3% by mass to 30% by mass.

[Photopolymerization initiator (H)] When the composition (III-1) for forming a protective film contains an energy ray-curable compound (G), a photopolymerization initiator may be included in order to more efficiently perform the polymerization reaction of the energy ray-curable compound (G) (H).

As a photoinitiator (H) of the composition (III-1) for protective film formation, the same thing as the photoinitiator in the adhesive agent composition (I-1) is mentioned.

The photopolymerization initiator (H) contained in the composition (III-1) for forming a protective film may be only one kind, or two or more kinds. In the case of two or more kinds, these photopolymerization initiators ( The combination and ratio of H) can be selected arbitrarily.

In the protective film forming composition (III-1), the content of the photopolymerization initiator (H) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the energy ray-curable compound (G) , more preferably 1 to 10 parts by mass, especially preferably 2 to 5 parts by mass.

[Color (I)] The protective film forming composition (III-1) and the thermosetting protective film forming film may contain a colorant (I). As a coloring agent (I), well-known coloring agents, such as an inorganic pigment, an organic pigment, and an organic dye, are mentioned, for example.

Examples of the aforementioned organic pigments and organic dyes include amine-based dyes, cyanine-based dyes, merocyanine-based dyes, crotonium-based dyes, squalenium-based dyes, azulenium-based dyes, Methyl dyes, naphthoquinone dyes, pyrylium dyes, phthalocyanine dyes, naphthalocyanine dyes, naphthalenamide dyes, azo dyes, condensed azo dyes, indigo dyes, pyrene Ketone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex dyes), dithiol metal complex dyes, indole phenol dyes, triallyl methane dyes, anthraquinone dyes, dioxazine dyes, naphthol dyes, and imine pigments, benzimidazolone pigments, pyranthrone pigments, and shihlin pigments, etc.

Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (Indium Tin Oxide, indium tin oxide) pigments, ATO (Antimony Tin Oxide, antimony tin oxide) pigments, etc.

The coloring agent (I) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds. The combination and ratio of the agents (I) can be selected arbitrarily.

When using a coloring agent (I), what is necessary is just to adjust content of the coloring agent (I) of a thermosetting protective film forming film suitably as needed. For example, the protective film is sometimes printed by laser irradiation, and by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, the light transmittance of the protective film can be adjusted, and the visibility of the printed characters can be adjusted. In addition, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, the designability of the protective film can be improved, or the grinding marks on the inner surface of the wafer can be made less visible. Considering this point, in the protective film forming composition (III-1), the ratio of the content of the coloring agent (I) (that is, the thermosetting protective film forming film) to the total content of all components other than the solvent is Among them, relative to the total mass of the thermosetting protective film forming film, the ratio of the content of the colorant (I) is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 7.5% by mass, especially preferably 0.1% by mass to 5% by mass. When the said content of a coloring agent (I) is more than the said lower limit, the effect by using a coloring agent (I) can be acquired more notably. Moreover, when the said content of a coloring agent (I) is below the said upper limit, the excessive fall of the translucency of a thermosetting protective film formation film is suppressed.

[General additive (J)] The protective film-forming composition (III-1) and the thermosetting protective film-forming film may contain general-purpose additives (J) within the range that does not impair the effect of the present invention. General-purpose additives (J) can be known additives, can be arbitrarily selected according to needs, and are not particularly limited, but examples of preferred additives include plasticizers, antistatic agents, antioxidants, getters, and the like.

The general-purpose additive (I) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds. In the case of two or more kinds, these general-purpose additives The combination and ratio of additives (I) can be selected arbitrarily. The content of the protective film-forming composition (III-1) and the general-purpose additive (I) of the thermosetting protective film-forming film is not particularly limited, and may be appropriately selected as necessary.

[solvent] The protective film forming composition (III-1) preferably further contains a solvent. The handling property of the protective film forming composition (III-1) containing a solvent becomes favorable. The aforementioned solvents are not particularly limited, but as preferred solvents, for example: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1- Alcohols such as butanol; Esters such as ethyl acetate and propyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides such as dimethylformamide and N-methylpyrrolidone (with amide bonded compounds), etc. The solvent contained in the protective film forming composition (III-1) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio of these solvents can be selected arbitrarily.

The solvent contained in the composition for forming a protective film (III-1) is preferably a methyl ethyl group from the viewpoint that the components contained in the composition for forming a protective film (III-1) can be more uniformly mixed. Ketones etc.

○Method for producing thermosetting protective film-forming composition The composition for protective film formation, such as the composition for protective film formation (III-1), is obtained by preparing each component which comprises this composition.

The production method of the composition for forming a thermosetting protective film can be produced by the same method as the production method of the adhesive composition described above, for example, except for the difference in the types of ingredients to be formulated.

○Adhesive layer for jigs The jig adhesive layer 16 is used to fix the protective film forming composite sheet 101 to a fixing jig 18 such as a ring frame. The adhesive layer 16 for the jig is formed by using the adhesive sheet for fixing the jig according to one embodiment of the present invention described above, and consists of the first adhesive layer 161, the core film 162, and the second adhesive layer 163 on the These are formed by laminating layers in the thickness direction.

The jig adhesive layer 16 is preferably ring-shaped.

○Manufacturing method of adhesive layer for jig The jig adhesive layer 16 composed of the ring-shaped first adhesive layer 161, the core material film 162 and the second adhesive layer 163, for example, can use an adhesive sheet for fixing the jig as shown in FIG. It is produced in the following manner.

The 2nd peeling film 152 which becomes a light surface peeling film is peeled and removed from the adhesive sheet for jig fixing shown in FIG. Then, a circular punching knife is touched from the side of the second adhesive layer 163 to cut the inner peripheral edges of the first adhesive layer 161 , the core material film 162 and the second adhesive layer 163 to remove the inner circular portion. Then, from the side of the second adhesive layer 163, contact the circular stamping knife in a concentric manner, and cut the outer peripheral edges of the first adhesive layer 161, the core material film 162 and the second adhesive layer 163, And remove the outer part. Thereby, the jig adhesive layer 16 formed by sequentially laminating the ring-shaped first adhesive layer 161 , the core material film 162 and the second adhesive layer 163 can be produced on the first release film 151 .

The composite sheet for forming a protective film provided with the adhesive agent for jigs of this embodiment can be suitably used for the manufacturing method of the wafer with a protective film mentioned later.

◇Manufacturing method of composite sheet for protective film formation The above-mentioned composite sheet for forming a protective film can be produced by laminating the above-mentioned layers in a corresponding positional relationship, and adjusting the shapes of some or all of the layers as necessary. The formation method of each layer is as described above.

The protective film forming film can be directly formed by applying a protective film forming composition on the adhesive layer laminated on the substrate. In this way, a new layer (hereinafter referred to as "second layer") is formed on any layer that has been laminated on the substrate (hereinafter referred to as "first layer") to form a continuous two-layer laminated structure (in other words, In the case of the laminated structure of the first layer and the second layer), the following method can be applied: coating the composition for forming the second layer on the first layer, and drying if necessary. Among them, the second layer is preferably formed in advance on the release film using the composition used to form the second layer, and the exposed surface of the formed second layer that is in contact with the aforementioned release film is the opposite side. Combine the exposed surface of the first layer to form a continuous two-layer laminated structure. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. The peeling film may be removed as necessary after forming the laminated structure.

