Support sheet, composite sheet for forming resin film, kit, and method for producing chip with resin film

Abstract

To provide a support sheet which allows a short seasoning period of a sticker layer to be kept, and which can eliminate a failure of delamination between a sticker layer and a base material of the support sheet, a composite sheet and a kit, for forming a resin film including the support sheet and a resin film-forming layer, and a method for manufacturing a resin film-attached chip.SOLUTION: A support sheet 10 comprises a sticker layer 12 provided on a base material 11, which is to be used in a method for manufacturing a resin film-attached chip 901. The sticker layer 12 is formed by coating a sticker composition containing an acrylic resin having a hydroxyl group and an isocyanate-based crosslinking agent. The proportion of the isocyanate-based crosslinking agent blended to one equivalent of the hydroxyl group of the acrylic resin is 0.07 eq. or more. The isocyanate-based crosslinking agent contains tolylene diisocyanate and hexamethylene diisocyanate. The proportion of the hexamethylene diisocyanate blended to one pt.mass of the tolylene diisocyanate is 0.3-4.0 pts.mass.SELECTED DRAWING: Figure 6D

Description

[Technical field]

[0001] The present invention relates to a support sheet, a composite sheet and kit for resin film formation that include the support sheet and a resin film forming layer, and a method for producing a chip with a resin film. [Background technology]

[0002] Some workpieces, such as semiconductor wafers, insulator wafers, and semiconductor device panels, have circuits formed on one surface (circuit surface) and further have protruding electrodes such as bumps on the surface (circuit surface). In order to protect the back surface of the chip formed by dicing such a workpiece, a protective film-forming film is used in the manufacturing process of a semiconductor device using a mounting method called the face-down method, and a protective film-forming composite sheet in which a protective film-forming film, an adhesive layer, and a base material are combined is used. In addition, a film-like adhesive is used to bond the chip to a lead frame, an organic substrate, and the like, and a dicing die bonding sheet in which a film-like adhesive, an adhesive layer, and a base material are combined is also used when dicing the workpiece.

[0003] Hereinafter, in this specification, the protective film-forming film or the film-like adhesive is referred to as a resin film-forming layer, and the composite sheet for protective film formation or the dicing die bonding sheet is referred to as a composite sheet for resin film formation. The protective film formed by the protective film-forming film or the bonding layer formed by the film-like adhesive is referred to as a resin film.

[0004] In semiconductor processing, a resin film forming layer for forming a protective film or a bonding layer is attached to the back surface of a workpiece. The resin film forming layer is laminated on a support sheet consisting of an adhesive layer and a substrate for supporting the resin film forming layer, and may be attached to the back surface of the workpiece in the form of a composite sheet for resin film formation, or may be attached to the back surface of the workpiece without being laminated on the support sheet. The resin film forming layer attached to the back surface of the wafer is cured by heat or energy rays as necessary, and then the workpiece is divided into chips through a dicing process on the support sheet, and the chips with the resin film are picked up. Alternatively, the resin film forming layer is not cured, and the chips with the resin film forming layer are picked up (see Patent Documents 1 to 3).

[0005] The acrylic adhesive used in the adhesive layer obtains a predetermined cohesive strength by crosslinking acrylic polymers as the main component. The crosslinking is performed by a crosslinking reaction between the acrylic polymer and a crosslinking agent. In particular, a crosslinking reaction in which a urethane bond is formed between an isocyanate group of the crosslinking agent and a hydroxyl group of the acrylic polymer is widely used. The crosslinking reaction usually proceeds after the adhesive composition is formed into a film and dried by heating, followed by a curing period of several days to several weeks in a normal temperature and humidity environment (hereinafter referred to as a "seasoning period"). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2019 / 082966 [Patent Document 2] International Publication No. 2020 / 218519 [Patent Document 3] International Publication No. 2020 / 196130 Summary of the Invention [Problem to be solved by the invention]

[0007] In the conventional method for manufacturing a chip with a resin film using a resin film forming layer or a composite sheet for forming a resin film, when dicing a workpiece or when picking up a chip with a resin film or a chip with a resin film forming layer, peeling may occur between the adhesive layer of the support sheet and the base material. The adhesive layer adjusted so that peeling does not occur between the adhesive layer of the support sheet and the base material tends to have a long seasoning period.

[0008] The present invention aims to provide a support sheet that can keep the seasoning period of the adhesive layer short and eliminate peeling defects between the adhesive layer of the support sheet and a substrate, a composite sheet and kit for resin film formation that include the support sheet and a resin film forming layer, and a method for manufacturing chips with a resin film. [Means for solving the problem]

[0009] The present invention provides the following support sheet, composite sheet and kit for forming a resin film, and method for producing a chip with a resin film.

[0010] [1] A support sheet having a pressure-sensitive adhesive layer provided on a substrate, The support sheet is used in a method for producing a chip with a resin film, in which a chip with a resin film is picked up by peeling it off from a third laminated composite sheet on which a plurality of chips with a resin film divided on the support sheet are fixed, or a chip with a resin film forming layer is picked up by peeling it off from a fourth laminated composite sheet on which a plurality of chips with a resin film forming layer divided on the support sheet are fixed, the pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive composition containing an acrylic resin having a hydroxyl group and an isocyanate-based crosslinking agent, The mixing ratio of the isocyanate-based crosslinking agent to 1 equivalent of a hydroxyl group of the acrylic resin is 0.07 equivalents or more, The isocyanate-based crosslinking agent contains tolylene diisocyanate and hexamethylene diisocyanate, The support sheet has a mixing ratio of 0.3 to 4.0 parts by mass of hexamethylene diisocyanate per 1 part by mass of tolylene diisocyanate.

[0011] [2] The support sheet according to [1], wherein the acrylic resin has a structural unit derived from a hydroxyalkyl (meth)acrylate. [3] The support sheet according to [1] or [2], wherein the constituent material of the substrate contains a polyolefin resin.

[0012] [4] A composite sheet for resin film formation, comprising: a support sheet according to any one of [1] to [3]; and a resin film forming layer provided on one surface of the support sheet. [5] The composite sheet for resin film formation described in [4], wherein the resin film forming layer is a protective film forming film. [6] The composite sheet for resin film formation described in [4], wherein the resin film forming layer is a film-like adhesive.

[0013] [7] A kit comprising a first laminate in which a first release film, a resin film forming layer and a second release film are laminated in that order, and a support sheet described in [1] or [2] used to support a workpiece to which the resin film forming layer is to be attached and the resin film forming layer. [8] The kit described in [7], wherein the resin film forming layer is a protective film forming film. [9] The kit described in [7], wherein the resin film forming layer is a film-like adhesive.

[0014]

[10] A method for manufacturing a resin-film-coated chip comprising: a chip; and a resin film provided on a back surface of the chip, the method comprising: The method for producing the resin-film-coated chip includes the steps of: attaching a resin film-forming layer of the composite sheet for resin film formation described in any one of [4] to [6] to the back surface of a workpiece to produce a first laminated composite sheet in which the support sheet, the resin film-forming layer, and the workpiece are laminated in this order in the thickness direction; A process of forming the resin film by curing the resin film forming layer in the first laminated composite sheet to produce a second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction; Dividing the work in the second laminated composite sheet and cutting the resin film to produce a third laminated composite sheet in which a plurality of chips with a resin film are fixed on the support sheet; and picking up the resin-film-coated chip in the third laminated composite sheet by separating it from the support sheet.

[11] A method for manufacturing a resin-film-coated chip comprising: a chip; and a resin film provided on a back surface of the chip, the method comprising: The method for producing the resin-film-coated chip includes the steps of: attaching a resin film-forming layer in the kit described in any one of [7] to [9] to a back surface of a workpiece, and producing a first laminate film in which the resin film-forming layer and the workpiece are laminated in a thickness direction; A process of forming the resin film by curing the resin film forming layer in the first laminate film, and producing a second laminate film in which the resin film and the workpiece are laminated in their thickness direction; A step of attaching an adhesive layer of the support sheet in the kit to a second laminate film to produce a second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction; Dividing the work in the second laminated composite sheet and cutting the resin film to produce a third laminated composite sheet in which a plurality of chips with a resin film are fixed on the support sheet; and picking up the resin-film-coated chip in the third laminated composite sheet by separating it from the support sheet.

[0015]

[12] A method for manufacturing a resin-film-coated chip comprising: a chip; and a resin film provided on a back surface of the chip, the method comprising: The method for producing the chip with resin film includes the steps of: attaching a resin film forming layer in a composite sheet for resin film formation described in any one of [4] to [6] to the back surface of a workpiece; or attaching a resin film forming layer in a kit described in any one of [7] to [9] to the back surface of a workpiece to produce a first laminated film in which the resin film forming layer and the workpiece are laminated in their thickness direction; and attaching an adhesive layer of a support sheet in the kit to the resin film forming layer in the first laminated film to produce a first laminated composite sheet in which the support sheet, the resin film forming layer, and the workpiece are laminated in this order in their thickness direction. A step of dividing the work in the first laminated composite sheet and cutting the resin film forming layer to produce a fourth laminated composite sheet in which a plurality of chips with a resin film forming layer are fixed on the support sheet; and picking up the chip with the resin film forming layer in the fourth laminated composite sheet by separating it from the support sheet.

[0016]

[13] The method for producing a resin film-coated chip according to any one of

[10] to

[12] , wherein the resin film-forming layer is a protective film-forming film.

[14] The method for producing a resin-film-attached chip described in

[12] , wherein the resin film-forming layer is a film-like adhesive. Effect of the Invention

[0017] According to the present invention, there is provided a support sheet that can keep the seasoning period of the adhesive layer short and eliminate peeling defects between the adhesive layer of the support sheet and a substrate, a composite sheet and kit for resin film formation that include the support sheet and a resin film forming layer, and a method for manufacturing a chip with a resin film. [Brief description of the drawings]

[0018] [Figure 1] FIG. 2 is a cross-sectional view showing a schematic example of a support sheet according to an embodiment of the present invention. [Diagram 2]1 is a cross-sectional view showing a schematic example of a composite sheet for resin film formation according to one embodiment of the present invention. [Diagram 3] FIG. 2 is a cross-sectional view showing a schematic diagram of another example of a composite sheet for resin film formation according to one embodiment of the present invention. [Figure 4] FIG. 2 is a cross-sectional view showing a schematic diagram of still another example of the composite sheet for resin film formation according to one embodiment of the present invention. [Diagram 5] FIG. 1 is a cross-sectional view showing a schematic example of a kit according to one embodiment of the present invention. [Figure 6A] 1A to 1C are cross-sectional views for illustrating a part of an example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 6B] 1A to 1C are cross-sectional views for illustrating a part of an example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 6C] 1A to 1C are cross-sectional views for illustrating a part of an example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 6D] 1A to 1C are cross-sectional views for illustrating a part of an example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 7A] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 7B] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 7C] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 7D] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 7E] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 8A]11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 8B] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. [Figure 8C] 11A to 11C are cross-sectional views for illustrating a schematic view of a portion of another example of a method for manufacturing a resin-film-coated chip according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] <<Support sheet>> The support sheet according to one embodiment of the present invention is a support sheet having an adhesive layer on a substrate, and the support sheet is used in a method for producing a chip with a resin film. The method for producing a chip with a resin film is to pick up a chip with a resin film in a third laminated composite sheet in which a plurality of chips with a resin film divided on the support sheet are fixed on the support sheet by separating the chip with the resin film from the support sheet, or to pick up a chip with a resin film forming layer in a fourth laminated composite sheet in which a plurality of chips with a resin film forming layer divided on the support sheet are fixed on the support sheet by separating the chip with the resin film forming layer from the support sheet.

[0020] When forming a plurality of chips with a resin film from the second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction, the workpiece can be easily divided and the resin film can be easily cut so that peeling does not occur between the adhesive layer of the support sheet and the base material. When picking up the chips with a resin film in the third laminated composite sheet by peeling them off from the support sheet, the chips with a resin film can be easily peeled off from the support sheet so that peeling does not occur between the adhesive layer of the support sheet and the base material.

[0021] When forming a plurality of chips with a resin film forming layer from the first laminated composite sheet in which the support sheet, the resin film forming layer, and the work are laminated in this order in the thickness direction, the work can be easily divided and the resin film forming layer can be easily cut so that peeling does not occur between the adhesive layer of the support sheet and the base material. When picking up the chips with the resin film forming layer in the fourth laminated composite sheet by peeling them off from the support sheet, the chips with the resin film forming layer can be easily peeled off from the support sheet so that peeling does not occur between the adhesive layer of the support sheet and the base material.

[0022] In this specification, the term "workpiece" refers to a wafer or a semiconductor device panel. Examples of "wafers" include semiconductor wafers made of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and insulator wafers made of insulators such as sapphire and glass. The term "semiconductor device panel" refers to an assembly in which a plurality of semiconductor devices, each of which has at least one electronic component sealed with a sealing resin layer, are arranged side by side in a plane. A circuit is formed on one surface of each of these workpieces, and in this specification, the surface of the workpiece on which the circuit is formed is referred to as the "circuit surface," and the surface of the workpiece opposite to the circuit surface is referred to as the "rear surface." The work is divided into chips by dicing or other means. In this specification, as in the case of the work, the surface of the chip on which the circuit is formed is referred to as the "circuit surface," and the surface of the chip opposite the circuit surface is referred to as the "back surface." Both the circuit surface of the workpiece and the circuit surface of the chip are provided with protruding electrodes such as bumps, pillars, etc. The protruding electrodes are preferably made of solder.

[0023] Fig. 1 is a cross-sectional view showing an example of the support sheet of the present embodiment. In the drawings used in the following description, in order to make the features of the present invention easier to understand, the main parts may be enlarged for convenience, and the dimensional ratios of each component may not necessarily be the same as the actual ones.

