TWI631154B - Curable resin film, sheet for forming first protective film and method for forming first protective film - Google Patents

Abstract

The curable resin film of the present invention is used for attaching and curing a bumped surface of a semiconductor wafer, thereby forming a first protective film on the aforementioned surface by heating at 160°C for 1 hour when curing its surface haze (h ₁₎ is 50 or less, or by ^2, the light quantity of ultraviolet irradiation 510mJ / cm ² illuminance in the condition 230mW / cm when cured while its surface haze (H ₂ ) Becomes 50 or less. The first protective film forming sheet includes a first support sheet, and the curable resin film is provided on one surface of the first support sheet.

Description

Curable resin film, first protective film forming sheet, and first protective film forming method

The present invention relates to a curable resin film and a sheet for forming a first protective film using the same.

This application claims priority based on Japanese Patent Application No. 2015-217095 filed on November 4, 2015 in Japan, and the contents thereof are incorporated herein.

Previously, a multi-pin LSI (Large Scale Integration; large scale integrated circuit) package used in MPU (Microprocessing Unit) or gate array was installed on a printed wiring board In this case, the flip chip mounting method has been used. The flip chip mounting method uses a bump electrode (bump) formed of eutectic solder, high temperature solder, gold, etc. on its connection pad portion as In a semiconductor wafer, these bumps are made to face and contact the corresponding terminal portions on the wafer mounting substrate by a so-called face down method, and fusion/diffusion bonding is performed.

The semiconductor wafer used in this mounting method is obtained, for example, by grinding or dicing the surface of the semiconductor wafer having bumps formed on the circuit surface on the side opposite to the circuit surface to be singulated. In the process of obtaining such a semiconductor wafer, in order to protect the circuit surface and bumps of the semiconductor wafer, a curable resin film is usually attached to the bump forming surface, and the film is cured to form on the bump forming surface Protective film. Regarding this curable resin film, typically, after being attached to the bump forming surface, the fluidity is increased by heating, and thus the top region including the bump and the upper region near it are penetrated through When exposed, one side spreads between the bumps, is in close contact with the circuit surface, and covers the surface of the bumps, especially the surface near the circuit surface, and fills the bumps. The protective film formed by curing the curable resin film in this state protects the bump in the state of being in close contact with the bump surface in the circuit surface.

Among such curable resin films, as a sheet for forming a protective film provided with a thermosetting resin film containing a thermosetting component, it has been disclosed that a thermoplastic resin layer having a specific thermal elastic modulus is laminated on the film, and furthermore The layer formed on the uppermost layer on the thermoplastic resin layer is a non-plastic thermoplastic resin layer at 25°C (see Patent Document 1). Furthermore, according to Patent Document 1, the protective film forming sheet can be said to be excellent in bump filling property of the protective film, wafer processability, electrical connection reliability after resin sealing, and the like.

On the other hand, the semiconductor wafer with the protective film formed as described above is divided by the dicing together with the protective film to become a semiconductor wafer. Cut It is performed by cutting the semiconductor wafer at a specific location, usually using a camera in the dicing device, observing the semiconductor wafer from the circuit surface side, and identifying the dicing line existing on the surface of the semiconductor wafer (that is, indicating that dicing is required The position of the line of the part) or the alignment mark (that is, the mark for positioning the part to be cut) specifies the cut position of the semiconductor wafer, thereby cutting. Therefore, in order to cut the semiconductor wafer with the protective film formed on the bump forming surface at an accurate position, the camera in the dicing device must accurately recognize the cutting line or the alignment mark of the semiconductor wafer through the protective film, The protective film is required to have appropriate optical characteristics. For example, the protective film must be transparent, but it is known that it may become white or the like depending on the content of the composition. The transparency is reduced. If the decrease in transparency becomes obvious, it is difficult to recognize the cutting line or the alignment mark with the camera.

In contrast, it is uncertain whether the protective film disclosed in Patent Document 1 has high transparency.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2005-028734.

An object of the present invention is to provide a curable resin film that can form a protective film with high transparency on the bump forming surface of a semiconductor wafer, and a protective film forming sheet using the same.

The first aspect of the present invention is a curable resin film, which is used for attaching and curing a bumped surface of a semiconductor wafer, thereby forming a first protective film on the surface; and When the curable resin film is cured by heating at 160° C. for 1 hour, the surface haze (h ₁ ) of the curable resin film after curing is 50 or less.

The second aspect of the present invention is a curable resin film, which is used for attaching and curing a bumped surface of a semiconductor wafer, thereby forming a first protective film on the aforementioned surface; and When the curable resin film is cured by irradiating ultraviolet light under the conditions of illuminance 230 mW/cm ² and light intensity 510 mJ/cm ² , the haze (h ₂ ) of the surface of the curable resin film after curing is 50 the following.

The curable resin film of the first aspect or the second aspect of the present invention may also contain a filler having an average particle diameter of 250 nm or less.

The third aspect of the present invention is a sheet for forming a first protective film, which is provided with the curable resin film of the first aspect or the second aspect on one surface of the first support sheet.