For example, the composite sheet 101 for protective film formation shown in FIG. 2 can be produced by the following procedure. The support sheet 10 having the adhesive layer 12 laminated on the base material 11 and the protective film forming film 13 on the peeling film are produced, and the adhesive layer 12 of the supporting sheet 10 and the protective film forming film 13 are bonded together. , The third laminate including the support sheet 10 composed of the base material 11 and the adhesive layer 12, the protective film forming film 13, and the release film was produced. The release film was removed from the aforementioned third laminate. According to the above-mentioned manufacturing method of the adhesive layer for the jig, on the first peeling film 151, a device consisting of the ring-shaped first adhesive layer 161, the core material film 162 and the second adhesive layer 163 is sequentially laminated. The adhesive layer 16 is used, and the protective film forming film 13 of the third laminate from which the peeling film has been removed is bonded to the adhesive layer 16 for a jig.

The composite sheet 101 for protective film formation as shown in FIG. 2 can also be manufactured by the following procedure. The 3rd laminated body provided with the support sheet 10 which consists of the base material 11 and the adhesive agent layer 12, the protective film formation film 13, and the peeling film was produced. The second peeling film 152 is peeled off and removed from the adhesive sheet 1 for jig fixing shown in FIG. 1 . Then, from the side of the second adhesive layer 163, the circular stamping knife is abutted, leaving the first peeling film 151, and the inner peripheral edges of the first adhesive layer 161, the core material film 162 and the second adhesive layer 163 are cut. , and remove the inner circular part, on the first release film 151, make the first adhesive layer 161, the core material film 162 and the second adhesive layer 163 which are sequentially laminated from the inner circular part. Four layered body. The protective film forming film 13 exposed by peeling off the peeling film from the third laminate is bonded to the second adhesive layer 163 exposed by removing the inner circular portion of the fourth laminate. Afterwards, from the side of the base material 11, a circular stamping knife is abutted against the outside in a manner concentric with the inside circle, leaving the first release film 151, and the base material 11 and the adhesive layer 12 are cut. The support sheet 10, the protective film forming film 13, the second adhesive layer 163, the core material film 162, and the outer periphery of the first adhesive layer 161 are formed, and the outer parts are removed.

Here, an example of the case where a protective film-forming film and a ring-shaped jig adhesive layer are sequentially laminated on the adhesive layer is given, but for example, a protective film-forming film and a non-ring-shaped ( For example, when a jig with a rectangular frame shape) is laminated with an adhesive layer, etc., the target laminated structure can be selected arbitrarily.

In this way, since any layer other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming in advance on the release film and sticking to the surface of the target layer, it can be appropriately selected and used as needed. What is necessary is just to manufacture the composite sheet for protective film formation by layering in such a process.

The aforementioned composite sheet for forming a protective film may be in the form of a single sheet, preferably in the form of a roll.

[Manufacturing method of wafer with protective film] The above-mentioned composite sheet for forming a protective film according to one embodiment of the present invention can be used in a method of manufacturing a wafer with a protective film including a wafer and a protective film provided on the inner surface of the wafer.

The method for manufacturing a wafer with a protective film in this embodiment includes the following steps: affixing the adhesive layer for the jig in the composite sheet for forming the protective film to the jig for fixing, and affixing it to the inner surface of the workpiece The protective film forming film in the protective film forming composite sheet according to an embodiment of the present invention is formed by laminating the protective film forming film on the support sheet and the workpiece sequentially in the thickness direction of these. The step of the first laminated composite sheet: in the state where the peripheral edge of the first laminated composite sheet is attached to the fixture for fixing, the first laminated composite sheet is heated to harden the protective film forming film to form the protective film. Film, thereby making the second laminated composite sheet formed by laminating the aforementioned protective film and the aforementioned workpieces sequentially in the thickness direction on the aforementioned supporting sheet; by dividing the aforementioned workpiece on the aforementioned supporting sheet, the aforementioned protective film The film-forming film or the protective film obtained by hardening the aforementioned protective film-forming film is cut to produce a third laminated composite sheet in which a plurality of wafers with protective film-forming films or wafers with protective films are fixed on the aforementioned support sheet and a step of picking up the aforementioned wafer with a protective film forming film or the aforementioned wafer with a protective film in the aforementioned third laminated composite sheet from the aforementioned support sheet.

In this specification, the term "work" means a wafer or a semiconductor device panel. Examples of "wafers" include: semiconductor wafers made of elemental semiconductors such as silicon, germanium, and selenium, or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; semiconductor wafers made of insulators such as sapphire and glass. insulator wafer. The so-called "semiconductor device panel" refers to an aggregate in which a plurality of semiconductor devices are arranged in a planar manner and at least one electronic component is sealed with a sealing resin layer. A circuit is formed on one side of the workpiece, and in this specification, the surface of the workpiece on which the circuit is formed is referred to as a "circuit surface". Furthermore, the surface on the opposite side to the circuit surface in the workpiece is referred to as an "inner surface". The workpiece is divided into wafers by means of dicing or the like. In this specification, similarly to the case of the workpiece, the surface of the wafer on which the circuit is formed is referred to as the "circuit surface", and the surface of the wafer opposite to the circuit surface is referred to as the "inner surface". Preferably, protruding electrodes such as bumps and pillars are provided on the circuit surface of the workpiece and the circuit surface of the chip. The protruding electrodes are preferably made of solder.

[Manufacturing Method of Wafer with Protective Film in First Embodiment] 5A to 5H are cross-sectional views schematically illustrating a method of manufacturing a wafer with a protective film according to the first embodiment. Here, when the protective film forming film 13 is thermosetting, the case where the protective film forming composite sheet 101 shown in FIG. 2 is used as an example is described to describe a method of manufacturing a wafer with a protective film.

The method of manufacturing a wafer with a protective film in the first embodiment is a method of manufacturing a wafer 901 with a protective film provided with a wafer 90 and a protective film 130 ′ provided on the inner surface 90 b of the wafer 90; and, the aforementioned protective film The manufacturing method of the wafer has the following steps: the adhesive layer 16 for the jig in the composite sheet 101 for forming the protective film is attached to the jig 18 for fixing, and the adhesive layer 16 for the jig in the composite sheet 101 for forming the protective film is attached to the inner surface 9b of the workpiece 9. The protective film forming film 13 in the composite sheet 101, thereby making the first laminated composite sheet 501 formed by laminating the protective film forming film 13 and the workpiece 9 sequentially in the thickness direction of the support sheet 10; In the state where the peripheral edge of a laminated composite sheet 501 is attached to the jig 18 for fixing, the first laminated composite sheet 501 is heated to harden the protective film forming film 13 to form a protective film 13', which is fabricated on the support sheet 10, the second laminated composite sheet 502 formed by laminating the protective film 13' and the workpiece 9 sequentially in the thickness direction; by dividing the workpiece 9 in the second laminated composite sheet 502 on the support sheet 10, Cutting the protective film 13' to make a third laminated composite sheet 503 in which a plurality of wafers 901 with protective films are fixed on the support sheet 10; The wafer 901 is torn off from the supporting sheet 10, thereby performing the step of picking.