[0024] The support sheet shown in FIG. 1 has a substrate 11 and an adhesive layer 12 provided on one surface 11a thereof.

[0025] The adhesive layer 12 is formed by applying an adhesive composition containing an acrylic resin having a hydroxyl group and an isocyanate-based crosslinking agent, the blending ratio of the isocyanate-based crosslinking agent relative to 1 equivalent of the hydroxyl group of the acrylic resin is 0.07 equivalents or more, the isocyanate-based crosslinking agent contains tolylene diisocyanate and hexamethylene diisocyanate, and the blending ratio of the hexamethylene diisocyanate relative to 1 part by mass of tolylene diisocyanate is 0.3 to 4.0 parts by mass.

[0026] The acrylic resin having a hydroxyl group and the isocyanate crosslinking agent in the pressure-sensitive adhesive composition undergo a crosslinking reaction to form a functional group. That is, the detection of a urethane bond formed by a crosslinking reaction between the acrylic resin having a hydroxyl group and the isocyanate crosslinking agent in the pressure-sensitive adhesive layer 12 suggests the possibility that the pressure-sensitive adhesive layer 12 was formed by applying a pressure-sensitive adhesive composition containing an acrylic resin having a hydroxyl group and an isocyanate crosslinking agent.

[0027] The blending ratio of the isocyanate crosslinking agent relative to one equivalent of the hydroxyl group of the acrylic resin refers to the blending ratio of the isocyanate crosslinking agent relative to one equivalent of the hydroxyl group of the acrylic resin in the adhesive composition used to produce the adhesive layer, and the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate refers to the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate in the adhesive composition used to produce the adhesive layer. The blending ratio of the isocyanate-based crosslinking agent relative to one equivalent of hydroxyl groups of the acrylic resin in the adhesive composition used to produce the adhesive layer, and the blending ratios of tolylene diisocyanate and hexamethylene diisocyanate can be easily determined from the content ratio of the skeletons of these compounds in the adhesive layer, since the skeletons of these compounds do not change before and after the crosslinking reaction during the seasoning period of the adhesive layer.

[0028] The adhesive layer 12 can keep the seasoning period short and eliminate peeling problems between the adhesive layer of the support sheet and the substrate when dicing the workpiece and when picking up chips with a resin film or chips with a resin film forming layer.

[0029] The support sheet is preferably transparent and may be colored depending on the purpose. When the resin film forming layer has energy ray curing properties, the support sheet is preferably one that transmits energy rays.

[0030] Next, each layer constituting the support sheet will be described in more detail.

[0031] Adhesive layer The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition containing an acrylic resin having a hydroxyl group and an isocyanate-based crosslinking agent, and drying the applied composition. The blending ratio of the isocyanate-based crosslinking agent to one equivalent of the hydroxyl group of the acrylic resin is 0.07 equivalents or more. By blending the isocyanate-based crosslinking agent at a blending ratio of 0.07 equivalents or more to one equivalent of the hydroxyl group, the adhesion between the substrate and the adhesive layer can be sufficiently maintained. The blending ratio of the isocyanate-based crosslinking agent is preferably 0.09 equivalents or more to one equivalent of the hydroxyl group of the acrylic resin, more preferably 0.11 equivalents or more, even more preferably 0.13 equivalents or more, and particularly preferably 0.15 equivalents or more.

[0032] The isocyanate-based crosslinking agent contains tolylene diisocyanate and hexamethylene diisocyanate. The pressure-sensitive adhesive layer containing tolylene diisocyanate as a crosslinking agent tends to have a rapid crosslinking reaction, and can shorten the seasoning period. The pressure-sensitive adhesive layer containing hexamethylene diisocyanate as a crosslinking agent has good adhesion to the object to be adhered.

[0033] The blending ratio of hexamethylene diisocyanate is 0.3 or more, preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.6 or more, relative to 1 part by mass of the tolylene diisocyanate. By being equal to or more than the lower limit, the effect of hexamethylene diisocyanate is such that the adhesion between the substrate and the pressure-sensitive adhesive layer is good.

[0034] The mixing ratio of hexamethylene diisocyanate relative to 1 part by mass of the tolylene diisocyanate is 4.0 or less, preferably 3.5 or less, more preferably 3.2 or less, and even more preferably 3.0 or less. By being below the upper limit, the seasoning period can be shortened due to the effect of the tolylene diisocyanate.

[0035] By mixing the hexamethylene diisocyanate in an amount of 0.3 to 4.0 parts by mass per 1 part by mass of the tolylene diisocyanate, the seasoning period of the adhesive layer can be kept short and the adhesion between the substrate and the adhesive layer can be well adjusted, thereby eliminating peeling problems between the adhesive layer of the support sheet and the substrate when dicing the workpiece and when picking up the chip with a resin film or the chip with a resin film forming layer.

[0036] The pressure-sensitive adhesive layer contains a hydroxyl group-containing acrylic resin. The hydroxyl group-containing acrylic resin can be obtained by polymerizing a monomer containing a hydroxyl group-containing monomer, and contains an acrylic polymer having a constituent unit derived from the hydroxyl group-containing monomer. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryloyl skeleton) such as vinyl alcohol and allyl alcohol.

[0037] The acrylic resin preferably has a structural unit derived from a hydroxyalkyl (meth)acrylate.

[0038] The pressure-sensitive adhesive layer may contain, in addition to an acrylic resin having a hydroxyl group, a pressure-sensitive adhesive resin such as a urethane resin, a rubber-based resin, a silicone resin, an epoxy-based resin, a polyvinyl ether, a polycarbonate, or an ester-based resin.

[0039] In this specification, the term "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only resins that are adhesive by themselves, but also resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness in the presence of a trigger such as heat or water.

[0040] The pressure-sensitive adhesive layer is in the form of a sheet or film. The adhesive layer may consist of one layer (single layer), or may consist of two or more layers. If it consists of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

[0041] The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably from 1 to 100 μm, more preferably from 1 to 60 μm, and particularly preferably from 1 to 30 μm. Here, "the thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer consisting of multiple layers means the total thickness of all layers that make up the adhesive layer.

[0042] The pressure-sensitive adhesive layer is preferably transparent, and may be colored depending on the purpose. In this embodiment in which the resin film forming layer has energy ray curing properties, the pressure-sensitive adhesive layer is preferably one that transmits energy rays.

[0043] The pressure-sensitive adhesive layer is preferably non-energy ray curable. When the pressure-sensitive adhesive layer is non-energy ray curable, examples of the non-energy ray curable pressure-sensitive adhesive composition include the pressure-sensitive adhesive composition (I-4) containing the non-energy ray curable pressure-sensitive adhesive resin (I-1a).

[0044] [Non-energy ray curable adhesive resin (I-1a)] The adhesive resin (I-1a) is an acrylic resin having a hydroxyl group. Examples of the acrylic resin include acrylic polymers having a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an alkyl (meth)acrylate ester. The (meth)acrylic acid alkyl ester may, for example, be one in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched.

[0045] The acrylic polymer may further contain, in addition to the constituent units derived from hydroxyl group-containing monomers and the constituent units derived from alkyl (meth)acrylates, constituent units derived from functional group-containing monomers other than hydroxyl group-containing monomers. Examples of the functional group-containing monomer include those in which the functional group reacts with a crosslinking agent described below to become a crosslinking starting point.

[0046] Examples of the functional group-containing monomer include carboxy group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers other than hydroxyl group-containing monomers.

[0047] The acrylic polymer may further contain a constituent unit derived from another monomer, in addition to the constituent unit derived from the (meth)acrylic acid alkyl ester and the constituent unit derived from the functional group-containing monomer. The other monomer is not particularly limited as long as it is copolymerizable with the (meth)acrylic acid alkyl ester and the like. Examples of the other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

[0048] In the pressure-sensitive adhesive composition (I-4), the structural unit contained in the acrylic resin such as the acrylic polymer may be of only one type, or may be of two or more types. When the structural unit is of two or more types, the combination and ratio thereof can be selected arbitrarily.

[0049] In the acrylic polymer, the proportion of the amount of the structural units derived from functional group-containing monomers relative to the total amount of the structural units is preferably 1 to 35% by mass.

[0050] The adhesive composition (I-4) may contain only one type of adhesive resin (I-1a), or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0051] In the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (I-4), the content of the pressure-sensitive adhesive resin (I-1a) relative to the total mass of the pressure-sensitive adhesive layer is preferably 5 to 99 mass%, and may be, for example, any one of 25 to 98 mass%, 45 to 97 mass%, and 65 to 96 mass%.

[0052] [Crosslinking agent] The pressure-sensitive adhesive composition (I-4) further contains an isocyanate-based crosslinking agent.

[0053] The crosslinking agent reacts with the hydroxyl groups to crosslink the adhesive resins (I-1a) together.

[0054] In the pressure-sensitive adhesive composition (I-4), the content of the isocyanate-based crosslinking agent is not limited as long as the mixing ratio of the isocyanate-based crosslinking agent is adjusted to be 0.09 equivalents or more per equivalent of the hydroxyl group of the acrylic resin. However, the content is preferably 0.01 to 50 parts by mass per 100 parts by mass of the pressure-sensitive adhesive resin (I-1a), and may be, for example, any one of 1 to 40 parts by mass, 5 to 35 parts by mass, and 10 to 30 parts by mass.

[0055] [Other additives] The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall into any of the above-mentioned components, as long as the effects of the present invention are not impaired. Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts). The reaction retarder is, for example, a component that suppresses the progress of unintended crosslinking reaction in the pressure-sensitive adhesive composition (I-4) during storage due to the action of a catalyst mixed in the pressure-sensitive adhesive composition (I-4). For example, the reaction retarder can be one that forms a chelate complex by chelation with the catalyst, and more specifically, one that has two or more carbonyl groups (-C(=O)-) in one molecule.

[0056] The other additives contained in the pressure-sensitive adhesive composition (I-4) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0057] The content of other additives in the pressure-sensitive adhesive composition (I-4) is not particularly limited and may be appropriately selected depending on the type of additive.

[0058] [solvent] The pressure-sensitive adhesive composition (I-4) may contain a solvent. By containing a solvent, the pressure-sensitive adhesive composition (I-4) has improved suitability for application to a surface to be coated.

[0059] The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; and alcohols such as 1-propanol and 2-propanol.

[0060] The pressure-sensitive adhesive composition (I-4) may contain only one type of solvent, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0061] The content of the solvent in the pressure-sensitive adhesive composition (I-4) is not particularly limited and may be appropriately adjusted.

[0062] Method for producing pressure-sensitive adhesive composition A pressure-sensitive adhesive composition such as the pressure-sensitive adhesive composition (I-4) can be obtained by blending the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive, for constituting the pressure-sensitive adhesive composition. The order of addition of the components when blending is not particularly limited, and two or more components may be added simultaneously. The method for mixing the components during blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, a method of mixing by adding ultrasound, etc. The temperature and time during addition and mixing of each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately. A temperature of 15 to 30°C is preferred.

[0063] Method for producing pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is obtained by applying a pressure-sensitive adhesive composition containing an acrylic resin having a hydroxyl group and an isocyanate-based crosslinking agent, and drying the applied composition. The pressure-sensitive adhesive composition may be applied by a known method, for example, a method using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Mayer bar coater, or a kiss coater.

[0064] The drying conditions for the adhesive composition are not particularly limited. However, when the adhesive composition contains a solvent, it is preferable to heat-dry it. And, the adhesive composition containing the solvent is preferably heat-dried under conditions of, for example, 70 to 130°C and 10 seconds to 5 minutes.

[0065] ○Base material The substrate is in the form of a sheet or film, and examples of the constituent materials thereof include various resins. Examples of the resin include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-based copolymers (copolymers obtained by using ethylene as a monomer) such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer; vinyl chloride-based resins (copolymers obtained by using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymer. resins having aromatic ring groups); polystyrene; polycycloolefins; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; copolymers of two or more of the above polyesters; poly(meth)acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; and polyether ketones.

[0066] The material constituting the substrate preferably contains a polyolefin resin, and among these, polyolefins other than polyethylene are preferred, and polypropylene is more preferred.

[0067] The resin may also be a polymer alloy such as a mixture of the polyester and another resin. The polymer alloy of the polyester and another resin is preferably one in which the amount of the resin other than the polyester is relatively small. Examples of the resin include crosslinked resins in which one or more of the resins exemplified above are crosslinked; and modified resins such as ionomers using one or more of the resins exemplified above.

[0068] The resin constituting the substrate may be of only one type, or of two or more types. When two or more types are used, the combination and ratio thereof can be selected arbitrarily.

[0069] The substrate may consist of one layer (single layer), or may consist of two or more layers. When the substrate consists of multiple layers, the multiple layers may be the same or different, and the combination of the multiple layers is not particularly limited.

[0070] The thickness of the substrate is preferably 50 to 300 μm, more preferably 60 to 100 μm. By setting the thickness of the substrate within such a range, the flexibility of the support sheet and the composite sheet for resin film formation and the suitability for attachment to a workpiece are further improved. Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of a substrate consisting of multiple layers means the total thickness of all layers constituting the substrate.

[0071] The substrate may contain, in addition to the main constituent materials such as the resin, various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, softeners (plasticizers), and the like.

[0072] The substrate is preferably transparent, and may be colored or have other layers deposited thereon depending on the purpose. In the case where the resin film-forming layer has energy ray curing properties, the substrate is preferably one that transmits energy rays.

[0073] In order to adjust the adhesiveness to the pressure-sensitive adhesive layer provided thereon, the surface of the substrate may be subjected to a roughening treatment such as sandblasting or solvent treatment, an oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone or ultraviolet irradiation treatment, flame treatment, chromic acid treatment, or hot air treatment, an oleophilic treatment, a hydrophilic treatment, etc. The surface of the substrate may be treated with a primer.