By using the sheet for forming a curable resin film and the first protective film of the present invention, a protective film with high transparency can be formed on the bump forming surface of the semiconductor wafer.

1, 2, 3‧‧‧‧Protection film

11‧‧‧The first substrate

11a‧‧‧The surface of the first substrate

12‧‧‧curable resin layer (curable resin film)

12'‧‧‧First protective film

13‧‧‧First adhesive layer

13a‧‧‧The surface of the first adhesive layer

14‧‧‧ First Middle Floor

101, 102, 103 ‧‧‧ first support film

101a, 102a, 103a

90‧‧‧ semiconductor wafer

90a‧‧‧Semiconductor wafer circuit surface

91‧‧‧Bump

91a‧‧‧Bump surface

FIG. 1 is a cross-sectional view schematically showing an example of a state where a first protective film is formed on a bump forming surface using the curable resin film of the present invention.

2 is a cross-sectional view schematically showing an embodiment of the first protective film forming sheet of the present invention.

3 is a cross-sectional view schematically showing another embodiment of the first protective film forming sheet of the present invention.

4 is a cross-sectional view schematically showing still another embodiment of the first protective film forming sheet of the present invention.

The curable resin film of the first aspect of the present invention is used for attaching and curing a bumped surface of a semiconductor wafer, thereby forming a first protective film on the aforementioned surface; and by applying When the curable resin film is heated at 160° C. for 1 hour to be cured, the haze (h ₁ ) on the surface of the curable resin film after curing becomes 50 or less. The first aspect of the curable resin film is a thermosetting resin film.

In addition, the curable resin film of the second aspect of the present invention is used to attach and cure the bumped surface of the semiconductor wafer, thereby forming the first protective film on the aforementioned surface, and when the pair of the resin film ² is irradiated with ultraviolet rays at a light quantity of 510mJ / cm ² the conditions in the illuminance of 230mW / cm and cured, the haze (H ₂₎ the surface of the resin film after curing is 50 or less . The curable resin film of the second aspect is an energy ray curable resin film.

In addition, the first protective film forming sheet of the present invention is provided with the curable resin film of the first aspect or the second aspect of the present invention described above on one surface of the first support sheet. In the sheet for forming the first protective film, the "curable resin film" is sometimes referred to as a "curable resin layer".

The first sheet for forming a protective film of the present invention is used by attaching the surface of the semiconductor wafer with bumps (ie, the circuit surface) via its curable resin layer (curable resin film). Moreover, the curable resin layer after the application increases the fluidity by heating, spreads between the bumps so as to cover the bumps, is in close contact with the circuit surface, and covers the surface of the bumps, especially near the circuit surface The surface is filled with bumps. The curable resin layer in this state is further cured by heating or irradiation of energy rays, and finally a first protective film is formed, and the bump is protected in a state of being in close contact with the bump surface in the aforementioned circuit surface. Regarding the semiconductor wafer after the sheet for forming the first protective film is attached, for example, the surface opposite to the circuit surface is polished, the first support sheet is removed, and then the bumps are heated by heating the curable resin layer The landfill and the formation of the first protective film are finally incorporated into the semiconductor device in a state where the first protective film is provided.

In addition, in this specification, the bump surface and the circuit surface of the semiconductor wafer may be collectively referred to as "bump forming surface".

By using the curable resin film of the present invention, the circuit surface of the semiconductor wafer and the portion near the aforementioned circuit surface of the bump, that is, the base is passed through the first protective film Fully protected.

For the curable resin film (thermosetting resin layer) of the first aspect of the present invention, the cured product obtained by heat curing at 160° C. for 1 hour (hereinafter sometimes simply referred to as “cured product (α )") The haze (h ₁ ) of the surface becomes 50 or less.

In addition, the curable resin film (energy ray-curable resin layer) of the second aspect of the present invention is obtained by irradiating ultraviolet rays under the conditions of illuminance 230mW/cm ² and light quantity 510mJ/cm ² The surface haze (h ₂ ) of the cured product (hereinafter sometimes simply referred to as “cured product (β)”) becomes 50 or less.

In this way, the curable resin film of the present invention can be formed in the form of its cured product (ie, the first protective film) with high transparency.

Therefore, after the first protective film is formed on the bump forming surface containing the circuit surface of the semiconductor wafer using the curable resin film of the present invention, when the semiconductor wafer is viewed from the circuit surface side, the first protective film can be interposed Use the camera to accurately identify the position and shape of the scribe lines or alignment marks that exist on the surface of the semiconductor wafer. Furthermore, when the semiconductor wafer is cut together with the first protective film by dicing to obtain the semiconductor wafer, the cut position of the semiconductor wafer can be accurately specified.

The cured product of the present invention ([alpha]) haze (h ₁₎ and the cured product (beta]) haze (h ₂₎ the surface of the surface for example by post-curing resin film of said type and amount of ingredients contained And adjust.

FIG. 1 is a cross-sectional view schematically showing an example of a state where a first protective film is formed on a bump forming surface using the curable resin film of the present invention. In addition, with regard to the drawings used in the following description, in order to make the characteristics of the present invention easier to understand, the parts that are essential parts are enlarged and shown for convenience, and the dimensional ratios of the constituent elements and the like are not necessarily the same as actual ones.