In the step of producing the aforementioned first laminated composite sheet in the method of manufacturing a wafer with a protective film in this embodiment, as shown in FIG. 5A and FIG. adhesive layer 16 for the jig, and attach the protective film forming film 13 in the protective film forming composite sheet 101 on the inner surface 9b of the workpiece 9, thereby making the protective film forming film 13 and the workpiece on the support sheet 10 9. The first laminated composite sheet 501 formed by laminating these sequentially in the thickness direction. In FIG. 5B , the first surface 13 a of the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the inner surface 9 b of the workpiece 9 . The peripheral portion of the first laminated composite sheet 501 is attached to the fixing jig 18 via the jig adhesive layer 16 . When using a workpiece provided with a back grinding tape on the circuit surface as the workpiece 9 , the back grinding tape is removed from the circuit surface of the workpiece 9 .

The attachment of the protective film forming film 13 to the workpiece 9 in the protective film forming composite sheet 101 can be performed by a known method. For example, the protective film forming film 13 may be attached to the workpiece 9 while being heated.

Then, in the step of producing the second laminated composite sheet, the first laminated composite sheet 501 is heated while the peripheral portion of the first laminated composite sheet 501 is attached to the fixing jig 18 ( FIG. 5C ). In this way, the protective film forming film 13 is hardened to form a protective film 13', and as shown in FIG. 5D, a second laminate consisting of the support sheet 10, the protective film 13', and the workpiece 9 is sequentially laminated in the thickness direction is produced. Composite sheet 502.

Reference numeral 13a' denotes a surface (sometimes referred to as "first surface" in this specification) that is the first surface 13a of the protective film forming film 13 in the protective film 13'. Reference numeral 13b' denotes a surface (sometimes referred to as "second surface" in this specification) that is the second surface 13b of the protective film forming film 13 in the protective film 13'.

Laser marking can be carried out by irradiating the protective film forming film 13 shown in FIG. 5B through the support sheet 10 (penetrating the support sheet 10), or by passing the support sheet 13' shown in FIG. 5D. The sheet 10 (through the support sheet 10 ) is irradiated with laser light for laser marking.

Then, in the step of making the third laminated composite sheet, the second laminated composite sheet 502 is cooled, and then, as shown in FIG. 5E , the workpiece 9 in the second laminated composite sheet 502 is divided on the supporting sheet 10. , and cut off the protective film 13'. The workpiece 9 is divided into individual pieces to form a plurality of wafers 90 .

The division of the workpiece 9 and the cutting of the protective film 13' can be performed by known methods. For example, the division of the workpiece 9 and the separation of the protective film 13' can be continuously performed by blade cutting, laser cutting by laser irradiation, or water cutting by spraying water containing abrasives. cut off. The protective film 13' is cut along the outer periphery of the wafer 90 regardless of the cutting method.

In this way, by dividing the workpiece 9 and cutting the protective film 13', the wafer 90 and the cut protective film provided on the inner surface of the wafer 90 (sometimes simply referred to as "protective film" in this specification) are obtained. 130' a plurality of wafers 901 with protective films. Reference numeral 130b' denotes a surface that is the second surface 13b' of the protective film 13' (sometimes referred to as "second surface" in this specification) among the protective film 130' after cutting.

In the step of manufacturing the aforementioned third laminated composite sheet, the third laminated composite sheet 503 in which the plurality of wafers 901 with protective films are fixed on the supporting sheet 10 is manufactured through the above steps.

Then, in the aforementioned picking step, as shown in FIG. 5F , the wafer 901 with the protective film in the third laminated composite sheet 503 is torn off from the supporting sheet 10 to be picked up.

In the aforementioned picking-up step, peeling occurs between the second surface 130b' of the protective film 130' in the wafer with protective film 901 and the first surface 12a of the adhesive layer 12 in the support sheet 10.

Here, a situation where the wafer 901 with a protective film is pulled off in the direction of arrow P by using a pull-off mechanism 7 such as a vacuum collet is shown. In addition, the sectional representation of the tear-off mechanism 7 is omitted here. The wafer 901 with a protective film can be picked up by a known method.

In the aforementioned picking step, the wafers 901 with a protective film are picked up for all the wafers 901 with a protective film of the target.

In the method of manufacturing a wafer with a protective film in this embodiment, the target wafer 901 with a protective film can be obtained by proceeding to the above-mentioned picking-up step.

After the aforementioned picking-up step, the fourth laminated composite sheet 504 remaining after the third laminated composite sheet 503 is pulled off the wafer 901 with a protective film is fixed by the adhesive layer 16 for the jig as shown in FIG. 5G Attached to the jig 18 for fixing. As shown in FIG. 5H , by peeling the fourth laminated composite sheet 504 from the fixing jig 18 , the fixing jig 18 returns to FIG. 5A for reuse.

In the method of manufacturing a wafer with a protective film according to the first embodiment, the second laminated composite sheet 502 is produced by heating the first laminated composite sheet 501 to harden the protective film forming film 13 to form the protective film 13'. , and then, the workpiece 9 in the second laminated composite sheet 502 is divided, and the protective film 13' is cut to produce a plurality of wafers 901 with protective films. When the protective film forming film 13 is thermosetting, the method of manufacturing the wafer with protective film of the present embodiment is not limited thereto, and the first laminated composite sheet 501 may not be heated, but as shown in FIG. 6A, The workpiece 9 in the first laminated composite sheet 501 is divided on the support sheet 10, and the protective film forming film 13 is cut to make the third laminated composite sheet 503. As shown in FIG. 6B, the obtained tool is picked up. A wafer 902 with a protective film is formed, and the protective film is thermally cured to obtain a wafer 901 with a protective film.

In the method for manufacturing a wafer with a protective film in this embodiment, since the adhesive layer 16 for the jig is formed using the adhesive sheet for fixing the jig of the above-mentioned embodiment, the fourth laminated composite sheet 504 is used for self-fixation. When the jig 18 is peeled off, the jig adhesive layer 16 can be easily peeled off from the fixing jig 18 without breaking.

[Method of Manufacturing Wafer with Protective Film of Second Embodiment] Using FIGS. 5A to 5B, FIGS. 6A to 6B, and FIGS. 5G to 5H, the protection film forming film 13 of the protective film forming composite sheet 101 shown in FIG. 2 is non-hardening. A method of manufacturing a wafer with a protective film will be described.

The method of manufacturing a wafer with a protective film in the second embodiment is a method of manufacturing a wafer 901 with a protective film provided with a wafer 90 and a protective film 130 ′ provided on the inner surface 90 b of the wafer 90; and, the aforementioned protective film The manufacturing method of the wafer has the following steps: the adhesive layer 16 for the jig in the composite sheet 101 for forming the protective film is attached to the jig 18 for fixing, and the adhesive layer 16 for the jig in the composite sheet 101 for forming the protective film is attached to the inner surface 9b of the workpiece 9. The protective film forming film 13 in the composite sheet 101, whereby the first laminated composite sheet 501 formed by laminating the protective film forming film 13 and the workpiece 9 sequentially in the thickness direction of the support sheet 10; by The step of dividing the workpiece 9 on the support sheet 10 and cutting the protective film forming film 13 to make a third laminated composite sheet 503 in which a plurality of wafers 902 with protective film forming films are fixed on the support sheet 10; And, the wafer 902 with the protective film forming film in the third laminated composite sheet 503 is pulled off from the support sheet 10, thereby performing the step of picking up.