[0074] The substrate may have adhesiveness on at least one surface thereof by containing a specific range of components (for example, a resin, etc.).

[0075] ○Method of manufacturing the substrate The substrate can be produced by a known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the resin.

[0076] The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition can be applied to the surface on which the adhesive layer is to be formed and dried to form the adhesive layer at the desired location. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the adhesive layer.

[0077] ◇ Manufacturing method of support sheet When the adhesive layer is provided on the substrate, for example, the adhesive composition is applied on the substrate, and dried as necessary, and then a seasoning period is provided. Also, for example, the adhesive composition is applied on a release film, and dried as necessary to form an adhesive layer on the release film, and the exposed surface of this adhesive layer is laminated on one surface of the substrate to laminate the adhesive layer on the substrate, and then a seasoning period is provided. In this case, the release film can be removed at any timing during the manufacturing process or the use process of the composite sheet for resin film formation.

[0078] <<Composite sheet for forming resin film>> A composite sheet for resin film formation according to one embodiment of the present invention comprises the support sheet according to one embodiment of the present invention described above, and a resin film formation layer provided on one surface of the support sheet. An example of the composite sheet for resin film formation of this embodiment will be described below with reference to the drawings.

[0079] FIG. 2 is a cross-sectional view that illustrates an example of the composite sheet for resin film formation of the present embodiment. In FIG. 2 and subsequent figures, the same components as those shown in the figures already described are given the same reference numerals as in the figures already described, and detailed description thereof will be omitted.

[0080] The composite sheet 101 for forming a resin film shown here is composed of a support sheet 10 and a resin film forming layer 13 provided on one side 10a (sometimes referred to as the "first side" in this specification) of the support sheet 10. The support sheet 10 is configured to include a base material 11 and an adhesive layer 12 provided on one surface (first surface) 11a of the base material 11. In the composite sheet 101 for resin film formation, the adhesive layer 12 is disposed between the base material 11 and the resin film formation layer 13. That is, the composite sheet for resin film formation 101 is configured by laminating a substrate 11, a pressure-sensitive adhesive layer 12, and a resin film formation layer 13 in this order in the thickness direction. The first surface 10a of the support sheet 10 is the same as the surface 12a of the pressure-sensitive adhesive layer 12 opposite the substrate 11 side (sometimes referred to as the "first surface" in this specification).

[0081] The composite sheet for resin film formation 101 further includes a jig adhesive layer 16 and a release film 15 on the resin film formation layer 13 . In the composite sheet 101 for resin film formation, the resin film forming layer 13 is laminated on the entire or almost entire surface of the first surface 12a of the adhesive layer 12, and the jig adhesive layer 16 is laminated on a part of the surface 13a of the resin film forming layer 13 opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in this specification), i.e., on a region near the periphery. Furthermore, a release film 15 is laminated on the region of the first surface 13a of the resin film forming layer 13 where the jig adhesive layer 16 is not laminated, and on the surface 16a of the jig adhesive layer 16 opposite to the resin film forming layer 13 side (sometimes referred to as the "first surface" in this specification). A support sheet 10 is provided on the surface 13b of the resin film forming layer 13 opposite to the first surface 13a (sometimes referred to as the "second surface" in this specification).

[0082] Not only in the case of the composite sheet 101 for forming a resin film, but also in the composite sheet for forming a resin film of this embodiment, the release film is of an optional configuration, and the composite sheet for forming a resin film of this embodiment may or may not have a release film.

[0083] The jig adhesive layer 16 is used to fix the composite sheet for resin film formation 101 to a jig such as a ring frame. The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure including a core sheet and layers containing an adhesive component provided on both sides of the core sheet.

[0084] The composite sheet 101 for resin film formation is used by removing the release film 15, attaching the back surface of a workpiece to the first surface 13a of the resin film formation layer 13, and further attaching the first surface 16a of the jig adhesive layer 16 to a jig such as a ring frame.

[0085] FIG. 3 is a cross-sectional view that illustrates a schematic diagram of another example of the composite sheet for resin film formation according to the present embodiment. The composite sheet 102 for resin film formation shown here is the same as the composite sheet 101 for resin film formation shown in Figure 2, except that the shape and size of the resin film formation layer are different, and the jig adhesive layer is laminated on the first surface of the pressure-sensitive adhesive layer rather than the first surface of the resin film formation layer.

[0086] More specifically, in the composite sheet 102 for resin film formation, the resin film forming layer 23 is laminated in a part of the region of the first surface 12a of the adhesive layer 12, that is, in the central region in the width direction (left and right direction in FIG. 3) of the adhesive layer 12. Furthermore, in the region of the first surface 12a of the adhesive layer 12 where the resin film forming layer 23 is not laminated, the jig adhesive layer 16 is laminated so as to surround the resin film forming layer 23 from the outside in the width direction without contact. A release film 15 is laminated on the surface (sometimes referred to as the "first surface" in this specification) 23a of the resin film forming layer 23 opposite the adhesive layer 12 side and the first surface 16a of the jig adhesive layer 16. A support sheet 10 is provided on the surface (sometimes referred to as the "second surface" in this specification) 23b of the resin film forming layer 23 opposite the first surface 23a.

[0087] FIG. 4 is a cross-sectional view that illustrates a schematic diagram of still another example of the composite sheet for resin film formation of the present embodiment. The composite sheet 103 for resin film formation shown here is the same as the composite sheet 102 for resin film formation shown in FIG.

[0088] The composite sheet for forming a resin film of this embodiment is not limited to that shown in Figures 2 to 4, and may be one in which some of the configurations shown in Figures 2 to 4 have been changed or deleted, or other configurations may be added to those described above, within the scope that does not impair the effects of the present invention.

[0089] ○Resin film forming layer The resin film forming layer is attached to the back surface of the work in the method for producing a chip with a resin film. The resin film forming layer may be a protective film forming film used to protect the back surface of the work or the chip obtained by dividing the work, or may be a film-like adhesive for bonding the chip formed by dicing the work to a lead frame, an organic substrate, or the like.

[0090] When the resin film forming layer is a protective film forming film, by using a composite sheet for resin film formation comprising the support sheet and the resin film forming layer, a chip with a protective film can be manufactured by the manufacturing method for a chip with a resin film described below, which comprises a chip and a protective film provided on the back surface of the chip.

[0091] When the resin film forming layer is a film-like adhesive, by using a composite sheet for resin film formation comprising the support sheet and the resin film forming layer, a chip with a film-like adhesive can be manufactured by the manufacturing method for a chip with a resin film described below, which comprises a chip and a film-like adhesive provided on the back surface of the chip.

[0092] Furthermore, by using the chip with the resin film, a substrate device can be manufactured. In this specification, the term "substrate device" refers to a device in which a chip with a resin film is flip-chip connected to a connection pad on a circuit board at a protruding electrode on the circuit surface of the chip, or a device in which a chip with a resin film is bonded to a circuit board via a film-like adhesive. For example, when a semiconductor wafer is used as the wafer, a semiconductor device can be used as the substrate device.

[0093] The resin film forming layer is energy ray curable and may be heat curable or may not be heat curable. When the resin film forming layer has both energy ray curable and heat curable properties, the contribution of the energy ray curing of the resin film forming layer to the formation of the resin film is greater than the contribution of heat curing.

[0094] In this specification, the term "energy rays" refers to electromagnetic waves or charged particle beams that have an energy quantum. Examples of energy rays include ultraviolet rays, radiation, and electron beams. 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 lamp as an ultraviolet ray source. Electron beams can be irradiated by generating them using an electron beam accelerator or the like. In this specification, "energy ray curable" means a property that is cured by irradiation with energy rays, and "non-energy ray curable" means a property that is not cured even when irradiated with energy rays. Moreover, the term "non-curable" means a property that does not cure by any means such as heating or irradiation with energy rays.

[0095] The resin film forming layer may be one layer (single layer) or may be two or more layers. When the resin film forming layer is made up of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0096] In this specification, not only in the case of a resin film forming layer, "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same", and further, "multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other".

[0097] The thickness of the resin film forming layer is preferably 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 5 to 60 μm. By making the thickness of the resin film forming layer equal to or greater than the lower limit, a resin film with higher protective ability can be formed. By making the thickness of the resin film forming layer equal to or less than the upper limit, the thickness of the chip with the resin film can be prevented from becoming excessive. Here, "thickness of the resin film forming layer" means the thickness of the entire resin film forming layer, for example, the thickness of a resin film forming layer consisting of multiple layers means the total thickness of all layers that make up the resin film forming layer.

[0098] <Composition for forming resin film> The resin film forming layer can be formed using a resin film forming composition containing its constituent materials. For example, the resin film forming layer can be formed by applying the resin film forming composition to the surface to be formed and drying it as necessary. The content ratio of the components that do not vaporize at room temperature in the resin film forming composition is usually the same as the content ratio of the components in the resin film forming layer. In this specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 18 to 28°C.

[0099] The resin film-forming composition may be applied by a known method, similar to the application of the pressure-sensitive adhesive composition.

[0100] The drying conditions of the resin film-forming composition are not particularly limited. However, when the resin film-forming composition contains a solvent described later, it is preferable to heat-dry it. The resin film-forming composition containing the solvent is preferably heat-dried, for example, at 70 to 130°C for 10 seconds to 5 minutes. However, the resin film-forming composition having thermosetting properties is preferably heat-dried so that the composition itself and the thermosetting resin film-forming layer formed from the composition are not thermally cured.

[0101] The resin film-forming composition may be energy ray-curable, may be heat-curable, or may not have curability. Hereinafter, an example will be described in which the resin film forming layer is an energy ray-curable protective film-forming film and the resin film forming composition for forming it is the energy ray-curable resin film forming composition (IV).

[0102] <Energy ray curable resin film forming composition (IV)> Examples of the composition for forming a resin film include an energy ray-curable resin film-forming composition (IV) (sometimes simply referred to as "composition (IV)" in this specification) containing an energy ray-curable component (a), an acrylic resin (b) having no energy ray-curable group, and an inorganic filler (d).

[0103] [Energy ray curable component (a)] The energy ray curable component (a) is a component that is cured by irradiation with energy rays, and provides the resin film forming layer with film-forming properties, flexibility, etc., and is also a component for forming a hard resin film after curing. The resin film forming layer forms a resin film with good properties by containing the energy ray curable component (a). In the resin film forming layer, the energy ray curable component (a) is preferably uncured and has adhesive properties, and more preferably is uncured and has adhesive properties.

[0104] Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80000 to 2000000, and a compound (a2) having an energy ray curable group and a molecular weight of 100 to 80000. The polymer (a1) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

[0105] (Polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000) An example of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 includes an acrylic resin (a1-1) obtained by reacting an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound with an energy ray-curable compound (a12) having a group reactive with the functional group and an energy ray-curable group such as an energy ray-curable double bond.

[0106] Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, a substituted amino group (a group having a structure in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom), an epoxy group, etc. However, from the viewpoint of preventing corrosion of circuits of a wafer, a chip, etc., it is preferable that the functional group is a group other than a carboxy group. Of these, the functional group is preferably a hydroxyl group.

[0107] Acrylic polymers having functional groups (a11) The acrylic polymer (a11) having a functional group may be, for example, a polymer obtained by copolymerizing an acrylic monomer having the functional group with an acrylic monomer not having the functional group. In addition to these monomers, a monomer other than the acrylic monomer (non-acrylic monomer) may also be copolymerized. The acrylic polymer (a11) may be a random copolymer or a block copolymer, and the polymerization method may be a known method.

[0108] Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

[0109] Examples of the hydroxyl group-containing monomer include the above-mentioned hydroxyalkyl (meth)acrylates; non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryloyl skeleton); and the like.

[0110] Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; and (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

[0111] The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer.

[0112] The acrylic monomer having a functional group constituting the acrylic polymer (a11) may be of only one kind, or of two or more kinds. When there are two or more kinds, the combination and ratio thereof can be selected arbitrarily.

[0113] Examples of the acrylic monomer not having a functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ethyl ... Examples of (meth)acrylic acid alkyl esters include those in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as sononyl, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate).

[0114] Examples of the acrylic monomer not having a functional group include alkoxyalkyl group-containing (meth)acrylic acid esters such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; (meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamide and derivatives thereof; and (meth)acrylic acid esters having a non-crosslinkable tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

[0115] The acrylic monomer not having a functional group constituting the acrylic polymer (a11) may be of only one kind or of two or more kinds, and when it is of two or more kinds, the combination and ratio thereof can be arbitrarily selected.

[0116] Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene. The non-acrylic monomer constituting the acrylic polymer (a11) may be of only one kind, or may be of two or more kinds. When it is of two or more kinds, the combination and ratio thereof can be selected arbitrarily.

[0117] In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is preferably 0.1 to 50 mass%, more preferably 1 to 40 mass%, and particularly preferably 3 to 30 mass%. When the ratio is in such a range, the content of the energy ray curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12) can adjust the degree of curing of the resin film to a preferred range.

[0118] The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be of only one kind, or may be of two or more kinds. When there are two or more kinds, the combination and ratio thereof can be selected arbitrarily.

[0119] In the composition (IV) and the resin film forming layer, the content of the acrylic resin (a1-1) relative to the total mass of the composition (IV) or the resin film forming layer is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, and particularly preferably 10 to 50 mass%.

[0120] Energy ray curable compounds (a12) The energy ray curable compound (a12) preferably has one or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11), and more preferably has an isocyanate group as the group. For example, when the energy ray curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

[0121] The number of the energy ray-curable groups that the energy ray-curable compound (a12) has in one molecule is not particularly limited, and can be appropriately selected in consideration of, for example, the physical properties required for the target resin film, such as the shrinkage rate. For example, the energy ray-curable compound (a12) preferably has 1 to 5, and more preferably 1 to 3, energy ray-curable groups in one molecule.