A plurality of bumps 91 are provided on the circuit surface 90a of the semiconductor wafer 90 shown here. The bump 91 has a shape in which a part of a ball is cut out by a flat surface, and a flat surface corresponding to the cut out portion is in contact with the circuit surface 90 a of the semiconductor wafer 90.

The first protective film 12' is formed using the curable resin film of the present invention, covers the circuit surface 90a of the semiconductor wafer 90, and further covers the top of the bump 91 on the surface 91a of the bump 91 and the vicinity thereof Area covered. In this way, the first protective film 12 ′ is in close contact with the surface 91 a other than the top of the bump 91 and its vicinity, and is also in close contact with the circuit surface 90 a of the semiconductor wafer 90 to fill the bump 91.

The aforementioned substantially spherical shape of the bump 91 is particularly advantageous in forming the first protective film using the curable resin film of the present invention.

Furthermore, the semiconductor wafer that is the object of use of the curable resin film of the present invention is not limited to that shown in FIG. 1, and a part of the configuration may be changed, deleted, or added within a range that does not impair the effect of the present invention. For example, in FIG. 1, as the bumps, the aforementioned substantially spherical shape ((by flat The shape of the surface is cut out of a part of the ball), but the following bumps can also be cited as the bumps of the preferred shape: such a substantially spherical shape in the height direction (in FIG. 1 is the semiconductor wafer The shape of the stretched in the direction perpendicular to the circuit surface 90a of 90), that is, the shape of the substantially spheroid of the long sphere (the part of the spheroid of the long sphere including the end of the long axis direction is cut off by a plane Convex shape; or the shape obtained by flattening the above-mentioned substantially spherical shape in the height direction, that is, the shape of a substantially spheroid spheroid (the shape of a spheroid spheroid by a flat surface Convex bumps including the shape cut off at one end in the short axis direction. Such a bump having a substantially spheroidal shape is particularly advantageous in forming the first protective film using the curable resin film of the present invention, similar to the aforementioned substantially spherical bump.

In addition, the shape of the bump described so far is only an example of a preferable one when the thermosetting resin film of the present invention is applied. In the present invention, the shape of the bump is not limited to these shapes.

Hereinafter, the structure of the present invention will be described in detail.

◎The first support film

The aforementioned first support sheet may be composed of one layer (single layer), or plural layers of more than two layers. In the case where the support sheet is composed of a plurality of layers, the constituent materials and thickness of the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.

Furthermore, in this specification, it is not limited to the case of the first support sheet. The so-called "multiple layers may be the same as or different from each other" means "to make all the layers phase At the same time, all the layers may be different, or only a part of the layers may be the same. Furthermore, "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

As a preferred first support sheet, for example, a first adhesive layer is laminated on the first substrate, a first intermediate layer is laminated on the first substrate, and the first intermediate layer is laminated on the first intermediate layer. The adhesive layer is composed of the first base material only.

Hereinafter, according to the type of the first support sheet, an example of the sheet for forming the first protective film of the present invention will be described with reference to the drawings. In addition, regarding the drawings used in the following description, in order to easily understand the characteristics of the present invention, for convenience, parts that are essential parts are enlarged and shown, and the dimensional ratios and the like of the respective constituent elements are not necessarily the same as actual ones.

2 is a cross-sectional view schematically showing an embodiment of the first protective film forming sheet of the present invention. The sheet 1 for forming a first protective film shown here is formed by stacking a first adhesive layer on a first substrate as a first support sheet. That is, the first protective film forming sheet 1 is configured by including the first adhesive layer 13 on the first base material 11 and the curable resin layer (curable resin film) 12 on the first adhesive layer 13. The first support sheet 101 is a laminate of the first base material 11 and the first adhesive layer 13, and is provided with curability on one surface 101a of the first support sheet 101, that is, on one surface 13a of the first adhesive layer 13 Resin layer 12.

In the sheet 1 for forming a first protective film, the curable resin layer 12 is formed by curing to form a cured product (α) whose surface has a haze (h ₁ ) of 50 or less and a surface haze (h ₂ ) of 50 The following cured product (β) forms the first protective film with high transparency.

3 is a cross-sectional view schematically showing another embodiment of the first protective film forming sheet of the present invention. In addition, in FIG. 3, the same constituent elements as those shown in FIG. 2 are denoted by the same symbols as in the case of FIG. 2, and detailed descriptions thereof are omitted. This situation is the same in the subsequent figures of FIG. 4.

The first protective film-forming sheet 2 shown here is a first support sheet formed by stacking a first intermediate layer on a first substrate and a first adhesive layer on the first intermediate layer. That is, the first protective film forming sheet 2 is provided with the first intermediate layer 14 on the first base material 11, the first adhesive layer 13 on the first intermediate layer 14, and the curing on the first adhesive layer 13 Resin layer (curable resin film) 12. The first support sheet 102 is a layered body in which the first base material 11, the first intermediate layer 14 and the first adhesive layer 13 are sequentially stacked on one surface 102a of the first support sheet 102, namely the first adhesive The curable resin layer 12 is provided on one surface 13a of the agent layer 13.