In the method of manufacturing a wafer with a protective film in the present embodiment, in the step of producing the aforementioned first laminated composite sheet, as in the method of manufacturing a wafer with a protective film in the first embodiment, as shown in FIGS. 5A and 5B , Attach the adhesive layer 16 for the jig in the protective film forming composite sheet 101 to the fixing jig 18, and attach the protective film forming film 13 in the protective film forming composite sheet 101 to the inner surface 9b of the workpiece 9, In this way, the first laminated composite sheet 501 in which the protective film forming film 13 and the workpiece 9 are sequentially laminated in the thickness direction on the support sheet 10 is produced.

Laser marking can be performed by irradiating the protective film forming film 13 shown in FIG. 5B through the support sheet 10 (penetrating the support sheet 10).

Then, in the step of producing the third laminated composite sheet, as shown in FIG. 6A , the workpiece 9 in the first laminated composite sheet 501 is divided on the support sheet 10, and the protective film forming film 13 is cut. The workpiece 9 is divided into individual pieces to form a plurality of wafers 90 .

The division of the workpiece 9 and the cutting of the protective film forming film 13 may be performed by known methods. For example, the division of the workpiece 9 and the formation of the protective film 13 can be performed continuously by blade cutting, laser cutting by laser irradiation, or water cutting by spraying water containing abrasives. cut off. The protective film forming film 13 is cut along the outer periphery of the wafer 90 regardless of the cutting method.

In this way, by dividing the workpiece 9 and cutting the protective film forming film 13, a plurality of protective film forming films 130 having the wafer 90 and the cut protective film forming film 130 provided on the inner surface 90b of the wafer 90 can be obtained. Wafer 902 for film formation. Reference numeral 130b denotes a surface that is the second surface 13b of the protective film-forming film 13 among the protective-film-forming films 130 after cutting (may be referred to as "second surface" in this specification).

In the step of manufacturing the aforementioned third laminated composite sheet, the third laminated composite sheet 503 in which the plurality of wafers 902 with protective film forming films are fixed on the support sheet 10 is manufactured through the above steps.

Then, in the aforementioned picking-up step, as shown in FIG. 6B , the wafer 902 with the protective film forming film in the third laminated composite sheet 503 is torn off from the support sheet 10 to thereby perform picking-up. When the protective film forming film is non-hardening, by picking up the wafer 902 with the protective film forming film, the protective film forming film 130 becomes the protective film 130'.

In the aforementioned pick-up step, peeling occurs between the second surface 130b' of the protective film forming film 130 in the wafer with protective film forming film 902 and the first surface 12a of the adhesive layer 12 in the support sheet 10.

Here, a situation in which the wafer 902 with a protective film forming film is pulled off in the direction of arrow P by using a pull-off mechanism 7 such as a vacuum collet is shown. In addition, the sectional representation of the tear-off mechanism 7 is omitted here.

In the aforementioned picking-up step, the pickup of such wafers 902 with a protective film forming film is carried out for all the wafers 902 with a protective film forming film of the target.

In the method of manufacturing a wafer with a protective film in this embodiment, the target wafer 901 with a protective film can be obtained by proceeding to the above-mentioned picking-up step.

After the aforementioned picking-up step, the remaining fourth laminated composite sheet 504 is removed from the third laminated composite sheet 503 by peeling off the wafer 902 with a protective film forming film, as shown in FIG. Attached to the jig 18 for fixing. As shown in FIG. 5H , by peeling the fourth laminated composite sheet 504 from the fixing jig 18 , the fixing jig 18 returns to FIG. 5A for reuse.

In the method for manufacturing a wafer with a protective film in this embodiment, since the adhesive layer 16 for the jig is formed using the adhesive sheet for fixing the jig of the above-mentioned embodiment, the fourth laminated composite sheet 504 is used for self-fixation. When the jig 18 is peeled off, the jig adhesive layer 16 can be easily peeled off from the fixing jig 18 without breaking.

The description of the method of manufacturing a wafer with a protective film of this embodiment so far is for the manufacture of a wafer with a protective film of this embodiment when the composite sheet 101 for forming a protective film as shown in FIG. 2 is used. The method will be described, but in the method of manufacturing a wafer with a protective film in this embodiment, a protective film forming composite sheet 102 or a protective film forming composite sheet 104 as shown in FIGS. 3 to 4 can also be used. The composite sheet for protective film formation of this embodiment other than the composite sheet 101 is used.

◇Manufacturing method of substrate device (method of using chip with protective film) After obtaining a wafer with a protective film by the above-mentioned manufacturing method, except that the wafer with a protective film is used instead of the previous wafer with a protective film, it can be produced in the same way as the previous method of manufacturing the substrate device. Fabricate substrate devices.

For example, there may be mentioned a manufacturing method having the following steps: a wafer with a protective film obtained by using the aforementioned protective film forming film is picked up from a support sheet, and the protruding electrodes on the wafer with a protective film are brought into contact with the electrodes on the circuit board. connection pads, and a flip-chip connection step of electrically connecting the protruding electrodes with the connection pads on the circuit substrate.

Hereinafter, the present invention will be described in more detail by specific examples. However, this invention is not limited at all by the Example shown below. In addition, the content of the components other than methyl ethyl ketone shown below is the content of the object which does not contain a solvent.

(Adhesive composition 1 for jigs) Adhesive resin (i) made by copolymerizing butyl acrylate (BA, 88 parts by mass), ethyl acrylate (EA, 10 parts by mass) and 4-hydroxybutyl acrylate (4HBA, 2 parts by mass) Acrylic polymer (weight average molecular weight 1,300,000, glass transition temperature Tg: -51°C) (15 parts by mass), xylylene diisocyanate (XDI)-based cross-linking agent (Soken Chemical Co., Ltd.) as the cross-linking agent (ii) Co., Ltd., product name "TD-75") (0.01 parts by mass), resin containing carbon black as a pigment ("MULTILAC (registered trademark) A-903 BLACK", manufactured by Toyocolor Co., Ltd., 2.82 parts by mass (of which 0.704 parts by mass of pigment)) and methyl ethyl ketone as a solvent were stirred to prepare adhesive composition 1 for jigs with a solid content concentration of 20 mass%.

(Adhesive composition 2 for jigs) Adhesive resin (i) made of butyl acrylate (BA, 89 parts by mass), 4-hydroxybutyl acrylate (4HBA, 1 part by mass) and acryloylmorpholine ester (ACMO, 10 parts by mass) Copolymerized acrylic polymer (weight average molecular weight 800,000, glass transition temperature Tg: -43°C) (34.3 parts by mass)), toluene diisocyanate-based crosslinking agent (Tosoh) as the crosslinking agent (ii) Co., Ltd., trade name "Coronate L", 0.05 parts by mass), resin containing carbon black as a pigment ("MULTILAC (registered trademark) A-903 BLACK", manufactured by Toyocolor Co., Ltd., 2.82 parts by mass (of which the pigment 0.704 parts by mass)) and methyl ethyl ketone as a solvent were stirred to prepare adhesive composition 2 for jigs with a solid content concentration of 20 mass%.