[0122] Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate; an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate; Examples of the isocyanate include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth)acrylate. Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

[0123] The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0124] In the acrylic resin (a1-1), the content ratio of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is in such a range, the adhesive strength of the cured product of the resin film forming layer is increased. In addition, when the energy ray curable compound (a12) is a monofunctional compound (having one of the groups in one molecule), the upper limit of the content ratio is 100 mol%, but when the energy ray curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

[0125] The weight average molecular weight (Mw) of the polymer (a1) is preferably from 100,000 to 2,000,000, and more preferably from 300,000 to 1,500,000. Here, the "weight average molecular weight" is as explained above.

[0126] The polymer (a1) contained in the composition (IV) and the resin film forming layer may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0127] (Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000) The energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000 includes a group containing an energy ray-curable double bond, and preferred examples thereof include a (meth)acryloyl group and a vinyl group.

[0128] The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples of the compound (a2) include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and a phenol resin having an energy ray-curable group.

[0129] Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth)acryloyl group are preferred.

[0130] The acrylate-based compound may, for example, be a polyfunctional monomer or oligomer, and is preferably a polyfunctional acrylate-based compound having two or more (meth)acryloyl groups in one molecule. Examples of the polyfunctional acrylate compounds include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also known as tricyclodecane dimethylol di(meth)acrylate), 1,10-decane diol di(meth)acrylate, 1, Bifunctional (meth)acrylates such as 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane ((meth)acrylates having two (meth)acryloyl groups in one molecule); Polyfunctional (meth)acrylates ((meth)acrylates having three or more (meth)acryloyl groups in one molecule) such as tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Examples of the polyfunctional (meth)acrylate oligomer include a polyfunctional urethane (meth)acrylate oligomer (a (meth)acrylate oligomer having two or more (meth)acryloyl groups in one molecule).

[0131] Among the compounds (a2), examples of the epoxy resin having an energy ray curable group and the phenolic resin having an energy ray curable group that can be used include those described in paragraph 0043 of JP 2013-194102 A. Although such resins also fall under the category of resins constituting the thermosetting component described below, they are treated as the compound (a2) in the composition (IV).

[0132] The weight average molecular weight of the compound (a2) is preferably from 100 to 30,000, and more preferably from 300 to 10,000.

[0133] The compound (a2) contained in the composition (IV) and the resin film forming layer may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0134] The resin film forming layer preferably contains the above-mentioned compound (a2) as the energy ray curable component (a), and more preferably contains a polyfunctional acrylate compound having two or more (meth)acryloyl groups in one molecule.

[0135] In composition (IV), the content ratio of the energy ray curable component (a) relative to the total content of all components other than the solvent (i.e., the content ratio of the energy ray curable component (a) in the resin film forming layer relative to the total mass of the resin film forming layer) is preferably 12 to 31 mass%, more preferably 14 to 28 mass%, and even more preferably 16 to 25 mass%.

[0136] [Acrylic resin (b) having no energy ray-curable group] The resin film forming layer preferably contains an acrylic resin (b) that does not have an energy ray-curable group (sometimes simply referred to as "acrylic resin (b)" in this specification).

[0137] The acrylic resin (b) is a component that imparts film-forming properties to the resin film forming layer.

[0138] The acrylic resin (b) may be a known one, and may be, for example, a homopolymer of one kind of acrylic monomer, a copolymer of two or more kinds of acrylic monomers, or a copolymer of one or more kinds of acrylic monomers and one or more kinds of monomers other than the acrylic monomers (non-acrylic monomers).

[0139] The acrylic resin (b) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

[0140] Examples of the acrylic monomer constituting the acrylic resin (b) include (meth)acrylic acid esters such as (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having a cyclic skeleton, (meth)acrylic acid esters containing a glycidyl group, (meth)acrylic acid esters containing a hydroxyl group, (meth)acrylic acid esters containing a substituted amino group, (meth)acrylic acid esters containing a carboxyl group, and (meth)acrylic acid esters containing an amino group; (meth)acrylamide; and (meth)acrylamide derivatives such as 4-(meth)acryloylmorpholine. Here, the term "substituted amino group" refers to a group having a structure in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom. Here, the term "functional group" refers to a group (reactive functional group) that can react with other groups, such as a glycidyl group, a hydroxyl group, a substituted amino group, a carboxyl group, and an amino group.

[0141] In this specification, the term "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acrylate" is a concept that includes both "acrylate" and "methacrylate", and "(meth)acryloyl group" is a concept that includes both "acryloyl group" and "methacryloyl group".

[0142] In this specification, when a structure in which one or more hydrogen atoms in a certain specific compound are replaced with a group other than a hydrogen atom is assumed, the compound having such a replaced structure is referred to as a "derivative" of the above-mentioned specific compound. In this specification, the term "group" includes not only an atomic group formed by bonding a plurality of atoms, but also a single atom.

[0143] Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isopropyl (meth)acrylate, and isopropyl (meth)acrylate. Examples of (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms include sononyl, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate).

[0144] Examples of the (meth)acrylic acid ester having no functional group and a cyclic skeleton include cycloalkyl (meth)acrylic acid esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; (Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (Meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester; (Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester are included.

[0145] The glycidyl group-containing (meth)acrylic acid ester may, for example, be glycidyl (meth)acrylate. Examples of the hydroxyl group-containing (meth)acrylic acid ester include those having a structure in which one or more hydrogen atoms are replaced with hydroxyl groups in either one of the (meth)acrylic acid alkyl esters not having the functional group and the cyclic skeleton and the (meth)acrylic acid esters not having the functional group and having the cyclic skeleton. Examples of the preferred hydroxyl group-containing (meth)acrylic acid esters include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. The substituted amino group-containing (meth)acrylic acid ester may, for example, be N-methylaminoethyl (meth)acrylate.

[0146] Examples of the non-acrylic monomer constituting the acrylic resin (b) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0147] The acrylic resin (b) at least a part of which is crosslinked with a crosslinking agent may be, for example, one in which a functional group in the acrylic resin (b) has reacted with a crosslinking agent. The functional group may be appropriately selected depending on the type of crosslinking agent, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, the functional group may be a hydroxyl group, a carboxyl group, an amino group, etc., and among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. When the crosslinking agent is an epoxy compound, the functional group may be a carboxyl group, an amino group, etc., and among these, a carboxyl group having high reactivity with an epoxy group is preferred. However, from the viewpoint of preventing corrosion of the circuits of the wafer or chip, the functional group is preferably a group other than a carboxyl group.

[0148] The acrylic resin (b) having a functional group may be, for example, one obtained by polymerizing a monomer having at least the functional group. More specifically, the acrylic resin (b) having a functional group can be, for example, one obtained by polymerizing one or more monomers selected from the group consisting of the glycidyl group-containing (meth)acrylic ester, the hydroxyl group-containing (meth)acrylic ester, the substituted amino group-containing (meth)acrylic ester, the carboxy group-containing (meth)acrylic ester, the amino group-containing (meth)acrylic ester, and the non-acrylic monomer having a structure in which one or more hydrogen atoms are substituted with the functional group.

[0149] In the acrylic resin (b), the ratio (content) of the amount of the structural units derived from the monomer having a functional group to the total amount of the structural units constituting the acrylic resin (b) is preferably 1 to 20 mass%, more preferably 2 to 10 mass%. When the ratio is in such a range, the degree of crosslinking in the acrylic resin (b) becomes a more preferable range.

[0150] The weight average molecular weight (Mw) of the acrylic resin (b) is preferably at least 10000, more preferably at least 20000, and further preferably at least 40000. In order to improve the film-forming properties of the composition (IV), the weight average molecular weight (Mw) of the acrylic resin (b) is preferably from 10000 to 2000000, and more preferably from 100000 to 1500000.

[0151] In this specification, unless otherwise specified, the "weight average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0152] The acrylic resin (b) contained in the composition (IV) and the resin film forming layer may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0153] In composition (IV), the ratio of the content of acrylic resin (b) to the total content of all components other than the solvent (i.e., the ratio of the content of acrylic resin (b) in the resin film forming layer to the total mass of the resin film forming layer) is preferably 8 mass% or more, more preferably 10 mass% or more, and may be, for example, any one of 12 mass% or more and 14 mass% or more.

[0154] In the composition (IV), the upper limit of the content ratio of the acrylic resin (b) to the total content of all components other than the solvent (i.e., the content ratio of the acrylic resin (b) to the total mass of the resin film forming layer in the resin film forming layer) is not particularly limited. The upper limit may be 27% by mass or less, preferably 25% by mass or less, more preferably 23% by mass or less, and even more preferably 21% by mass or less.

[0155] In composition (IV), the ratio of the content of acrylic resin (b) to the total content of all components other than the solvent (i.e., the ratio of the content of acrylic resin (b) in the resin film forming layer to the total mass of the resin film forming layer) can be appropriately adjusted within a range set by any combination of any of the lower limit values ​​and upper limit values ​​described above. For example, in one embodiment, the ratio is preferably from 8 to 27% by mass, more preferably from 10 to 25% by mass, and may be any of from 12 to 23% by mass, and from 14 to 21% by mass.

[0156] When the composition (IV) and the resin film forming layer contain an energy ray curable component (a) and an acrylic resin (b), the content of the energy ray curable component (a) in the composition (IV) and the resin film forming layer is preferably 70 to 310 parts by mass, more preferably 80 to 280 parts by mass, and still more preferably 85 to 250 parts by mass, per 100 parts by mass of the content of the acrylic resin (b).

[0157] In composition (IV), the ratio of the total content of the energy ray curable component (a) and the acrylic resin (b) to the total content of all components other than the solvent (i.e., the ratio of the total content of the energy ray curable component (a) and the acrylic resin (b) to the total mass of the resin film forming layer in the resin film forming layer) is preferably 10 to 60 mass%, and may be, for example, either 20 to 50 mass% or 30 to 45 mass%. When the ratio is in such a range, the effect of using the energy ray curable component (a) and the acrylic resin (b) is further enhanced.

[0158] [Other ingredients] The composition (IV) and the resin film forming layer may contain other components that do not fall under either the energy ray curable component (a) or the acrylic resin (b), as long as the effects of the present invention are not impaired. Examples of the other components include a photopolymerization initiator (c); an inorganic filler (d); a coupling agent (e); a crosslinking agent (f); a colorant (g); a thermosetting component (h); a general-purpose additive (z); and a polymer (b0) that does not fall under the acrylic resin (b) and does not have an energy ray-curable group (b0) (sometimes referred to in this specification as "another polymer (b0) that does not have an energy ray-curable group" or "polymer (b0)").

[0159] (Photopolymerization initiator (c)) When the composition (IV) and the resin film forming layer contain a photopolymerization initiator (c), the polymerization (curing) reaction of the energy ray-curable component (a) can be efficiently promoted.

[0160] Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. Examples of suitable compounds include acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone. Examples of the photopolymerization initiator include photosensitizers such as amines.

[0161] The photopolymerization initiator (c) contained in the composition (IV) and the resin film forming layer may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0162] When a photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the composition (IV) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, per 100 parts by mass of the energy ray-curable component (a).

[0163] (Inorganic filler (d)) When the composition (IV) and the resin film forming layer contain an inorganic filler (d), the thermal expansion coefficient of the cured product (e.g., a resin film) of the resin film forming layer can be more easily adjusted by adjusting the amount of the inorganic filler (d) in the composition (IV) and the resin film forming layer. For example, the reliability of the package obtained by using the resin film forming layer is further improved by optimizing the thermal expansion coefficient of the resin film for the object on which the resin film is formed. In addition, by using a resin film forming layer containing an inorganic filler (d), the moisture absorption rate of the cured product (e.g., a resin film) of the resin film forming layer can be reduced and the heat dissipation can be improved.

[0164] Examples of the inorganic filler (d) include powders of inorganic materials such as silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; beads made by shaping these inorganic materials; surface-modified products of these inorganic materials; single crystal fibers of these inorganic materials; and glass fibers. Among these, the inorganic filler (d) is preferably silica or alumina.

[0165] The inorganic filler (d) contained in the composition (IV) and the resin film forming layer may be of only one type, or of two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0166] In the composition (IV), the ratio of the content of the inorganic filler (d) to the total content of all components other than the solvent (i.e., the ratio of the content of the inorganic filler (d) in the resin film forming layer to the total mass of the resin film forming layer) is preferably 35 to 75 mass%, and may be, for example, either 45 to 70 mass% or 50 to 65 mass%. By having the ratio in such a range, the effect of using the inorganic filler (d) is enhanced without impairing the properties of the resin film forming layer.

[0167] (Coupling Agent (e)) When the composition (IV) and the resin film forming layer contain a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and adhesion of the resin film forming layer to an adherend are improved. In addition, the cured product of the resin film forming layer (e.g., a resin film) is improved in water resistance without impairing heat resistance.

[0168] The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group possessed by the acrylic resin (b), the energy ray-curable component (a), etc., and is more preferably a silane coupling agent. Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2- Examples of the silane include bis(3-(aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazole silane.

[0169] The coupling agent (e) contained in the composition (IV) and the resin film forming layer may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0170] When the coupling agent (e) is used, the content of the coupling agent (e) in the composition (IV) and the resin film forming layer is preferably 0.03 to 20 parts by mass relative to 100 parts by mass of the total content of the energy ray curable component (a) and the acrylic resin (b). When the content of the coupling agent (e) is equal to or greater than the lower limit, the effects of using the coupling agent (e), such as improved dispersibility of the inorganic filler (d) in the resin and improved adhesion of the resin film forming layer to the adherend, are more significantly obtained. When the content of the coupling agent (e) is equal to or less than the upper limit, the generation of outgassing is more suppressed.