In other words, the first protective film forming sheet 2 is included in the first protective film forming sheet 1 shown in FIG. 2, and further includes a first intermediate layer 14 between the first base material 11 and the first adhesive layer 13.

In the sheet 2 for forming the first protective film, the curable resin layer 12 is formed by curing to form the cured product (α) whose surface haze (h ₁ ) is 50 or less, and the surface haze (h ₂ ) is 50 The following cured product (β) forms the first protective film with high transparency.

4 is a cross-sectional view schematically showing still another embodiment of the first protective film forming sheet of the present invention.

The sheet 3 for forming the first protective film shown here uses only the first base material as the first support sheet. That is, the first protective film forming sheet 3 is configured by including the curable resin layer (curable resin film) 12 on the first base material 11. The first support sheet 103 is composed of only the first base material 11, and is directly in contact with one surface 103 a of the first support sheet 103, that is, one surface 11 a of the first base material 11, and is provided with a curable resin layer 12.

In other words, the first protective film forming sheet 3 is formed by removing the first adhesive layer 13 in the first protective film forming sheet 1 shown in FIG. 2.

In the sheet 3 for forming a first protective film, the curable resin layer 12 is formed by curing to form a cured product (α) whose surface has a haze (h ₁ ) of 50 or less and a surface haze (h ₂ ) of 50 The following cured product (β) forms the first protective film with high transparency.

Next, the structure of the first support sheet will be described in detail.

○The first substrate

The first substrate is in the form of a sheet or a film, and as its constituent material, for example, various resins can be cited.

Examples of the resin include low density polyethylene (LDPE) and linear low density polyethylene (Linear) Low Density Polyethylene (LLDPE), high density polyethylene (High Density Polyethylene; HDPE) and other polyethylene; polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin and other polyethylene Olefin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norcamene copolymer and other ethylene-based copolymers (obtained by using ethylene as a monomer Copolymer); polyvinyl chloride, vinyl chloride copolymer and other vinyl chloride resins (resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polynaphthalene Ethylene formate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalene dicarboxylate, all aromatic polyesters with aromatic ring groups in all structural units Etc. polyester; copolymer of two or more of the aforementioned polyesters; poly(meth)acrylate; polyurethane; polyacrylate urethane; polyimide; polyamide; polycarbonate Fluorine resin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polyphenolic; Polyether ketone, etc.

In addition, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the aforementioned polyester and other resins is preferably a relatively small amount of resins other than polyester.

In addition, as the resin, for example, a cross-linked resin obtained by cross-linking one or more types of the resins exemplified so far; one or more types of the resins exemplified so far are used Modified resin such as ionomer.

In addition, in this specification, "(meth)acrylic acid" refers to a package Contains the concepts of "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the so-called "(meth)acrylate" includes the concepts of both "acrylate" and "methacrylate", and the so-called "(meth)acrylic" "Base" is a concept that includes both "acryloyl" and "methacryloyl".

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

The first substrate may be only one layer (single layer), or plural layers of more than two layers. In the case of plural layers, the plural layers may be the same as or different from each other, and the combination of plural layers is not Specially limited.

The thickness of the first substrate is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm, further preferably 15 μm to 300 μm, and particularly preferably 20 μm to 150 μm.

Here, the "thickness of the first substrate" refers to the thickness of the entire first substrate, for example, the thickness of the first substrate composed of a plurality of layers refers to the total thickness of all layers constituting the first substrate .

The first base material is preferably one with a higher thickness accuracy, that is, a thickness-independent variation is suppressed regardless of the location. Among the above-mentioned constituent materials, examples of materials that can be used to constitute such a high-precision first base material include: Polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc.

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

The first substrate may be transparent or opaque, or colored according to the purpose, or may be vapor-deposited with other layers.

In the case where the first adhesive layer or the curable resin layer described below has energy ray curability, the first substrate preferably transmits energy ray.

The first substrate can be manufactured by a known method. For example, the first base material containing resin can be manufactured by molding the resin composition containing the aforementioned resin.

○First adhesive layer

The first adhesive layer is in the form of a sheet or a film and contains an adhesive.

Examples of the adhesive include acrylic resins (adhesives composed of resins having a (meth)acryloyl group), and urethane-based resins (resin composed of resins having urethane bonds). Consists of adhesives), rubber-based resins (adhesives composed of resins with a rubber structure), silicone-based resins (adhesives composed of resins with siloxane bonds), epoxy-based resins (including Adhesive composed of epoxy resin), polyvinyl ether, poly The adhesive resin such as carbonate is preferably an acrylic resin.

Furthermore, in the present invention, the so-called "adhesive resin" includes the concept of both adhesive resins and adhesive resins. For example, not only the resin itself has adhesive properties, but also additives and additives. A resin that exhibits adhesion by using other components in combination, or a resin that exhibits adhesion by the presence of a trigger such as heat or water.

The first adhesive layer may be only one layer (single layer), or plural layers of more than two layers. In the case of plural layers, the plural layers may be the same as or different from each other. No particular limitation.