(Adhesive composition 3 for jigs) Acrylic polymer (weight average molecular weight 900000, glass Transition temperature Tg: -53°C) (33.4 parts by mass)), xylylenediisocyanate (XDI)-based crosslinking agent (manufactured by Soken Chemical Co., Ltd., trade name "TD-75") as the crosslinking agent (ii) ") (0.13 parts by mass), a resin containing carbon black as a pigment ("MULTILAC (registered trademark) A-903 BLACK", manufactured by Toyocolor Co., Ltd., 2.82 parts by mass (0.704 parts by mass of the pigment)), and The solvent methyl ethyl ketone was stirred to prepare the adhesive composition 3 for jigs with a solid content concentration of 20% by mass.

(Adhesive composition 4 for jigs) Adhesive resin (i) was prepared by copolymerizing butyl acrylate (BA, 89 parts by mass), 4-hydroxybutyl acrylate (4HBA, 1 part by mass) and dimethylacrylamide (10 parts by mass). Acrylic polymer (weight average molecular weight 900,000, glass transition temperature Tg: -44°C) (37.4 parts by mass)), xylylene diisocyanate (XDI) as crosslinking agent (ii) Chemical Co., Ltd., product name "TD-75") (0.13 parts by mass), resin containing carbon black as a pigment ("MULTILAC (registered trademark) A-903 BLACK", manufactured by Toyocolor Co., Ltd., 2.82 parts by mass (wherein the pigment is 0.704 parts by mass))) and methyl ethyl ketone as a solvent were stirred to prepare adhesive composition 4 for jigs with a solid content concentration of 20 mass%.

(Adhesive composition 5 for jigs) Adhesive resin (i) made by copolymerization of butyl acrylate (BA, 69.5 parts by mass), methyl acrylate (MA, 30 parts by mass) and 2-hydroxyethyl acrylate (2HEA, 0.5 parts by mass) Acrylic polymer (weight average molecular weight: 500,000, glass transition temperature Tg: -38°C) (100 parts by mass)), as the crosslinking agent (ii), toluene diisocyanate-based crosslinking agent ("Coronate L", 5 parts by mass), and methyl ethyl ketone as a solvent were stirred to prepare adhesive composition 5 for jigs with a solid content concentration of 20 mass%.

[Example 1] In Example 1, the adhesive sheet 1 for jig fixing shown in FIG. 1 and the composite sheet 101 for protective film formation provided with the protective film forming film shown in FIG. 2 were manufactured as follows.

(1) Production of adhesive sheets for jig fixing A release film (SP-PET381031 manufactured by Lintec Co., Ltd.) formed by forming a silicone-based release agent layer on one side of a polyethylene terephthalate (PET) film with a thickness of 38 μm (as On the peeling-treated surface of the first peeling film), apply the adhesive composition 1 for jigs obtained above, heat and dry at 115° C. for 3 minutes, and form a first peeling surface with a thickness of 5 μm on the peeling-treated surface of the first peeling film. Adhesive layer. On one side of a non-stretched polypropylene film (manufactured by SunTox Co., Ltd., trade name "TP02", thickness 40 μm, hereinafter referred to as "core film A") with corona treatment on both sides as the core film The first surface is attached to the exposed surface of the first adhesive layer. After that, a release film (manufactured by Lintec Co., Ltd., product name "SP") formed by forming a polysiloxane-based release agent layer on one side of a polyethylene terephthalate (PET) film with a thickness of 38 μm was used. -PET381130") (as the second release film) (as the second release film) is similarly coated with the adhesive composition 1 for jigs obtained above, heated and dried at 115°C for 3 minutes, and applied to the release treatment surface of the second release film A second adhesive layer with a thickness of 5 μm was formed on it. By attaching the exposed surface of the second adhesive layer to the second surface of the other side of the core material film A, the first adhesive layer, the core material film, and the second adhesive layer are sequentially formed in the thickness direction of these The jig fixing adhesive sheet of Example 1 formed by lamination. The adhesive sheet for jig fixing in Example 1 is formed by sequentially laminating the first release film, the first adhesive layer, the core film A, the second adhesive layer, and the second release film.

(2) Fabrication of the first laminate including the protective film forming film The following components (a) to (g) were mixed, diluted with methyl ethyl ketone so that the solid content concentration became 50% by mass, and a composition for forming a protective film was prepared.

(a) Polymer composition: (meth)acrylate copolymer (20 mass parts of n-butyl acrylate, 50 mass parts of methyl acrylate, 15 mass parts of glycidyl methacrylate, and 15 mass parts of 2-hydroxyethyl acrylate 120 parts by mass of a copolymer obtained by copolymerization (weight average molecular weight: 800,000, glass transition temperature: -5.6°C) (in terms of solid content, the same applies hereinafter). (b-1) Thermosetting component: 75 parts by mass of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828", epoxy equivalent 184 g/eq to 194 g/eq). (b-2) Thermosetting component: 25 parts by mass of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent 800 g/eq to 900 g/eq). (c) Thermally active latent epoxy resin hardener: 3 parts by mass of dicyandiamine (manufactured by ADEKA Co., Ltd.: Adeka Hardener EH3636AS, amount of active hydrogen: 21 g/eq). (d) Hardening accelerator: 3 parts by mass of 2-phenyl-4,5-dimethylolimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "Curezol 2PHZ"). (e) Filler: 290 parts by mass of silica filler (manufactured by Admatechs Co., Ltd., product name "SC2050MA", average particle diameter: 0.5 μm). (f) Coloring agent: 1.2 parts by mass of carbon black (manufactured by Mitsubishi Chemical Corporation, product name "#MA650", average particle diameter: 28 nm). (g) Silane coupling agent: (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") 2 parts by mass.

As the third release film, a release film (manufactured by Lintec Corporation, product name "SP-PET381031") was prepared. As the fourth release film, a release film (manufactured by Lintec Corporation, product name "SP-PET381130") was prepared.

First, on the peeling surface of the third peeling film, the above-mentioned protective film-forming composition was applied with a knife coater so that the thickness of the finally obtained protective film-forming film could be 25 μm, and dried. , forming a protective film to form a film. After that, the release surface of the fourth release film was laminated on the protective film forming film to obtain a first laminate composed of the third releasing film, the protective film forming film (thickness: 25 μm), and the fourth releasing film.

(3) Fabrication of the second laminate including the support sheet The following components (h) and (i) were mixed and diluted with methyl ethyl ketone so that the solid content concentration became 25% by mass to prepare an adhesive composition.

(h) Adhesive main agent: (meth)acrylate copolymer (60 mass parts of 2-ethylhexyl acrylate, 30 mass parts of methyl methacrylate and 10 mass parts of 2-hydroxyethyl acrylate obtained by copolymerization Copolymer, weight average molecular weight: 600,000) 100 parts by mass. (i) Crosslinking agent: 20 parts by mass of xylene diisocyanate adduct of trimethylolpropane (manufactured by Mitsui Takeda Chemical Co., Ltd., product name "Takenate D110N").

As the fifth release film, a release film (manufactured by Lintec Corporation, product name "SP-PET381031") in which a silicone-based release agent layer was formed on one side of a PET film with a thickness of 38 μm was prepared.

On the peeling surface of the fifth peeling film, the aforementioned adhesive composition was applied so that the thickness of the finally obtained adhesive layer would be 5 μm, and dried at 100° C. for 1 minute to form an adhesive layer. Afterwards, a polypropylene film (thickness: 80 μm) was attached to the adhesive layer as a substrate to obtain a second laminate composed of a support sheet (consisting of the substrate and the adhesive layer) and a fifth release film.