[0171] (Crosslinking agent (f)) When the acrylic resin (b) has a functional group capable of bonding with other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, or an isocyanate group, the composition (IV) and the resin film forming layer may contain a crosslinking agent (f). The crosslinking agent (f) is a component for bonding the functional group in the acrylic resin (b) with other compounds to form a crosslink, and by crosslinking in this way, the initial adhesive strength and cohesive strength of the resin film forming layer can be adjusted.

[0172] 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), and aziridine crosslinking agents (crosslinking agents having an aziridinyl group).

[0173] Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates, and adducts of the aromatic polyisocyanate compounds, etc.; and terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyisocyanate compounds, etc. with polyol compounds. The "adduct" refers to a reaction product of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound with a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane, as described below. Moreover, the term "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

[0174] More specific examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; a compound in which one or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or a portion of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, and the like.

[0175] Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine, and the like.

[0176] (Colorant (g)) When the composition (IV) and the resin film forming layer contain the colorant (g), the light transmittance of the resin film forming layer can be adjusted by adjusting the content of the colorant (g). By adjusting the light transmittance in this way, for example, the visibility of the laser mark when the resin film forming layer or the resin film is laser marked can be adjusted. In addition, the design of the resin film can be improved, and the grinding marks on the back surface of the wafer can be made less visible.

[0177] Examples of the colorant (g) include known ones such as inorganic pigments, organic pigments, and organic dyes.

[0178] The colorant (g) contained in the composition (IV) and the resin film forming layer may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0179] (Thermosetting component (h)) When the composition (IV) and the resin film-forming layer contain an energy ray-curable component (a) and a thermosetting component (h), the adhesive strength of the resin film-forming layer to the substrate is improved by heating, and the strength of the cured product of the resin film-forming layer (e.g., a resin film) is also improved.

[0180] Examples of the thermosetting component (h) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins, with epoxy-based thermosetting resins being preferred.

[0181] The epoxy thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2). The epoxy-based thermosetting resin contained in the composition (IV) and the resin film forming layer may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0182] Epoxy resin (h1) The epoxy resin (h1) may be any known substance, such as a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenylene skeleton type epoxy resin, or another epoxy compound having two or more functional groups.

[0183] Heat hardener (h2) The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1). The thermosetting agent (h2) may be, for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. The functional group may, for example, be a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, or an anhydride group of an acid group, and is preferably a phenolic hydroxyl group, an amino group, or an anhydride group of an acid group, and more preferably a phenolic hydroxyl group or an amino group.

[0184] Among the heat curing agents (h2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Among the heat curing agents (h2), examples of amine-based curing agents having an amino group include dicyandiamide.

[0185] The thermosetting agent (h2) contained in the composition (IV) and the resin film forming layer may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0186] (General-purpose additives (z)) The general-purpose additive (z) may be a known one and can be selected according to the purpose without any particular limitation.Preferred general-purpose additive (z) includes, for example, a plasticizer, an antistatic agent, an antioxidant, a gettering agent, an ultraviolet absorbing agent, etc.

[0187] The general-purpose additive (z) contained in the composition (IV) and the resin film forming layer may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0188] When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the composition (IV) and the resin film forming layer is not particularly limited and may be appropriately selected depending on the purpose. For example, when the general-purpose additive (z) is an ultraviolet absorber, the ratio of the content of the general-purpose additive (z) (ultraviolet absorber) to the total content of all components other than the solvent in the composition (IV) (i.e., the ratio of the content of the general-purpose additive (z) (ultraviolet absorber) to the total mass of the resin film forming layer in the resin film forming layer) is preferably 0.1 to 5 mass%. When the ratio is equal to or greater than the lower limit, the effect of using the general-purpose additive (z) is more pronounced. When the ratio is equal to or less than the upper limit, excessive use of the general-purpose additive (z) is suppressed.

[0189] (Other polymers (b0) having no energy ray-curable groups) The other polymer (b0) having no energy ray-curable group imparts film-forming properties to the resin film-forming layer. The polymer (b0) is not particularly limited as long as it does not fall under the category of the acrylic resin (b). The polymer (b0) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

[0190] Examples of the polymer (b0) include an acrylic resin having a weight average molecular weight of more than 1,100,000, an acrylic resin having a dispersity of 3.0 or less (in this specification, these acrylic resins may be referred to as "other acrylic resins"); and a polymer other than an acrylic resin that does not have an energy ray-curable group.

[0191] [solvent] Composition (IV) preferably further contains a solvent. Composition (IV) containing a solvent has good handleability. The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. The solvent contained in the composition (IV) may be only one type, or may be two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0192] A more preferred example of the solvent contained in composition (IV) is methyl ethyl ketone, etc., which allows the components contained in composition (IV) to be mixed more uniformly.

[0193] The content of the solvent in the composition (IV) is not particularly limited, and may be appropriately selected depending on, for example, the types of components other than the solvent.

[0194] Up to this point, the resin film forming layer is an energy ray curable protective film forming film, and the resin film forming composition for forming it is an energy ray curable resin film forming composition (IV) has been described, but it is not limited thereto, and the same applies when the resin film forming layer is a thermosetting protective film forming film, a non-curable protective film forming film, or a film-like adhesive. By changing and using the resin film forming composition to a known thermosetting protective film forming composition, a known non-curable protective film forming composition, and a known adhesive composition, a thermosetting protective film forming film, a non-curable protective film forming film, and a film-like adhesive can be formed.

[0195] Method for producing resin film-forming composition The energy ray-curable resin film-forming composition such as composition (IV) can be obtained by blending the respective components constituting the composition. The resin film-forming composition can be produced by the same method as the pressure-sensitive adhesive composition described above, except that the types of ingredients used are different. A thermosetting composition for forming a protective film, a non-curable composition for forming a protective film, and an adhesive composition can also be produced in the same manner.

[0196] ◇Manufacturing method of composite sheet for resin film formation The composite sheet for resin film formation can be produced by laminating the above-mentioned layers so as to have a corresponding positional relationship, and adjusting the shape of some or all of the layers as necessary. The method for forming each layer is as described above.

[0197] It is possible to directly form a resin film-forming layer by applying a resin film-forming composition on the pressure-sensitive adhesive layer already laminated on the substrate. In this way, when forming a new layer (hereinafter abbreviated as "second layer") on any layer (hereinafter abbreviated as "first layer") already laminated on the substrate to form a continuous two-layer laminate structure (in other words, a laminate structure of the first layer and the second layer), a method of applying a composition for forming the second layer on the first layer and drying it as necessary can be applied. However, it is preferable to form the second layer in advance on a release film using a composition for forming the second layer, and then bond the exposed surface of the second layer opposite to the side in contact with the release film to the exposed surface of the first layer to form a continuous two-layer laminate structure. In this case, it is preferable to coat the composition on the release-treated surface of the release film. The release film can be removed as necessary after the laminate structure is formed. Here, we have given an example of laminating a resin film-forming layer onto an adhesive layer, but the target laminate structure can be selected arbitrarily, for example, when laminating a layer (film) other than the resin film-forming layer onto the adhesive layer.

[0198] In this way, all layers other than the substrate that constitute the composite sheet for forming a resin film can be formed in advance on a release film and laminated by bonding it to the surface of the desired layer, so the composite sheet for forming a resin film can be manufactured by appropriately selecting the layers that will undergo such a process as necessary.

[0199] In addition, the composite sheet for resin film formation is usually stored in a state where a release film is attached to the surface of the outermost layer (e.g., resin film forming layer, protective film forming film, film-like adhesive) on the opposite side to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for resin film formation, a composition for protective film formation, an adhesive composition, etc., is applied onto this release film (preferably its release-treated surface), and dried as necessary to form a layer constituting the outermost layer on the release film, and the remaining layers are laminated on the exposed surface opposite the side in contact with the release film by any of the above-mentioned methods, and the release film is not removed and the laminated state is left as it is, thereby obtaining a composite sheet for resin film formation with a release film (i.e., a composite sheet for protective film formation, a dicing die bonding sheet, etc.).

[0200] <<Kit>> A kit according to one embodiment of the present invention comprises a first laminate in which a first release film, a resin film forming layer and a second release film are laminated in that order, and the support sheet used to support the workpiece to which the resin film forming layer is to be attached and the resin film forming layer. An example of the kit of this embodiment will be described below with reference to the drawings.

[0201] FIG. 5 is a cross-sectional view illustrating a schematic example of the kit of the present embodiment. The kit of this embodiment comprises a first laminate 5 in which a first release film 151, a resin film forming layer 13 and a second release film 152 are laminated in this order, and a support sheet 10 used to support the workpiece to which the resin film forming layer 13 is to be attached and the resin film forming layer 13, and the support sheet 10 is a support sheet according to one embodiment of the present invention described above.

[0202] The resin film forming layer 13 shown here has a first release film 151 on one of its surfaces (sometimes referred to as the "first surface" in this specification) 13a, and a second release film 152 on the other surface (sometimes referred to as the "second surface" in this specification) 13b opposite the first surface 13a. Such a resin film forming layer 13 is suitable for storage, for example, in a roll form.

[0203] The resin film forming layer 13 can be formed using the above-mentioned resin film forming composition.

[0204] Both the first release film 151 and the second release film 152 may be of known types. The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other, for example, in that the peeling forces required to peel them from the resin film formation layer 13 are different from each other.

[0205] 5, one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the surface to be attached to the back surface of the work (not shown). Then, the remaining other of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the surface to be attached to the back surface of the support sheet.

[0206] Figure 5 shows an example in which a release film is provided on both sides (first side 13a and second side 13b) of the resin film-forming layer 13, but the release film may be provided on only one side of the resin film-forming layer 13, i.e., only the first side 13a or only the second side 13b.

[0207] The kit of this embodiment can perform both the formation of the resin film and the dicing in an in-line process by using the resin film formation layer 13 and the support sheet 10 in combination. Here, "in-line process" refers to a process "in a device in which multiple devices (machines) performing one or multiple steps are connected together, or in the same device, including multiple steps and the transportation connecting the steps, in which the workpieces are transported one by one between one step and the next step."

[0208] When the resin film forming layer is a protective film forming film, a kit including the support sheet and the resin film forming layer can be used to manufacture a chip with a protective film, comprising a chip and a protective film provided on the back surface of the chip, by the manufacturing method for a chip with a resin film described below.

[0209] When the resin film forming layer is a film-like adhesive, a kit including the support sheet and the resin film forming layer can be used to manufacture a chip with a film-like adhesive, comprising a chip and a film-like adhesive provided on the back surface of the chip, by the method for manufacturing a chip with a resin film described below, and the chip is die-bonded to the circuit surface of the substrate by the film-like adhesive.

[0210] <<Method of manufacturing chips with resin coating>> The support sheet according to the above-mentioned embodiment of the present invention, the composite sheet for forming a resin film comprising the support sheet, and the kit comprising the support sheet can be used in a method for manufacturing a chip with a resin film comprising a chip and a resin film provided on the back surface of the chip.

[0211] <Manufacturing method 1> The manufacturing method according to the first embodiment is a method for manufacturing a resin film-coated chip including a chip and a resin film provided on a back surface of the chip, The method for producing the resin-film-coated chip includes the steps of: attaching a resin film-forming layer in the composite sheet for resin film formation according to the embodiment of the present invention described above to the back surface of a workpiece to produce a first laminated composite sheet in which the support sheet, the resin film-forming layer, and the workpiece are laminated in this order in the thickness direction; A process of forming the resin film by curing the resin film forming layer in the first laminated composite sheet to produce a second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction; Dividing the work in the second laminated composite sheet and cutting the resin film to produce a third laminated composite sheet in which a plurality of chips with a resin film are fixed on the support sheet; and picking up the resin-film-attached chip in the third laminated composite sheet by separating it from the support sheet. Hereinafter, the manufacturing method according to the first embodiment may be referred to as "manufacturing method 1" in this specification.

[0212] Hereinafter, manufacturing method 1, manufacturing method 2 and manufacturing method 3 will be described in order with reference to the drawings.

[0213] 6A to 6D are cross-sectional views for typically explaining manufacturing method 1. Here, manufacturing method 1 will be explained by taking as an example a case where a composite sheet 101 for resin film formation in FIG. 2 having a support sheet 10 shown in FIG. 1 is used.

[0214] In the step of producing the first laminated composite sheet in manufacturing method 1, as shown in Fig. 6A, the resin film forming layer 13 in the composite sheet 101 for resin film formation is attached to the back surface 9b of the work 9 to produce a first laminated composite sheet 501 in which the support sheet 10, the resin film forming layer 13 and the work 9 are laminated in this order in the thickness direction. The first surface 13a of the resin film forming layer 13 in the composite sheet 101 for resin film formation is attached to the back surface 9b of the work 9.

[0215] The resin film forming layer 13 in the composite sheet for resin film formation 101 can be attached to the workpiece 9 by a known method. For example, the resin film forming layer 13 may be attached to the workpiece 9 while being heated.

[0216] Next, in the step of producing the second laminated composite sheet of manufacturing method 1, the resin film forming layer 13 in the first laminated composite sheet 501 is hardened to form a resin film 13', thereby producing a second laminated composite sheet 502 in which the support sheet 10, the resin film 13' and the workpiece 9 are stacked in this order in the thickness direction, as shown in Figure 6B.

[0217] Reference numeral 13a' denotes a surface of the resin film 13' that was the first surface 13a of the resin film-formed layer 13 (sometimes referred to as the "first surface" in this specification). Reference numeral 13b' denotes a surface of the resin film 13' that was the second surface 13b of the resin film-formed layer 13 (sometimes referred to as the "second surface" in this specification).