The thickness of the first adhesive layer is preferably 1 μm to 1000 μm, more preferably 5 μm to 500 μm, and particularly preferably 10 μm to 100 μm.

Here, the "thickness of the first adhesive layer" refers to the total thickness of the first adhesive layer, for example, the thickness of the first adhesive layer composed of a plurality of layers refers to all the components that constitute the first adhesive layer The total thickness of the layers.

The first adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. The first adhesive layer formed using an energy ray-curable adhesive can easily adjust the physical properties before and after curing.

In the present invention, the "energy rays" refer to those with energy quanta in electromagnetic waves or charged particle beams. Examples thereof include ultraviolet rays, radiation, E-beam etc.

Ultraviolet rays can be irradiated by using a high-pressure mercury lamp, fusion H lamp, xenon lamp, black light, LED (Light Emitting Diode) lamp, or the like as an ultraviolet source. Regarding the electron beam, the one generated by an electron beam accelerator or the like can be irradiated.

In the present invention, "energy ray curability" refers to the property of curing by irradiation of energy rays, and "non-energy ray curability" refers to the property of not curing even when irradiated with energy rays.

<<First Adhesive Composition>>

The first adhesive layer can be formed using a first adhesive composition containing an adhesive. For example, by applying the first adhesive composition on the surface of the first adhesive layer to be formed and drying if necessary, the first adhesive layer can be formed on the target site. The more specific method for forming the first adhesive layer will be described in detail later together with the method for forming other layers. The ratio of the contents of the components in the first adhesive composition that do not vaporize at ordinary temperature is generally the same as the ratio of the contents of the aforementioned components of the first adhesive layer. In addition, the "normal temperature" in this specification means the temperature which is not particularly cold or hot, that is, an ordinary temperature, for example, the temperature of 15 to 25 degreeC etc. are mentioned.

The application of the first adhesive composition may be carried out by a well-known method, and examples include an air knife coater, a blade coater, a bar coater, a gravure coater, and a roll coater. , Roller knife coating machine, curtain type The method of various coating machines such as coating machine, mode coating machine, blade coating machine, screen coating machine, wire rod coating machine, anastomotic coating machine and so on.

The drying conditions of the first adhesive composition are not particularly limited. When the first adhesive composition contains a solvent described later, it is preferable to perform heat drying. The first adhesive composition containing a solvent is preferably dried under conditions of 70°C to 130°C and 10 seconds to 5 minutes, for example.

When the first adhesive layer is energy ray curable, the first adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable first adhesive composition, for example, the following adhesives Compositions, etc.: The first adhesive composition (I-1), which contains a non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes simply referred to as "adhesive resin (I-1a)"), And energy ray-curable compounds; the first adhesive composition (I-2), which contains the energy ray-curable with an unsaturated group introduced into the side chain of the non-energy-ray-curable adhesive resin (I-1a) Adhesive resin (I-2a) (hereinafter sometimes simply referred to as "adhesive resin (I-2a)"); and a first adhesive composition (I-3), which contains the aforementioned adhesive resin (I-2a) ), and energy ray curable low molecular compounds.

<First Adhesive Composition (I-1)>

As described above, the first adhesive composition (I-1) contains the non-energy ray-curable adhesive resin (I-1a) and the energy ray-curable compound.

[Adhesive resin (I-1a)]

The aforementioned adhesive resin (I-1a) is preferably an acrylic resin.

Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from alkyl (meth)acrylate.

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

Examples of the aforementioned (meth)acrylic acid alkyl ester include those having 1 to 20 carbon atoms which constitute the alkyl group of the alkyl ester, and the alkyl group is preferably linear or branched.

More specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A Group) Tridecyl acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate Ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), (meth)acrylic Undecyl acid, eicosyl (meth)acrylate, etc.

In terms of improving the adhesive force of the first adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group. Furthermore, in terms of further improving the adhesion of the first adhesive layer, the carbon number of the aforementioned alkyl group is preferably 4 to 12, more preferably 4 to 8. In addition, the alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group is preferably an alkyl acrylate.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate.

Examples of the functional group-containing monomer include: the reaction of the functional group with a cross-linking agent described later to become a starting point for cross-linking, or the reaction of the functional group with an unsaturated group in an unsaturated group-containing compound, by This can introduce unsaturated groups into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.

That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.

Examples of the aforementioned hydroxyl group-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxy(meth)acrylate. Propyl, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Group) hydroxyalkyl acrylate; non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) etc.

Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylene unsaturated dicarboxylic acids such as maleic acid and citraconic acid (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Group) carboxyalkyl acrylate etc.

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

The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one kind, or two or more kinds, and in the case of more than two kinds, the combination and ratio of these may be arbitrarily selected.

In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1% by mass to 35% by mass, and more preferably 3% by mass to 32% by mass relative to the total amount of the structural unit. Particularly preferably, it is 5% to 30% by mass.

The aforementioned acrylic polymer may have structural units derived from other monomers in addition to structural units derived from alkyl (meth)acrylate and structural units derived from functional group-containing monomers.

The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate or the like.

Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylic amide.