(4) Production of the third laminated body The fourth release film was peeled from the first laminate obtained in (2) above to expose the protective film forming film. On the other hand, the fifth release film was peeled off from the second laminate obtained in the above (3) to expose the adhesive layer. In such a way that the exposed adhesive layer is in contact with the exposed protective film to form a film, the first laminate and the second laminate are bonded at a rate of 0.5m/min to obtain a support sheet (made of a substrate and an adhesive layer) constituted), a protective film forming film, and a third release film are laminated to form a third laminate.

(5) Production of composite sheets for protective film formation The second peeling film 152 was peeled off from the jig fixing adhesive sheet 1 of Example 1 and removed. Then, from the side of the second adhesive layer 163, the circular stamping knife is abutted, leaving the first peeling film 151, and the inner peripheral edges of the first adhesive layer 161, the core material film 162 and the second adhesive layer 163 are cut. , and remove the inner circular part, make the first adhesive layer 161, the core material film 162 and the second adhesive layer 163 laminated in sequence on the first release film 151 with the inner circular part removed. laminated body. At this time, the diameters of the inner peripheral edges of the first adhesive layer 161 , the core material film 162 , and the second adhesive layer 163 were set to 185 mm.

The third release film was peeled off from the third laminate, and the exposed protective film-forming film 13 was bonded to the second adhesive layer 163 exposed by removing the inner circular portion in the fourth laminate at a rate of 0.5 m/min. Afterwards, from the side of the base material 11, the circular stamping knife is abutted against the outside in such a way that it is concentric with the inside circle, leaving the first release film 151 in the adhesive sheet 1 for fixing the jig. The outer peripheral edges of the support sheet 10, the protective film forming film 13, the second adhesive layer 163, the core material film 162, and the first adhesive layer 161 composed of the base material 11 and the adhesive layer 12 are punched, and the outer edges are removed. For the part, the composite sheet 101 for protective film formation of Example 1 was produced. At this time, the diameter of the outer peripheral edge of the composite sheet 101 for protective film formation of Example 1 which has the adhesive agent layer 16 for jigs was 210 mm.

The composite sheet 101 for forming a protective film in Example 1 is an adhesive sheet (that is, the support sheet 10) formed by laminating the adhesive layer 12 (thickness: 5 μm) on the substrate 11, and the adhesive layer laminated on the adhesive sheet The protective film forming film 13 on the side 12, the annular adhesive layer 16 for jigs laminated on the peripheral portion of the protective film forming film 13 on the side opposite to the adhesive sheet, and the adhesive layer 16 for jigs laminated on the adhesive layer 16 and The protective film forming film 13 is constituted by the first release film 151 on the opposite side. The protective film-forming composite sheet 101 of Example 1 corresponds to the laminate in FIG. 2 having the release film 15 .

[Example 2] Except that the core film of the adhesive sheet for jig fixing in Example 1 was changed to a linear low-density polyethylene film (manufactured by AICELLO Co., Ltd., trade name "N-606", thickness 40 μm) with corona treatment on both sides. , hereinafter referred to as "core material film B"), the jig fixing adhesive sheet of Example 2 was produced in the same manner as the jig fixing adhesive sheet of Example 1.

[Example 3] In addition to changing the core film of the adhesive sheet for jig fixing in Example 1 to a non-stretched polypropylene film (manufactured by Japan MATAI Co., Ltd., trade name "MK12", thickness 40 μm, hereinafter referred to as The adhesive sheet for jig fixing of Example 3 was produced in the same manner as the adhesive sheet for jig fixing of Example 1 except for "core material film C".

[Example 4] Except that the core material film in the adhesive sheet for jig fixing in Example 1 was changed to a non-stretched polypropylene film (thickness 50 μm, Young’s modulus at 23°C 460 MPa and F-5 value (5 Stress at tensile time) 20MPa film, hereinafter referred to as "core material film D"), the adhesive sheet for fixing the jig of Example 4 was produced in the same manner as the adhesive sheet for fixing the jig of Example 1. piece.

[Example 5] Except that the core film of the jig fixing adhesive sheet in Example 1 was changed to a polyvinyl chloride film (manufactured by Okamoto Co., Ltd., trade name "OSGP42B-D23", thickness 50 μm, hereinafter referred to as "core film E") ), the adhesive sheet for jig fixing of Example 5 was produced in the same manner as the adhesive sheet for jig fixing of Example 1.

[Example 6] In the adhesive sheet for jig fixing of Example 5, except that the adhesive composition 1 for jig is changed to the adhesive composition 2 for jig, it is made in the same manner as the adhesive sheet for fixing jig of Example 5. The adhesive sheet for jig fixing of Example 6 was produced.

[Example 7] Except changing the adhesive composition 1 for jig in the adhesive sheet for fixing jig of Example 5 to the adhesive composition 3 for jig, it is made in the same manner as the adhesive sheet for fixing jig of Example 5. The adhesive sheet for jig fixing of Example 7 was produced.

In the composite sheet for forming a protective film of Example 1, the adhesive sheet for fixing jigs of Example 1 is changed to the adhesive sheets for fixing jigs of Examples 2 to 7, and the protective film of Example 1 is used. In the same manner as the composite sheet for formation, the composite sheets for protective film formation of Examples 2 to 7 were produced.

[Comparative example 1] Except changing the adhesive composition 1 for jig in the adhesive sheet for fixing jig of Example 4 to the adhesive composition 4 for jig, it is made in the same manner as the adhesive sheet for fixing jig of Example 2. The jig fixing adhesive sheet of Comparative Example 1 was produced.

[Comparative example 2] The jig fixing sheet of Comparative Example 2 was produced in the same manner as the jig fixing adhesive sheet of Comparative Example 1, except that the core material film in the jig fixing adhesive sheet of Comparative Example 1 was changed to the aforementioned core material film B. Use an adhesive sheet.

[Comparative example 3] The jig fixing sheet of Comparative Example 3 was produced in the same manner as the jig fixing adhesive sheet of Comparative Example 1, except that the core material film in the jig fixing adhesive sheet of Comparative Example 1 was changed to the aforementioned core material film E. Use an adhesive sheet.

[Comparative example 4] In addition to changing the jig adhesive composition 4 in the jig fixing adhesive sheet of Comparative Example 1 to jig adhesive composition 5, and changing the core material film to a different type of plasticizer from the core material film E Except for the polyvinyl chloride film (manufactured by Okamoto Co., Ltd., trade name "OSGP42B", thickness 50 μm, hereinafter referred to as "core material film I"), the method was the same as that of the adhesive sheet for fixing the jig of Comparative Example 1. The adhesive sheet for jig fixing of Comparative Example 4 was produced.

In the protective film-forming composite sheet of Example 1, the adhesive sheet for jig fixing of Example 1 was changed to the adhesive sheet for jig fixing of Comparative Example 1 to Comparative Example 4, and the protective film of Example 1 was used. In the same manner as the composite sheet for formation, the composite sheets for protective film formation of Comparative Examples 1 to 4 were produced.