[0218] When the resin film forming layer 13 is thermosetting, the resin film forming layer 13 can be cured by heating the resin film forming layer 13. When the resin film forming layer 13 is energy ray curable, the resin film forming layer 13 is irradiated with energy rays from the outside of the support sheet 10 side of the first laminated composite sheet 501 through the support sheet 10 (through the support sheet 10).

[0219] When the resin film forming layer 13 is a protective film forming film, the resin film forming layer 13 shown in Figure 6A may be laser marked by irradiating it with a laser through the support sheet 10 (through the support sheet 10), or the resin film 13' shown in Figure 6B may be laser marked by irradiating it with a laser through the support sheet 10 (through the support sheet 10).

[0220] Next, in the step of producing the third laminated composite sheet in the manufacturing method 1, as shown in FIG. 6C, the work 9 in the second laminated composite sheet 502 is divided on the support sheet 10, and the resin film 13' is cut. The work 9 is divided into individual pieces to become a plurality of chips 90. Since the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate in the adhesive layer 12 is appropriately controlled, the adhesive force between the adhesive layer 12 and the resin film 130' after cutting is sufficiently maintained, and the risk of division failure can be reduced, and the adhesive force between the adhesive layer 12 and the base material 11 is also sufficiently maintained, and the risk of peeling failure between the adhesive layer 12 and the base material 11 can also be reduced.

[0221] The division of the workpiece 9 and the cutting of the resin film 13' may be performed by a known method. For example, the division of the workpiece 9 and the cutting of the resin film 13' can be performed successively by dicing such as blade dicing, laser dicing by irradiating a laser, or water dicing by spraying water containing an abrasive. The resin film 13' is cut along the outer periphery of the chip 90, regardless of the cutting method.

[0222] In this manner, by dividing the workpiece 9 and cutting the resin film 13', a plurality of chips 901 with resin film are obtained, each chip 90 having a resin film (sometimes simply referred to as "resin film" in this specification) 130' after cutting provided on the back surface 90b of the chip 90. Reference numeral 130b' denotes a surface of the resin film 130' after cutting that was the second surface 13b' of the resin film 13' (sometimes referred to as "second surface" in this specification).

[0223] In the step of producing the third laminated composite sheet in manufacturing method 1, the third laminated composite sheet 503 in which the plurality of resin-film-coated chips 901 are fixed on the support sheet 10 is produced as described above.

[0224] Next, in the picking up step of manufacturing method 1, as shown in FIG. 6D, chip 901 with resin film in third laminated composite sheet 503 is picked up by being pulled away from support sheet 10. In the picking up step, peeling occurs between second surface 130b' of resin film 130' in resin-film-coated chip 901 and first surface 12a of adhesive layer 12 in support sheet 10.

[0225] Here, a case is shown in which a separating means 7 such as a vacuum collet is used to separate the resin film-coated chip 901 in the direction of the arrow P. Note that a cross-sectional view of the separating means 7 is omitted here. The resin film-coated chip 901 can be picked up by a known method.

[0226] On the other hand, if the adhesive layer 12 is non-energy ray curable, the resin film-coated chip 901 can be simply pulled away from the adhesive layer 12, and since there is no need to harden the adhesive layer 12, the resin film-coated chip 901 can be picked up in a simplified process.

[0227] In the picking up step, such picking up of the resin-coated chips 901 is performed for all of the intended resin-coated chips 901 .

[0228] In the manufacturing method 1, the intended chip 901 with a resin film is obtained by carrying out the steps up to the picking up step.

[0229] So far, we have explained manufacturing method 1 in the case of using a composite sheet 101 for forming a resin film having a support sheet 10 shown in Figure 2. However, in manufacturing method 1, a composite sheet for forming a resin film of this embodiment other than the composite sheet 101 for forming a resin film, such as the composite sheet 102 for forming a resin film or the composite sheet 103 for forming a resin film shown in Figures 3 to 4, may also be used.

[0230] <Manufacturing method 2> The manufacturing method according to the second embodiment is a method for manufacturing a resin film-coated chip including a chip and a resin film provided on a back surface of the chip, The method for producing the resin-coated chip includes the steps of: attaching the resin-coated layer in the kit according to the embodiment of the present invention to the back surface of a workpiece, and producing a first laminated film in which the resin-coated layer and the workpiece are laminated in the thickness direction; A process of forming the resin film by curing the resin film forming layer in the first laminate film, and producing a second laminate film in which the resin film and the workpiece are laminated in their thickness direction; A step of attaching an adhesive layer of the support sheet in the kit to a second laminate film to produce a second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction; Dividing the work in the second laminated composite sheet and cutting the resin film to produce a third laminated composite sheet in which a plurality of chips with a resin film are fixed on the support sheet; and picking up the resin-film-attached chip in the third laminated composite sheet by separating it from the support sheet. Hereinafter, the production method according to the second embodiment will be referred to as "production method 2" in this specification.

[0231] 7A to 7E are cross-sectional views for typically explaining manufacturing method 2. Here, manufacturing method 2 will be explained by taking as an example a case where kit 1 in Fig. 5 including support sheet 10 shown in Fig. 1 is used.

[0232] In the step of producing the first laminated film in the manufacturing method 2, the resin film forming layer 13 in the kit 1 is attached to the back surface 9b of the work 9 to produce a first laminated film 601 in which the resin film forming layer 13 and the work 9 are laminated in their thickness direction as shown in Fig. 7A. In this case, as in the manufacturing method 1, the first surface 13a of the resin film forming layer 13 in the composite sheet 101 for resin film formation is attached to the back surface 9b of the work 9.

[0233] Here, the first release film 151 is removed from the first laminate 5 of the kit 1 shown in FIG. 5, and the first surface 13a of the resin film-formed layer 13 is attached to the back surface 9b of the work 9. Alternatively, the second release film 152 may be removed from the resin film-formed layer 13 of the kit 1 shown in FIG. 5, and the second surface 13b of the resin film-formed layer 13 may be attached to the back surface 9b of the work 9. A circular punching blade may be applied to the first laminate 5 of the kit 1 shown in FIG. 5 from the side of the first release film 151 to peel off the first release film 151, and the circular outer side of the resin film-formed layer 13 may be removed together with the first release film 151, and the resulting circular first surface 13a of the resin film-formed layer 13 may be attached to the back surface 9b of the work 9.

[0234] The resin film forming layer 13 can be attached to the workpiece 9 by a known method. For example, the resin film forming layer 13 may be attached to the workpiece 9 while being heated.

[0235] Next, in the step of producing the second laminate film in manufacturing method 2, the resin film forming layer 13 in the first laminate film 601 is hardened to form a resin film 13', thereby producing a second laminate film 602 in which the resin film 13' and the workpiece 9 are laminated in their thickness direction, as shown in Figure 7B.

[0236] When the resin film forming layer 13 is thermosetting, the resin film forming layer 13 can be cured by heating the resin film forming layer 13. When the resin film forming layer 13 is energy ray curable, in the step of producing the second laminated film, the resin film forming layer 13 is irradiated with energy rays from the outside of the resin film forming layer 13 side of the first laminated film 601 through the second release film 152 (through the second release film 152) to form a resin film 13'. In the process of producing the second laminate film, the second release film 152 may be removed from the resin film forming layer 13 in the first laminate film 601 to expose the second surface 13b of the resin film forming layer 13, and then the resin film forming layer 13 may be irradiated with energy rays to form a resin film 13'.

[0237] When the resin film forming layer 13 is a protective film forming film, the resin film forming layer 13 shown in Figure 7A may be laser-marked by irradiating it with a laser through the second peeling film 152 (through the second peeling film 152), or the resin film 13' shown in Figure 7B may be laser-marked by irradiating it with a laser through the second peeling film 152 (through the second peeling film 152).

[0238] Next, in the step of producing the second laminated composite sheet in manufacturing method 2, first, the second release film 152 is removed from the resin film 13' in the second laminated film 602. Then, one surface 10a of the support sheet 10 (sometimes referred to as the "first surface" in this specification) is attached to the second surface 13b' of the resin film 13' newly exposed as a result, as shown in Fig. 7C. The support sheet 10 shown here is configured to include a base material 11 and an adhesive layer 12 provided on one surface 81a of the base material 11, and the adhesive layer 12 in the support sheet 10 is attached to a resin film 13'. A surface 12a of the adhesive layer 12 facing the resin film 13' (sometimes referred to as the "first surface" in this specification) is the same as the first surface 10a of the support sheet 10.

[0239] Next, in the step of producing the third laminated composite sheet, in a state where the support sheet 10 is provided on the resin film 13' side of the second laminated film 602, as shown in FIG. 7D, the work 9 in the second laminated film 602 is divided and the resin film 13' is cut. The work 9 is divided into individual pieces to become a plurality of chips 90. Since the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate in the adhesive layer 12 is appropriately controlled, the adhesive force between the adhesive layer 12 and the resin film 130' after cutting is sufficiently maintained, and the risk of division failure can be reduced, and the adhesive force between the adhesive layer 12 and the base material 11 is also sufficiently maintained, and the risk of peeling failure between the adhesive layer 12 and the base material 11 can also be reduced.

[0240] The step of preparing the third laminated composite sheet can be carried out in the same manner as the step of preparing the third laminated composite sheet in Production Method 1. In the manufacturing method 2 as well, the resin film 13' is cut along the outer periphery of the chip 90, regardless of the cutting method used.

[0241] In this manner, by dividing the work 9 and cutting the resin film 13', a plurality of resin-film-coated chips 901 are obtained, each chip 90 comprising a resin film 130' after cutting provided on the back surface 90b of the chip 90.

[0242] These protective film-attached chips 901 obtained in the step of producing the third laminated composite sheet in Production Method 2 are the same as the protective film-attached chips 901 obtained in the step of producing the third laminated composite sheet in Production Method 1.

[0243] In the step of producing the third laminated composite sheet in manufacturing method 2, the third laminated composite sheet 503 in which the plurality of resin-film-coated chips 901 are fixed on the support sheet 10 is produced as described above.

[0244] Next, in the picking up step of manufacturing method 2, chip 901 with resin film on supporting sheet 10 is picked up by being pulled away from supporting sheet 10 as shown in FIG. 7E. The picking up step in the manufacturing method 2 can be carried out in the same manner as the picking up step in the manufacturing method 1.

[0245] Since the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate in the adhesive layer 12 is appropriately controlled, the adhesive strength between the adhesive layer 12 and the resin film 130' can be made smaller than the adhesive strength between the adhesive layer 12 and the substrate 11, and the resin film-coated chip 901 can be easily picked up by picking up the resin film-coated chip 901.

[0246] In manufacturing method 2, by carrying out the steps up to the picking up step, the intended chip with resin film 901 is obtained. The chip with resin film 901 obtained by manufacturing method 2 is the same as the chip with resin film 901 obtained by manufacturing method 1.

[0247] <Manufacturing method 3> A manufacturing method according to a third embodiment is a method for manufacturing a resin film-coated chip including a chip and a resin film provided on a back surface of the chip, The method for producing the resin film-coated chip includes the steps of: attaching a resin film forming layer in a composite sheet for resin film formation according to the embodiment of the present invention described above to the back surface of a workpiece, or attaching a resin film forming layer in a kit according to the embodiment of the present invention described above to the back surface of a workpiece to produce a first laminated film in which the resin film forming layer and the workpiece are laminated in their thickness direction; and further attaching an adhesive layer of a support sheet in the kit to the resin film forming layer in the first laminated film to produce a first laminated composite sheet in which the support sheet, resin film forming layer and workpiece are laminated in this order in their thickness direction. A step of dividing the work in the first laminated composite sheet and cutting the resin film forming layer to produce a fourth laminated composite sheet in which a plurality of chips with a resin film forming layer are fixed on the support sheet; and picking up the chips with the resin film forming layer in the fourth laminated composite sheet by separating them from the support sheet. Hereinafter, the manufacturing method according to the third embodiment will be referred to as "manufacturing method 3" in this specification.

[0248] 8A to 8C are cross-sectional views for typically explaining manufacturing method 3. Here, manufacturing method 3 will be explained by taking as an example a case where a composite sheet 101 for resin film formation in FIG. 2 having a support sheet 10 shown in FIG. 1 is used.

[0249] In the step of producing the first laminated composite sheet in manufacturing method 3, as shown in FIG. 8A, the resin film forming layer 13 in the composite sheet for resin film formation 101 is attached to the rear surface 9b of the workpiece 9 to produce a first laminated composite sheet 501 in which the support sheet 10, the resin film forming layer 13 and the workpiece 9 are stacked in this order in the thickness direction. The first laminated composite sheet 501 in FIG. 8A is the same as the first laminated composite sheet 501 in FIG. 6A.

[0250] The resin film forming layer 13 in the composite sheet for resin film formation 101 can be attached to the workpiece 9 by a known method. For example, the resin film forming layer 13 may be attached to the workpiece 9 while being heated.

[0251] When the resin film forming layer 13 is a protective film forming film, the resin film forming layer 13 shown in FIG. 8A may be irradiated with a laser through the support sheet 10 (transmitted through the support sheet 10) to perform laser marking.

[0252] Next, in the step of producing the fourth laminated composite sheet in the manufacturing method 3, as shown in FIG. 8B, the work 9 in the first laminated composite sheet 501 is divided, and the resin film forming layer 13 is cut. The work 9 is divided into individual pieces to form a plurality of chips 90. Since the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate in the adhesive layer 12 is appropriately controlled, the adhesive force between the adhesive layer 12 and the resin film forming layer 130 after cutting is sufficiently maintained, and the risk of division failure can be reduced, and the adhesive force between the adhesive layer 12 and the substrate 11 is also sufficiently maintained, and the risk of peeling failure between the adhesive layer 12 and the substrate 11 can also be reduced.