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

The aforementioned acrylic polymer can be used as the non-energy ray-curable adhesive resin (I-1a).

On the other hand, an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) and a functional group in the acrylic polymer can be used as the above energy ray curable Adhesive resin (I-2a).

In addition, the "energy ray polymerizability" in the present invention refers to the property of being polymerized by irradiating energy rays.

The adhesive resin (I-1a) contained in the first adhesive composition (I-1) can There is only one kind, or two or more kinds. In the case of more than two kinds, the combination and ratio of these can be arbitrarily selected.

In the first adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5% by mass to 99% by mass, more preferably 10% by mass to 95% by mass, and particularly preferably 15% by mass % To 90% by mass.

[Energy Ray Curable Compound]

Examples of the energy ray-curable compound contained in the first adhesive composition (I-1) include monomers or oligomers that have an energy-ray polymerizable unsaturated group and can be cured by irradiation with energy ray .

Among the energy ray-curable compounds, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth) Base) acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylate aminomethacrylate Ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc.

Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above.

In view of the relatively large molecular weight and the difficulty in reducing the storage elastic modulus of the first adhesive layer, the energy ray-curable compound is preferably (meth)acrylic acid urethane or (meth)acrylic acid amine group Formate oligomers.

The aforementioned energy ray curable compound contained in the first adhesive composition (I-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily select.

In the first adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass To 85% by mass.

[Crosslinking agent]

When using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), the first The adhesive composition (I-1) preferably further contains a crosslinking agent.

The cross-linking agent reacts with the functional group, for example, to cross-link the adhesive resin (I-1a).

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of these diisocyanates; B Epoxy-based cross-linking agent such as glycol glycidyl ether (cross-linking agent with glycidyl group); aziridine-based cross-linking such as hexa[1-(2-methyl)-aziridinyl]triphosphoric triazine Linking agent (crosslinking agent with aziridine group); metal chelate-based crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate-based crosslinking agent (Crosslinking agent with isocyanuric acid skeleton) etc.

The cross-linking agent is preferably an isocyanate-based cross-linking agent in terms of improving the cohesive force of the adhesive and improving the adhesive force of the first adhesive layer, and easy to obtain.

The crosslinking agent contained in the first adhesive composition (I-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the aforementioned first adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 with respect to 100 parts by mass of the content of the adhesive resin (I-1a). Mass parts to 20 parts by mass, particularly preferably 1 part by mass to 10 parts by mass.

[Photopolymerization initiator]

The first adhesive composition (I-1) may further contain a photopolymerization initiator. The first adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide and other acetylphosphine oxide compounds; benzylphenyl sulfide, tetramethylthiuram monosulfide and other sulfide compounds; 1-hydroxycyclohexyl phenyl ketone and other α-keto alcohol compounds; azo Azo compounds such as bisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diethyl amide; benzoyl amide; dibenzoyl amide; di Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone ; 2-chloroanthraquinone and so on.

In addition, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a light sensitizer such as amine; and the like can also be used.

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

In the first adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03, relative to the content of the energy ray curable compound of 100 parts by mass. Mass parts to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-1) may contain other additives that are not equivalent to any of the above components as long as the effects of the present invention are not impaired.

Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, and coloring. Agents (pigments, dyes), sensitizers, tackifiers, reaction retarders, crosslinking accelerators (catalysts) and other well-known additives.

Furthermore, the so-called reaction delay agent is suppressed in the first adhesive composition (I-1) during storage by the action of a catalyst mixed into the first adhesive composition (I-1), for example Not the target of the cross-linking reaction. Examples of the reaction delay agent include those that form a chelate complex by a chelate compound against a catalyst, and more specifically include those having two or more carbonyl groups (-C(=O)-) in one molecule.

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

In the first adhesive composition (I-1), the content of other additives is not particularly limited, as long as it is appropriately selected according to its type.

[Solvent]

The first adhesive composition (I-1) may contain a solvent. Since the first adhesive composition (I-1) contains a solvent, the applicability to the surface to be coated is improved.

The solvent is preferably an organic solvent. 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; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

As the aforementioned solvent, for example, without removing the self-adhesive resin (I-1a) used in the production of the adhesive resin (I-1a), it can be directly used in the first adhesive composition (I-1), or in When manufacturing the first adhesive composition (I-1), a solvent of the same or different type as that used in manufacturing the adhesive resin (I-1a) may be additionally added.

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

In the first adhesive composition (I-1), the content of the solvent is not particularly limited as long as it is appropriately adjusted.

<First Adhesive Composition (I-2)>

As described above, the first adhesive composition (I-2) is contained in the non-energy ray-curable adhesive resin (I-1a) and the energy ray-curable adhesive resin having an unsaturated group introduced into the side chain (I-2a).

[Adhesive resin (I-2a)]

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

The aforementioned unsaturated group-containing compound is capable of bonding with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the aforementioned energy ray polymerizable unsaturated group Group of compounds.

Examples of the energy ray polymerizable unsaturated group include (meth)acryloyl, vinyl (ethenyl), allyl (2-propenyl) and the like, preferably (meth)acryloyl.

Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include, for example, isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amine groups, and groups that can be bonded to carboxyl groups or epoxy groups The resulting hydroxyl and amine groups.

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

The adhesive resin (I-2a) contained in the first adhesive composition (I-2) may be only one kind, or may be two or more kinds. In the case of two or more kinds, the combination and ratio of these may be Choose arbitrarily.

In the first adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass, more preferably 10% by mass to 95% by mass, and particularly preferably 10% by mass % To 90% by mass.

[Crosslinking agent]

For example, when using the same acrylic polymer having the structural unit derived from a functional group-containing monomer as the adhesive resin (I-1a) as the adhesive resin (I-2a), the first adhesive The agent composition (I-2) may further contain a crosslinking agent.

Examples of the crosslinking agent in the first adhesive composition (I-2) include the same ones as in the first adhesive composition (I-1).

The crosslinking agent contained in the first adhesive composition (I-2) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the aforementioned first adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 with respect to 100 parts by mass of the content of the adhesive resin (I-2a). Mass parts to 20 parts by mass, particularly preferably 1 part by mass to 10 parts by mass.

[Photopolymerization initiator]

The first adhesive composition (I-2) may further contain a photopolymerization initiator. The first adhesive composition (I-2) containing the photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the first adhesive composition (I-2) include the same as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator contained in the first adhesive composition (I-2) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected .

In the first adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass of the adhesive resin (I-2a). 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-2) may contain other additives that are not equivalent to any of the above components as long as the effect of the present invention is not impaired.

Examples of the other additives in the first adhesive composition (I-2) include the same as the other additives in the first adhesive composition (I-1).

The other additives contained in the first adhesive composition (I-2) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the first adhesive composition (I-2), the content of other additives is not particularly limited, as long as it is appropriately selected according to its type.

[Solvent]

The first adhesive composition (I-2) can also contain a solvent for the same purpose as the case of the first adhesive composition (I-1).

Examples of the solvent in the first adhesive composition (I-2) include the same as the solvent in the first adhesive composition (I-1).

The solvent contained in the first adhesive composition (I-2) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the first adhesive composition (I-2), the content of the solvent is not particularly limited as long as it is appropriately adjusted.

<First Adhesive Composition (I-3)>

As described above, the first adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable low-molecular compound.

In the first adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass, more preferably 10% by mass to 95% by mass, and particularly preferably 15% by mass % To 90% by mass.

[Energy Ray Curable Low Molecular Compound]

Examples of the energy ray-curable low-molecular compound contained in the first adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy ray The polymer may be the same as the energy ray-curable compound contained in the first adhesive composition (I-1).

The aforementioned energy ray-curable low-molecular compound contained in the first adhesive composition (I-3) may be only one kind, or may be two or more kinds. In the above case, these combinations and ratios can be arbitrarily selected.

In the first adhesive composition (I-3), the content of the energy ray-curable low-molecular compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). It is more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]

The first adhesive composition (I-3) may further contain a photopolymerization initiator. The first adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the first adhesive composition (I-3) include the same as the photopolymerization initiator in the first adhesive composition (I-1).

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

In the first adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray-curable low-molecular compound. The part by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-3) may contain other additives that are not equivalent to any of the above components as long as the effects of the present invention are not impaired.

Examples of the aforementioned other additives include the same as the other additives in the first adhesive composition (I-1).

The other additives contained in the first adhesive composition (I-3) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the first adhesive composition (I-3), the content of other additives is not particularly limited, as long as it is appropriately selected according to its type.

[Solvent]

The first adhesive composition (I-3) can also contain a solvent for the same purpose as the case of the first adhesive composition (I-1).

Examples of the solvent in the first adhesive composition (I-3) include the same as the solvent in the first adhesive composition (I-1).

The solvent contained in the first adhesive composition (I-3) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the first adhesive composition (I-3), the content of the solvent is not particularly limited as long as it is appropriately adjusted.

<First adhesive composition other than the first adhesive composition (I-1) to (I-3)>

So far, the first adhesive composition (I-1), the first adhesive composition (I-2) and the first adhesive composition (I-3) have been described, but as such All the first adhesive compositions other than the three first adhesive compositions that contain ingredients and are specified (referred to as "other than the first adhesive compositions (I-1) to (I-3) in this specification The first adhesive composition") can also be used in the same way.

As the first adhesive composition other than the first adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable adhesive composition, non-energy ray-curable adhesives can also be cited Composition.

Examples of the non-energy ray-curable adhesive composition include acrylic resin (resin having (meth)acryloyl group), and urethane resin (resin having urethane bond). ), rubber-based resin (resin with rubber structure), silicone-based resin (resin with siloxane bond), epoxy resin (resin with epoxy group), polyethylene ether or polycarbonate, etc. The resin is preferably one containing acrylic resin.

The first adhesive composition other than the first adhesive composition (I-1) to (I-3) preferably contains one or two or more crosslinking agents, the content of which can be set to be the same as that of the above-mentioned first adhesive The composition (I-1) and the like are the same.