[Tensile test before heating] The jig fixing adhesive sheets of Examples 1 to 7 and Comparative Examples 1 to 4 were cut into strips with a width of 10 mm and a length of 80 mm. The second peeling film 152 is peeled off from the second adhesive layer 163 , and further, the first peeling film 151 is peeled off from the first adhesive layer 161 . The universal tensile test was used for the test piece before heating of the adhesive sheet for jig fixing, which is composed of the first adhesive layer 161, the core material film 162, and the second adhesive layer 163 laminated in the thickness direction. Machine ("AUTOGRAPH" manufactured by Shimadzu Corporation), under the environment of 23 ℃ and 50% RH, the distance between chucks is 50 mm, and the tensile speed is 200 mm/min. The tensile test is carried out to obtain the elongation at break before heating Degree (X0)[%]. The results are shown in Table 1.

[Tensile test after heating] The jig fixing adhesive sheets of Examples 1 to 7, and Comparative Examples 1 to 4 were cut into strips with a width of 10 mm and a length of 80 mm, heated at 130° C. for 2 hours, and left to cool. The second peeling film 152 is peeled off from the second adhesive layer 163 , and further, the first peeling film 151 is peeled off from the first adhesive layer 161 . A universal tensile test was used for the heated test piece of the jig fixing adhesive sheet composed of the first adhesive layer 161, the core material film 162, and the second adhesive layer 163 laminated sequentially in the thickness direction. Machine (manufactured by Shimadzu Corporation "AUTOGRAPH"), under the environment of 23 ℃ and 50% RH, the distance between chucks is 50 mm, and the tensile speed is 200 mm/min. The tensile test is carried out to obtain the breaking strength after heating (Ah) [N/10mm], and elongation at break (Xh) [%] after heating. The results are shown in Table 1.

[Measurement of 180° tear-off adhesion (Bh) after heating] Cut the jig-fixing adhesive sheets of Examples 1 to 7, and Comparative Examples 1 to 4 into strips with a width of 10 mm and a length of 250 mm, and make the first stick on the side of the fixing jig The adhesive layer 161 is exposed. The exposed first adhesive layer of the test pieces of Examples 1 to 7, and Comparative Examples 1 to 4 before heating was attached to a SUS304 plate (manufactured by PALTECH Co., Ltd.) by making a 2 kg roller back and forth once. "SUS304♯1200HL (hairline), thickness 1000μm, size 70mm×150mm") on the ♯1200HL polished surface. Heat at 130°C for 2 hours. After leaving to cool until it reaches room temperature (23°C), use a universal tensile testing machine ("AUTOGRAPH" manufactured by Shimadzu Corporation) in an environment of 23°C and 50%RH to make the first test piece before heating The surface of the adhesive layer and SUS304 in contact with each other is at an angle of 180°, and the test piece before heating is peeled off from the SUS304 at a peeling speed of 300mm/min, and the first adhesive layer of the test piece before heating at this time is measured And the peel force between SUS304. Among the measured values when the test piece was peeled over a length of 50 mm before heating, the measured value corresponding to the initial peeled length of 5 mm and the measured value corresponding to the final peeled length of 5 mm were respectively excluded, and the average of the remaining measured values was taken as the pair after heating The 180° pull-off adhesion of SUS (Bh) (N/10mm). The results are shown in Table 1.

(Calculation of Ratio (Ah/Bh)) For the adhesive sheets for fixing jigs of Examples 1 to 7, and Comparative Examples 1 to 4, the ratio (Ah/Bh) can be obtained by dividing the aforementioned breaking strength (Ah) by the aforementioned 180° peel-off adhesive force (Bh) to calculate and obtain. The results are shown in Table 1.

(Calculation of ratio (Xh/X0)) For the jig fixing adhesive sheets of Examples 1 to 7, and Comparative Examples 1 to 4, the ratio (Xh/X0) can be obtained by dividing the aforementioned elongation at break (Xh) by the aforementioned elongation at break (X0 ) to calculate and obtain. The results are shown in Table 1.

(Evaluation of Peelability of Adhesive Sheet for Jig Fixing) From the protective film forming composite sheets of Examples 1 to 7, and Comparative Examples 1 to 4, the first release film is peeled off respectively, and the central part of the exposed protective film forming film is attached to a silicon wafer (diameter 6 inches, thickness 350μm, ♯2000), and the first adhesive layer of the exposed jig fixing adhesive sheet is loaded on the ring frame for cutting, and it is crimped by a laminator at 70°C and 0.3m/min , and leave for 20 minutes. With the first adhesive layer of the jig fixing adhesive sheet attached to the ring frame for dicing, heat at 130°C for 2 hours to harden the thermosetting protective film forming film, and then leave to cool to room temperature (23°C). Then, the protective film of the silicon wafer and the part following the silicon wafer was peeled off from the supporting sheet, and the protective film forming composite sheets of Examples 1 to 7 and Comparative Examples 1 to 4 were removed from the support sheet. The formers were peeled under conditions of peeling speeds of 11 mm/s and 23 mm/s so that the surfaces that were in contact with each other formed an angle of 180°. Observe the state of the jig fixing adhesive sheet after peeling off. The peelability of the jig fixing adhesive sheet was evaluated according to the following criteria. The results are shown in Table 1. A: When peeling off, the adhesive layer for jigs was not broken. B: When peeling off, the adhesive layer for jigs was not broken, but cracks occurred. C: When peeling, the adhesive layer for jigs was broken.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Adhesive composition for jig 1 1 1 1 1 2 3 4 4 4 5 Core film A B C D. E. E. E. D. B E. I Elongation at break before heating (X0)[%] 603 780 1029 1101 330 330 330 1101 780 330 320 Breaking strength after heating (Ah) [N/10mm] 20 12 26 13 14 14 14 13 12 14 12 Elongation at break after heating (Xh)[%] 579 499 663 718 364 364 364 718 499 364 343 180°Tear-off Adhesion (Bh)[N/10mm] 5.96 6.36 6.24 6.36 6.16 6.88 8.32 11.52 11.08 11.32 9.92 Ratio (Ah/Bh) 3.36 1.89 4.17 2.04 2.27 2.03 1.68 1.13 1.08 1.24 1.21 Ratio (Xh/X0) 0.960 0.640 0.644 0.652 1.103 1.103 1.103 0.652 0.640 1.103 1.072 Peelability (peeling speed: 23mm/s) ○ ○ ○ ○ ○ ○ △ x x x x Peelability (peeling speed: 11mm/s) ○ ○ ○ ○ ○ ○ ○ x x x x

The adhesive sheets for fixing jigs of Examples 1 to 7, and the composite sheets for forming protective films of Examples 1 to 7 formed using these adhesive sheets for fixing jigs, were used in the production of protective films. When wafering, the adhesive layer for the jig can be easily peeled off from the jig for fixing without breaking. In the test pieces of the adhesive sheets for fixture fixing of Examples 1 to 7 heated at 130°C for 2 hours, the breaking strength (Ah), 180° tear-off adhesive force (Bh), and the ratio (Ah/Bh) Within the specified numerical range, not only after the heating step when the protective film forming film is thermosetting, even when the protective film forming film is energy ray curable or the protective film forming film is non-curable, the When manufacturing a wafer with a protective film, the adhesive layer for the jig can also be easily peeled off from the jig for fixing without breaking. Furthermore, when the composite sheet for forming a protective film is poorly adhered to the workpiece, the adhesive layer for jigs can be maintained without breaking even in the step of peeling off the workpiece to make the workpiece reusable (reworked). Self-fixing jigs are easily peeled off. [Industrial availability]

The present invention is applicable to the manufacture of various substrate devices represented by semiconductor devices.