[0253] The division of the work 9 and the cutting of the resin film-formed layer 13 may be performed by a known method. For example, the division of the work 9 and the cutting of the resin film-formed layer 13 are performed along the outer periphery of the chip 90 by dicing such as blade dicing, laser dicing by laser irradiation, or water dicing by spraying water containing an abrasive, regardless of the cutting method.

[0254] In this manner, by dividing the workpiece 9 and cutting the resin film-formed layer 13, a plurality of chips 902 with a resin film-formed layer are obtained, each chip 90 including a resin film-formed layer (sometimes simply referred to as a "resin film" in this specification) 130 after cutting provided on the back surface 90b of the chip 90. Reference numeral 130b indicates the surface of the resin film-formed layer 130 after cutting that was the second surface 13b of the resin film-formed layer 13 (sometimes referred to as the "second surface" in this specification).

[0255] In the step of producing the third laminated composite sheet in manufacturing method 3, a fourth laminated composite sheet 504 in which a plurality of chips 902 with a resin film forming layer are fixed on the support sheet 10 is produced as described above.

[0256] Next, in the picking up step of manufacturing method 3, as shown in FIG. 8C, chips 902 with resin film formation layer in fourth laminated composite sheet 504 are picked up by being pulled away from support sheet 10. In the picking up step, peeling occurs between the second surface 130b of the resin film forming layer 130 in the resin film forming layer-attached chip 902 and the first surface 12a of the pressure-sensitive adhesive layer 12 in the support sheet 10.

[0257] Here, a case is shown in which a separating means 7 such as a vacuum collet is used to separate the chip 902 with the resin film formation layer in the direction of the arrow P. Note that a cross-sectional view of the separating means 7 is omitted here. The chip 902 with the resin film forming layer can be picked up by a known method.

[0258] If the adhesive layer 12 is non-energy ray curable, the chip 901 with the resin film can be simply pulled away from the adhesive layer 12, and since there is no need to harden the adhesive layer 12, the chip 902 with the resin film forming layer can be picked up in a simplified process.

[0259] When a non-curable resin film forming layer is used, a curing process is not required, so at the point when the resin film forming layer 130 after cutting is pulled away from the support sheet, the resin film forming layer 130 is deemed to have changed into a resin film 130', and the chip 902 with the resin film forming layer is deemed to have changed into a chip 901 with a resin film.

[0260] Similarly, even when a curable resin film forming layer is used, if the resin film forming layer 130 after cutting is uncured, at the time the resin film forming layer 130 is pulled away from the support sheet, the resin film forming layer 130 is deemed to have changed into a resin film 130', and the chip 902 with the resin film forming layer is deemed to have changed into a chip 901 with a resin film.

[0261] In the picking up step, the picking up of such chips 902 with a resin film formation layer is performed for all of the desired chips 902 with a resin film formation layer.

[0262] In the manufacturing method 3, the intended chip 901 with a resin film is obtained by carrying out the steps up to the picking up step.

[0263] So far, we have explained manufacturing method 1 in the case of using a composite sheet 101 for forming a resin film having a support sheet 10 shown in Figure 2. However, in manufacturing method 3, a composite sheet for forming a resin film of this embodiment other than the composite sheet 101 for forming a resin film, such as the composite sheet 102 for forming a resin film or the composite sheet 103 for forming a resin film shown in Figures 3 to 4, may also be used.

[0264] ◇ Manufacturing method of substrate device (method of using chip with resin film) After obtaining a chip with a resin film by the above-mentioned manufacturing method, a substrate device can be manufactured in the same manner as the conventional substrate device manufacturing method, except that this chip with a resin film is used instead of a conventional chip with a protective film or a chip with a protective film-forming film, or a chip with a film-like adhesive.

[0265] For example, when the resin film forming layer is a protective film forming film and the resin film-coated chip is a protective film-coated chip, a manufacturing method can be mentioned that includes a flip chip connection step in which the resin film-coated chip obtained using the protective film forming film is picked up from a support sheet, and the protruding electrode on the resin film-coated chip is brought into contact with a connection pad on a circuit board, thereby electrically connecting the protruding electrode and the connection pad on the circuit board.

[0266] In the case where the resin film forming layer is a protective film forming film and the chip with a resin film is a chip with a protective film forming film, the chip with a resin film forming layer obtained using the protective film forming film is picked up from a support sheet, and if necessary, cured by heat or energy rays, and the protruding electrode on the chip with a resin film is brought into contact with a connection pad on a circuit board, thereby electrically connecting the protruding electrode and the connection pad on the circuit board, a manufacturing method that includes a flip chip connection step.

[0267] In the case where the resin film forming layer is a film-like adhesive and the chip with resin film is a chip with a film-like adhesive, a manufacturing method can be mentioned which has a connection step in which a chip with a resin film forming layer obtained using the film-like adhesive is picked up from a support sheet, and the chip with a resin film is attached to a circuit board via the film-like adhesive. EXAMPLES

[0268] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the following examples.

[0269] <Raw materials for resin production> The full names of the raw materials for producing the resins, which are abbreviated in the present examples and comparative examples, are shown below. 2EHMA: 2-Ethylhexyl methacrylate HEA: 2-hydroxyethyl acrylate BA: n-butyl acrylate MA: Methyl acrylate ACrMO: 4-Acryloylmorpholine

[0270] <Production of Pressure-Sensitive Adhesive Composition (I-4)-1> A non-energy ray curable pressure-sensitive adhesive composition (I-4)-1 was prepared, which contained an acrylic resin (100 parts by mass) which is a copolymer having a weight average molecular weight of 600,000 and is obtained by copolymerizing 2EHMA (80 parts by mass) and HEA (20 parts by mass), a tolylene diisocyanate-based crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (5.0 parts by mass as a crosslinking agent component), and a hexamethylene diisocyanate-based crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (12.5 parts by mass as a crosslinking agent component), and further contained methyl ethyl ketone as a solvent.

[0271] <Production of Pressure-Sensitive Adhesive Composition (I-4)-2> A pressure-sensitive adhesive composition (I-4)-2 was prepared in the same manner as pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (10.0 parts by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (7.5 parts by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0272] <Production of Pressure-Sensitive Adhesive Composition (I-4)-3> Pressure-sensitive adhesive composition (I-4)-3 was prepared in the same manner as pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (6.0 parts by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (2.0 parts by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0273] <Production of Pressure-Sensitive Adhesive Composition (I-4)-4> Pressure-sensitive adhesive composition (I-4)-4 was prepared in the same manner as pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (3.0 parts by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (2.0 parts by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0274] <Production of Pressure-Sensitive Adhesive Composition (I-4)-5> Pressure-sensitive adhesive composition (I-4)-5 was prepared in the same manner as pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (1.0 part by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (4.0 parts by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0275] <Production of Pressure-Sensitive Adhesive Composition (I-4)-6> A pressure-sensitive adhesive composition (I-4)-6 was prepared in the same manner as for pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (15.0 parts by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (2.5 parts by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0276] <Production of Pressure-Sensitive Adhesive Composition (I-4)-7> Pressure-sensitive adhesive composition (I-4)-7 was prepared in the same manner as pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (4.0 parts by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (1.0 part by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0277] <Production of Pressure-Sensitive Adhesive Composition (I-4)-8> A pressure-sensitive adhesive composition (I-4)-8 was prepared in the same manner as for pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate-based crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (1.0 part by mass as a crosslinking agent component) and a hexamethylene diisocyanate-based crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (1.0 part by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0278] <Production of Pressure-Sensitive Adhesive Composition (I-4)-9> A pressure-sensitive adhesive composition (I-4)-9 was prepared in the same manner as for pressure-sensitive adhesive composition (I-4)-1, except that the blending ratio of a tolylene diisocyanate crosslinking agent ("BHS8515" manufactured by Toyochem Co., Ltd.) (2.5 parts by mass as a crosslinking agent component) and a hexamethylene diisocyanate crosslinking agent ("Coronate HL" manufactured by Tosoh Corporation) (15.0 parts by mass as a crosslinking agent component) to the acrylic resin (100 parts by mass) was changed.

[0279] <Manufacture of Support Sheet> [Example 1] A release film ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) made of polyethylene terephthalate film, one side of which had been subjected to a release treatment by silicone treatment, was used. The pressure-sensitive adhesive composition (I-4)-1 obtained above was applied to the release-treated surface, and the resulting film was dried by heating at 100° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm. Next, a polypropylene film (thickness 80 μm, colorless) was attached as a substrate to the exposed surface of the adhesive layer to produce a support sheet with release film of Example 1, in which the substrate, adhesive layer and release film were laminated in this order in the thickness direction.

[0280] [Examples 2 to 5] Support sheets with release films of Examples 2 to 5 were produced in the same manner as in Example 1, except that the adhesive composition (I-4)-1 of Example 1 was changed to adhesive compositions (I-4)-2 to (I-4)-5.

[0281] [Comparative Examples 1 to 4] Support sheets with release films of Comparative Examples 1 to 4 were produced in the same manner as in Example 1, except that the adhesive composition (I-4)-1 in Example 1 was changed to adhesive compositions (I-4)-6 to (I-4)-9.

[0282] <Seasoning period measurement> A number of support sheets with release films were prepared for each of Examples 1 to 5 and Comparative Examples 1 to 4, and the sheets were left to stand in an environment of 23°C and a relative humidity of 50% for curing, while the adhesive strength shown below was measured every other day (once every two days).

[0283] The release film was peeled off from the support sheet with release film, and the exposed adhesive layer of the support sheet was attached to the mirror surface of a silicon wafer with a 2 kg roller and left to stand at a temperature of 23° C. for 30 minutes. Next, using a general-purpose tensile tester (Shimadzu AG-IS MS), the support sheet was peeled off from the silicon wafer at the same temperature at a peeling speed of 300 mm / min so that the exposed adhesive layer of the support sheet and the surfaces of the silicon wafer that had been in contact with each other formed an angle of 180°, a so-called 180° peel test was performed. The first 25 mm was ignored, and the peel force was measured for the subsequent 50 mm, and the average value was taken as the adhesive force (mN / 25 mm) of the adhesive layer of the support sheet to the silicon wafer. The day when the change in adhesive strength from the previous measurement became 10% or less was determined as the end date of seasoning, and the number of days in the seasoning period was determined as the period from when the adhesive composition was applied to the release-treated surface of the release film and the substrate was attached to the adhesive layer to produce a support sheet to the end date of seasoning. In addition, when the number of days in the seasoning period was 14 days or less, it was evaluated as good A, and when the number of days in the seasoning period was 15 days or more, it was evaluated as poor B. The evaluation results are shown in Tables 1 and 2.

[0284] <Measurement of adhesion to substrate> The support sheets with release film of Examples 1 to 5 and Comparative Examples 1 to 4 were cured for the number of days of the seasoning period under an environment of 23°C and 50% relative humidity, and then cut to obtain square keying test sheets with sides of 200 mm. 21 lines (400 squares) were cut in a checkerboard pattern at 5 mm intervals in both the vertical and horizontal directions in the center of the main surface of the adhesive layer side of this substrate adhesion test sheet. Each line cut completely cuts the adhesive layer, but the cut depth into the substrate is shallow. Five rows of cellophane adhesive tape (Nichiban Co., Ltd. Cellotape (registered trademark) No. 405) were attached to the main surface of the adhesive layer side of the substrate adhesion test sheet thus obtained so that the tapes overlap each other, and the entire checkerboard cut was covered with the attached cellophane adhesive tape. In this state, it was left in an environment of 23°C and 50% relative humidity for 20 minutes. Thereafter, while holding the keying test sheet with one hand, one end of the cellophane adhesive tape was held with the other hand, and the cellophane adhesive tape was quickly peeled off in the direction normal to the main surface of the substrate adhesion test sheet. The grid-cut cuts on the substrate adhesion test sheet after peeling off the cellophane adhesive tape were visually observed, and the number of squares that did not peel off even partially was counted as the number of adhered squares, and the non-peeling rate (unit: %) was calculated using the following formula. A non-peeling rate of 90% or more was judged as excellent (A), a non-peeling rate of 80% or more but less than 90% was judged as good (B), and a non-peeling rate of less than 80% was judged as poor (C). The results are shown in Tables 1 and 2. Non-peeling rate (%) = Number of attached masses / 400 x 100

[0285] [Table 1]

[0286] [Table 2]

[0287] <Raw materials for producing the resin film-forming composition> The resin film forming composition used for forming the resin film forming layer will be described below. Here, the resin film forming layer is an example of a protective film forming film used for protecting the back surface of a workpiece or a chip obtained by dividing the workpiece. The raw materials used in the production of the resin film-forming composition are shown below. [Energy ray curable component (a)] (a)-1: Urethane acrylate (KJ Chemicals' "Quick cure 8100EA70") (a)-2: ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd., a trifunctional ultraviolet-curable compound) [Acrylic resin (b) having no energy ray-curable group] (b)-1: An acrylic resin (weight average molecular weight 700,000, glass transition temperature 2° C.) which is a copolymer of BA (33 parts by mass), MA (27 parts by mass), ACrMO (25 parts by mass), and HEA (15 parts by mass). [Photopolymerization initiator (c)] (c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (BASF "Omnirad (registered trademark) 369") (c)-2: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (BASF "Omnirad (registered trademark) 127D") [Inorganic filler (d)] (d)-1: Silica filler (fused silica filler, average particle size 8 μm) [Colorant (g)] (g)-1: Black pigment (a pigment obtained by mixing 32 parts by mass of a phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone red pigment (Pigment Red 177), and pigmenting the mixture such that the total amount of the three pigments / amount of styrene acrylic resin was 1 / 3 (mass ratio).) (z)-1: Hydroxyphenyltriazine-based ultraviolet absorber (BASF "Tinuvin (registered trademark) 479")

[0288] <Production of resin film-forming composition (IV)-1> Energy ray curable component (a)-1 (10.1 parts by mass), energy ray curable component (a)-2 (12.4 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) not having an energy ray curable group, photopolymerization initiator (c)-1 (0.1 parts by mass), photopolymerization initiator (c)-2 (0.5 parts by mass), inorganic filler (d)-1 (58.4 parts by mass), colorant (g)-1 (3 parts by mass) and general-purpose additive (z)-1 (0.8 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to obtain an energy ray curable resin film forming composition (IV)-1 having a total concentration of 45% by mass of all components other than the solvent. Note that the blending amounts of all components other than the solvent shown here are the blending amounts of the target product excluding the solvent.