1: Adhesive sheet for jig fixing 7: Pull-off mechanism 10, 20: Support sheet 10a, 20a: One side surface (first surface) of support sheet 101, 102, 104: Composite sheet for protective film formation 11: Base material 11a: Base One side surface (first surface) of material 11 12: adhesive layer 12a: one side surface (first surface) of adhesive layer 13, 23, 130: protective film forming film 13a, 23a: one of protective film forming film Side surfaces (first surface) 13b, 23b, 130b: the other side surface (second surface) of the protective film forming film 13': protective film 13a': one side surface (first surface) 13b of the protective film ': the other side of the protective film (second surface) 130': cut protective film 130b': the second surface of the protective film 15: release film 151: first release film 152: second release film 16: Adhesive layer 16a for jig: one side (first surface) of the adhesive layer for jig 161: first adhesive layer 162: core material film 163: second adhesive layer 18: jig 501 for fixing : first laminated composite sheet 502: second laminated composite sheet 503: third laminated composite sheet 504: fourth laminated composite sheet 9: workpiece 9b: inner surface of workpiece 90: wafer 90b: inner surface of wafer 901: protective film Wafer 902: a wafer with a protective film forming film

[ Fig. 1 ] is a cross-sectional view schematically showing an example of an adhesive sheet for fixing a jig according to an embodiment of the present invention. [ Fig. 2] Fig. 2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 3] Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 4] Fig. 4 is a cross-sectional view schematically showing yet another example of the composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 5A] Fig. 5A is a cross-sectional view schematically illustrating part of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 5B] Fig. 5B is a cross-sectional view schematically illustrating part of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 5C] Fig. 5C is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 5D ] is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 5E ] is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [FIG. 5F] is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 5G ] is a cross-sectional view schematically illustrating part of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 5H ] is a cross-sectional view schematically illustrating part of a method of manufacturing a wafer with a protective film according to an embodiment of the present invention. [ Fig. 6A] Fig. 6A is a cross-sectional view schematically illustrating part of a method of manufacturing a wafer with a protective film according to a second embodiment of the present invention. [ Fig. 6B ] is a cross-sectional view schematically illustrating part of a method of manufacturing a wafer with a protective film according to a second embodiment of the present invention. [ Fig. 7] Fig. 7 is a partial cross-sectional view schematically illustrating an example of a conventional method of manufacturing a wafer with a protective film.

1: Adhesive sheet for jig fixing

151: The first release film

152: Second release film

161: first adhesive layer

162: core film

163: second adhesive layer

Claims (12)

An adhesive sheet for fixing a jig, which is used for a protective film forming composite sheet provided with a protective film forming film; The first adhesive layer, the core material film, and the second adhesive layer are sequentially laminated in the thickness direction of these layers; The breaking strength (Ah) obtained by the tensile test of the test piece after heating the above-mentioned fixture-fixing adhesive sheet at 130°C for 2 hours is relative to the 180° peel-off adhesion force of the test piece to SUS304 after heating at 130°C for 2 hours (Bh) ratio (Ah/Bh) is 1.25 or more. The adhesive sheet for fixture fixing as described in claim 1, wherein the aforementioned 180° tear-off adhesive force (Bh) is 2.0N/10mm to 12N/10mm. The adhesive sheet for fixing a jig according to claim 1 or 2, wherein the breaking strength (Ah) is 6N/10mm or more. The adhesive sheet for fixing a jig as described in any one of Claims 1 to 3, wherein the first adhesive layer and the second adhesive layer are formed of an adhesive composition for a jig containing an acrylic resin, and the aforementioned The weight average molecular weight of the acrylic resin is more than 700,000. The adhesive sheet for jig fixing according to claim 4, wherein the acrylic resin does not have a structural unit derived from (meth)acrylic acid. The adhesive sheet for fixture fixing according to any one of Claims 1 to 5, wherein the constituent material of the core film includes linear low-density polyethylene, non-extended polypropylene or polyvinyl chloride. The adhesive sheet for fixture fixing as described in any one of claims 1 to 6, wherein the elongation at break obtained from the tensile test of the test piece after the above-mentioned adhesive sheet for fixture fixing is heated at 130°C for 2 hours ( Xh) is 100% or more. The adhesive sheet for fixture fixing as described in any one of claims 1 to 7, wherein the elongation at break obtained from the tensile test of the test piece after the above-mentioned adhesive sheet for fixture fixing is heated at 130°C for 2 hours ( Xh) The ratio (Xh/X0) to the elongation at break (X0) obtained by the tensile test of the test piece before heating is 0.10 to 1.50. A composite sheet for forming a protective film, comprising: a support sheet, a protective film forming film provided on one side of the support sheet, and a film provided on the one side of the support sheet or on the protective film. forming an adhesive layer for jigs near the periphery of the first surface on the opposite side of the support sheet in the film; The aforementioned jig adhesive layer is formed using the jig fixing adhesive sheet described in any one of Claims 1 to 8. The composite sheet for forming a protective film according to claim 9, wherein the protective film forming film is thermosetting. A method of manufacturing a wafer with a protective film, the aforementioned wafer with a protective film comprises: a wafer, and a protective film disposed on the inner surface of the aforementioned wafer; and, the manufacturing method of the aforementioned wafer with a protective film has the following steps: Attach the adhesive layer for the jig in the composite sheet for forming a protective film to the jig for fixing, and attach the protective film in the composite sheet for forming a protective film as described in claim 9 or 10 on the inner surface of the workpiece Forming a film, whereby the first laminated composite sheet is formed by laminating the protective film forming film on the supporting sheet and the aforementioned workpieces sequentially in the thickness direction; By dividing the workpiece on the support sheet and cutting the protective film forming film or the protective film obtained by hardening the protective film forming film, a plurality of wafers with protective film forming films or wafers with protective film forming films are produced. A step in which the chip of the protective film is fixed on the third laminated composite sheet on the aforementioned support sheet; and The step of picking up the wafer with the protective film forming film or the wafer with the protective film in the third laminated composite sheet is pulled off from the support sheet. A method of manufacturing a wafer with a protective film, the aforementioned wafer with a protective film comprises: a wafer, and a protective film disposed on the inner surface of the aforementioned wafer; and, the manufacturing method of the aforementioned wafer with a protective film has the following steps: Attach the adhesive layer for the jig in the composite sheet for forming a protective film to the jig for fixing, and attach the protective film forming film in the composite sheet for forming a protective film as described in Claim 10 on the inner surface of the workpiece , the step of making a first laminated composite sheet formed by laminating the aforementioned protective film forming film on the aforementioned supporting sheet and the aforementioned workpieces sequentially in the thickness direction of these; In the state where the peripheral edge of the first laminated composite sheet is attached to the jig for fixing, the first laminated composite sheet is heated so that the protective film forming film is hardened to form the protective film, thereby being fabricated on the support. The second laminated composite sheet formed by laminating the aforementioned protective film and the aforementioned workpieces sequentially in the thickness direction on the sheet; By dividing the aforementioned workpiece in the aforementioned second laminated composite sheet on the aforementioned support sheet, the aforementioned protective film is cut to produce a third laminated composite sheet in which a plurality of wafers with protective films are fixed on the aforementioned support sheet steps; and The step of picking up is carried out by tearing off the aforementioned wafer with the protective film in the aforementioned third laminated composite sheet from the aforementioned supporting sheet.

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