[0289] <Production of resin film forming layer> A release film (second release film, "SP-PET382150" manufactured by Lintec Corporation, thickness 38 μm) made of polyethylene terephthalate film, one side of which had been treated for release by silicone treatment, was used, and the resin film forming composition (IV)-1 obtained above was applied to the release-treated surface, followed by drying at 100°C for 2 minutes to produce an energy ray-curable resin film forming layer having a thickness of 25 μm.

[0290] Furthermore, by bonding the release-treated surface of a release film (first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) to the exposed surface of the obtained resin film forming layer that did not have the second release film, a resin film forming layer with a release film was obtained, which was composed of a resin film forming layer, a first release film provided on one surface of the resin film forming layer, and a second release film provided on the other surface of the resin film forming layer.

[0291] <Evaluation of resin film forming layer> Measurement of storage modulus of resin film forming layer Using the multiple resin film forming layers with release films obtained as described above, the exposed surfaces of the resin film forming layers were bonded together while removing the first or second release films, to produce a test piece (resin film forming layer test piece) (thickness 200 μm, length 30 mm in the tensile direction in the tensile mode) which was a laminate of multiple resin film forming layers. Next, using an automatic dynamic viscoelasticity measuring device (A&D's "Leovibron DDV-01FP"), the storage modulus E' of the resin film forming layer test piece was measured in the temperature range from -10°C to 140°C under the measurement conditions of tensile method (tensile mode), chuck distance 20 mm, amplitude 5 μm, frequency 11 Hz, heating rate 3°C / min, and constant heating rate.

[0292] Measurement of storage modulus of resin film Using the multiple resin film forming layers with release films obtained as described above, a laminate (thickness 50 μm) of multiple resin film forming layers was produced by removing the first or second release film and bonding the exposed surfaces of the resin film forming layers together. Next, the laminate was irradiated with ultraviolet light from both sides using a device for irradiating ultraviolet light ("RAD2000m / 8" manufactured by Lintec Corporation) at an illuminance of 200 mW / cm. 2 , light intensity 300mJ / cm 2 The resin film forming layer was cured to form a resin film by irradiating it with ultraviolet light twice under the conditions of 1. In this manner, a laminate of multiple resin films was obtained, and then the width of the laminate was adjusted to 5 mm to prepare a test piece (resin film test piece) (thickness 50 μm). Next, using a dynamic mechanical analyzer ("DMA Q800" manufactured by TA Instruments), the storage modulus E' of the resin film test piece was measured in the temperature range from 0°C to 300°C under the following measurement conditions: tensile method (tensile mode), chuck distance 20 mm, amplitude 5 μm, frequency 11 Hz, heating rate 3°C / min, and constant heating rate.

[0293] The resin film forming layer can be used as a protective film forming film.

[0294] <Production of composite sheet for resin film formation> [Examples 6 to 10, Comparative Examples 5 to 8] The release film was removed from the support sheet with release film of Examples 1 to 5 and Comparative Examples 1 to 4 obtained above. The second release film was also removed from the resin film forming layer obtained above. Then, the exposed surface of the pressure-sensitive adhesive layer obtained by removing the release film was bonded to the exposed surface of the resin film forming layer obtained by removing the second release film, thereby producing composite sheets for resin film formation of Examples 6 to 10 and Comparative Examples 5 to 8, which were configured by laminating the base material, the pressure-sensitive adhesive layer, the resin film forming layer, and the first release film in this order in the thickness direction.

[0295] <Manufacturing chips with resin film> [Example 11] In the composite sheet for resin film formation of Example 6 obtained above, the first release film was removed from the resin film formation layer. Then, using a tape laminating device ("Adwill RAD-2700" manufactured by Lintec Corporation), the newly exposed surface of this resin film formation layer was heat-laminated to the ground surface of a silicon wafer (thickness 300 μm) with a lamination temperature of 70° C., a lamination pressure of 0.3 MPa, and a lamination speed of 0.3 mm / s, thereby laminating the composite sheet for resin film formation to the silicon wafer. In this way, the first laminated composite sheet was produced.

[0296] Next, an ultraviolet ray irradiation device ("RAD2000m / 8" manufactured by Lintec Corporation) was used to irradiate the sample at an illuminance of 200 mW / cm 2 , light intensity 300mJ / cm 2 The resin film forming layer was irradiated twice with ultraviolet light through the substrate and the pressure-sensitive adhesive layer under the above conditions to harden the resin film forming layer and form a resin film. In this manner, a second laminated composite sheet was produced.

[0297] Next, the second laminated composite sheet was subjected to blade dicing using a dicing device (DISCO Corp.'s "DFD6362") to divide the silicon wafer into silicon chips measuring 3 mm x 3 mm, and the resin film was cut along the periphery of the silicon chip to produce multiple chips with the resin film. In this way, a third laminated composite sheet was produced in which multiple silicon chips with the resin film were fixed on the support sheet.

[0298] In the adhesive layer 12 of the support sheet of Example 1, the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate was appropriately controlled, so that the adhesive strength between the adhesive layer 12 and the resin film 130' after cutting was sufficiently maintained, and no separation failure was observed during blade dicing. The adhesive strength between the adhesive layer 12 and the substrate 11 was also sufficiently maintained, and no peeling failure was observed between the adhesive layer 12 and the substrate 11. These resin-coated silicon chips were dried together with the sheet at 125°C for 24 hours.

[0299] Next, the silicon chip with the resin film in the third laminated composite sheet was picked up by separating it from the support sheet.

[0300] In the pressure-sensitive adhesive layer 12 of the support sheet of Example 1, the blending ratio of tolylene diisocyanate and hexamethylene diisocyanate was appropriately controlled, so that no peeling failure was observed between the pressure-sensitive adhesive layer 12 and the substrate 11.

[0301] By the above steps, the intended chip with a resin film was obtained according to Example 11. The chip with a resin film according to Example 11 can be flip-chip connected to a connection pad on a circuit board as a chip with a protective film and used as an element of a substrate device.

[0302] [Examples 12 to 15] Chips with resin film of Examples 12 to 15 were produced in the same manner as in Example 11, except that the composite sheet for resin film formation of Examples 7 to 10 was used instead of the composite sheet for resin film formation of Example 6. As in Example 11, no separation failure was observed during blade dicing, and no peeling failure was observed between the adhesive layer 12 and the substrate 11. No peeling failure was observed between the adhesive layer 12 and the substrate 11 during pick-up.

[0303] [Comparative Examples 9 to 12] The resin film-coated chips of Comparative Examples 9 to 12 were produced in the same manner as in Example 11, except that the composite sheets for resin film formation of Comparative Examples 5 to 8 were used instead of the composite sheet for resin film formation of Example 6. In all of Comparative Examples 9 to 12, slight division defects were observed during blade dicing, and slight peeling defects were also observed between the adhesive layer 12 and the substrate 11. During pick-up, slight peeling defects were observed between the adhesive layer 12 and the substrate 11. [Industrial Applicability]

[0304] The present invention can be used in the manufacture of various substrate devices, including semiconductor devices. [Explanation of symbols]

[0305] 1... kit, 5... first laminate, 10...support sheet, 10a...one side (first side) of the support sheet, 11...Base material, 12...adhesive layer, 13, 23 ... resin film forming layer, 13' ... resin film, 13b' ... other surface (second surface) of the resin film, 130 ... resin film forming layer after cutting, 130' ... resin film after cutting, 101, 102, 103...Composite sheet for forming resin film, 501...first laminated composite sheet, 502...second laminated composite sheet, 503...third laminated composite sheet, 504...fourth laminated composite sheet, 16... jig adhesive layer, 15... release film, 15... release film, 151... first release film, 152... second release film, 601: first laminate film; 602: second laminate film; 9... workpiece, 9b... back surface of workpiece, 90... chip, 90b... back surface of chip, 901... chip with resin film, 902... chip with resin film forming layer

Claims

1. A support sheet having a pressure-sensitive adhesive layer provided on a substrate, The support sheet is used in a method for producing a chip with a resin film, in which a chip with a resin film is picked up by peeling it off from a third laminated composite sheet on which a plurality of chips with a resin film divided on the support sheet are fixed, or a chip with a resin film forming layer is picked up by peeling it off from a fourth laminated composite sheet on which a plurality of chips with a resin film forming layer divided on the support sheet are fixed, the pressure-sensitive adhesive layer is non-energy ray curable and is formed by applying a pressure-sensitive adhesive composition containing an acrylic resin having a hydroxyl group and an isocyanate-based crosslinking agent; The mixing ratio of the isocyanate-based crosslinking agent relative to 1 equivalent of a hydroxyl group of the acrylic resin is 0.07 equivalents or more, The isocyanate-based crosslinking agent contains tolylene diisocyanate and hexamethylene diisocyanate, The blending ratio of the hexamethylene diisocyanate to 1 part by mass of the tolylene diisocyanate is 0.3 to 4.0 parts by mass.

2. A support sheet as described in claim 1, wherein the adhesive layer has a mixing ratio of the isocyanate-based crosslinking agent to 1 equivalent of a hydroxyl group of the acrylic resin of 0.15 equivalents or more.

3. The support sheet according to claim 1 or 2, wherein the acrylic resin has a structural unit derived from a hydroxyalkyl (meth)acrylate.

4. The support sheet according to any one of claims 1 to 3, wherein a constituent material of the substrate contains a polyolefin resin.

5. A composite sheet for resin film formation, comprising: a support sheet according to any one of claims 1 to 4; and a resin film forming layer provided on one surface of the support sheet.

6. The composite sheet for resin film formation according to claim 5 , wherein the resin film forming layer is a protective film forming film.

7. The composite sheet for resin film formation according to claim 5 , wherein the resin film forming layer is a film-like adhesive.

8. A kit comprising a first laminate in which a first release film, a resin film forming layer and a second release film are laminated in this order, and a support sheet described in any one of claims 1 to 3, which is used to support a workpiece to which the resin film forming layer is to be attached and the resin film forming layer.

9. The kit according to claim 8 , wherein the resin film forming layer is a protective film forming film.

10. The kit according to claim 8 , wherein the resin film forming layer is a film-like adhesive.

11. A method for manufacturing a resin-film-coated chip comprising: a chip; and a resin film provided on a back surface of the chip, the method comprising: The method for producing the chip with the resin film includes the steps of: attaching a resin film forming layer of the composite sheet for resin film formation according to any one of claims 5 to 7 to the back surface of a workpiece to produce a first laminated composite sheet in which the support sheet, the resin film forming layer, and the workpiece are laminated in this order in the thickness direction; A process of forming the resin film by curing the resin film forming layer in the first laminated composite sheet to produce a second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction; dividing the work in the second laminated composite sheet and cutting the resin film to produce a third laminated composite sheet in which a plurality of chips with a resin film are fixed on the support sheet; and picking up the resin-film-coated chip in the third laminated composite sheet by separating it from the support sheet.

12. A method for manufacturing a resin-film-coated chip comprising: a chip; and a resin film provided on a back surface of the chip, the method comprising: The method for producing the resin-coated chip includes the steps of: attaching a resin film-forming layer in the kit according to any one of claims 8 to 10 to a back surface of a workpiece, and producing a first laminated film in which the resin film-forming layer and the workpiece are laminated in the thickness direction; A process of forming the resin film by curing the resin film forming layer in the first laminate film, and producing a second laminate film in which the resin film and the workpiece are laminated in a thickness direction thereof; A step of attaching an adhesive layer of a support sheet in the kit to a second laminate film to produce a second laminated composite sheet in which the support sheet, the resin film, and the workpiece are laminated in this order in the thickness direction; dividing the work in the second laminated composite sheet and cutting the resin film to produce a third laminated composite sheet in which a plurality of chips with a resin film are fixed on the support sheet; and picking up the resin-film-coated chip in the third laminated composite sheet by separating it from the support sheet.

13. A method for manufacturing a resin-film-coated chip comprising: a chip; and a resin film provided on a back surface of the chip, the method comprising: The method for producing the chip with resin film includes the steps of: attaching a resin film forming layer in a composite sheet for resin film formation according to any one of claims 5 to 7 to the back surface of a workpiece; or attaching a resin film forming layer in a kit according to any one of claims 8 to 10 to the back surface of a workpiece to produce a first laminated film in which the resin film forming layer and the workpiece are laminated in their thickness direction; and attaching an adhesive layer of a support sheet in the kit to the resin film forming layer in the first laminated film to produce a first laminated composite sheet in which the support sheet, the resin film forming layer, and the workpiece are laminated in this order in their thickness direction. A step of dividing the work in the first laminated composite sheet and cutting the resin film formed layer to produce a fourth laminated composite sheet in which a plurality of chips with a resin film formed layer are fixed on the support sheet; A method for producing a chip with a resin film, comprising a step of picking up the chip with the resin film forming layer in the fourth laminated composite sheet by separating it from the support sheet.

14. The method for producing a resin film-attached chip according to any one of claims 11 to 13, wherein the resin film-forming layer is a protective film-forming film.

15. The method for producing a resin-film-attached chip according to claim 13, wherein the resin film-forming layer is a film-like adhesive.

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