<<Manufacturing method of the first adhesive composition>>

The first adhesive composition such as the first adhesive composition (I-1) to (I-3) can be used to constitute the first adhesive by using the adhesive and components other than the adhesive as required It is obtained by mixing each component of the agent composition.

The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, it can be used by mixing the solvent with any formulation component other than the solvent and diluting the formulation component in advance; or without diluting any formulation component other than the solvent in advance, and combining the solvent with These blending ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, as long as it is appropriately selected from known methods such as the following methods: a method of rotating a stirrer or a stirring blade to mix, a method of mixing using a mixer, and applying Ultrasonic mixing method.

The addition of each component and the temperature and time at the time of mixing are not particularly limited as long as each formulated component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15°C to 30°C.

○The first middle layer

The first intermediate layer is in the form of a sheet or a film, and its constituent material may be appropriately selected according to the purpose, and is not particularly limited.

For example, in order to suppress the situation where the shape of the bumps present on the surface of the semiconductor is reflected on the protective film covering the surface of the semiconductor and the protective film is deformed, as the preferred constituent material of the first intermediate layer, the first intermediate layer In terms of further improvement of the adhesion, (meth)propane Enoic acid carbamate, etc.

The first intermediate layer may be only one layer (single layer), or plural layers of more than two layers. In the case of plural layers, the plural layers may be the same as or different from each other, and the combination of the plural layers is not Specially limited.

The thickness of the first intermediate layer can be adjusted appropriately according to the height of the bumps on the surface of the semiconductor to be protected. In terms of easily absorbing the influence of the bumps with a relatively high height, it is preferably 50 μm to 600 μm. It is more preferably 70 μm to 500 μm, and particularly preferably 80 μm to 400 μm.

Here, the "thickness of the first intermediate layer" refers to the total thickness of the first intermediate layer, for example, the thickness of the first intermediate layer composed of a plurality of layers refers to the total thickness of all layers constituting the first intermediate layer .

<<Composition for Forming the First Intermediate Layer>>

The first intermediate layer can be formed using a composition for forming a first intermediate layer containing its constituent material. For example, the composition for forming the first intermediate layer is coated on the surface of the first intermediate layer to be formed, and if necessary, dried or cured by irradiation with energy rays, whereby the first intermediate layer can be formed at the target site. The more specific formation method of the first intermediate layer will be described in detail later together with the formation methods of other layers. The ratio of the contents of the components that do not vaporize at ordinary temperature in the composition for forming the first intermediate layer is generally the same as the ratio of the contents of the aforementioned components of the first intermediate layer. The so-called "normal temperature" here is as explained above.

The application of the composition for forming the first intermediate layer may be carried out by a well-known method, and examples include air knife coaters, blade coaters, bar coaters, gravure coaters, and roll coaters. Cloth machine, roll knife coater, curtain coater, mode coater, blade coater, screen coater, wire rod coater, stapling coater, etc. .

The drying conditions of the composition for forming the first intermediate layer are not particularly limited. For example, the composition for forming a first intermediate layer containing a solvent described below is preferably dried by heating. In this case, for example, it is preferably dried at 70° C. to 130° C. for 10 seconds to 5 minutes.

In the case where the composition for forming the first intermediate layer has energy ray curability, it is preferably cured after being irradiated with energy ray after drying.

Examples of the composition for forming the first intermediate layer include, for example, a composition for forming the first intermediate layer (II-1) containing a urethane (meth)acrylate.

<Composition for Forming the First Intermediate Layer (II-1)>

As described above, the first intermediate layer forming composition (II-1) contains (meth)acrylic acid urethane.

[(Meth)acrylic acid carbamate]

(Meth)acrylic acid urethane is a compound having at least a (meth)acryloyl group and a urethane bond in one molecule, and has energy ray polymerizability.

(Meth)acrylic acid carbamates can be monofunctional (having only one (meth)acryl acetyl group in one molecule), or can be difunctional or more (having more than two (a Base) propylene amide base), that is, multi-functional. Among them, in the present invention, it is preferable to use at least a monofunctional urethane (meth)acrylate.

Examples of the aforementioned (meth)acrylic acid urethane contained in the first intermediate layer forming product include: reacting a polyol compound and a polyisocyanate compound to obtain a terminal isocyanate urethane prepolymer, It is further obtained by reacting a (meth)acrylic compound having a hydroxyl group and a (meth)acryloyl group with the aforementioned terminal isocyanate urethane prepolymer. The "terminal isocyanate urethane prepolymer" herein refers to a prepolymer having an urethane bond and having an isocyanate group at the end of the molecule.

The (meth)acrylic acid urethane contained in the first intermediate layer forming composition (II-1) may be only one kind, or may be two or more kinds. In the case of two or more kinds, The combination and ratio can be arbitrarily selected.

(Polyol compound)

The aforementioned polyol compound is not particularly limited as long as it has two or more hydroxyl groups in one molecule.

The aforementioned polyol compound may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio of these may be arbitrarily selected.

Examples of the aforementioned polyol compound include alkylene glycols, polyether polyols, polyester polyols, and polycarbonate polyols.

The polyhydric alcohol compound may be any of difunctional diols, trifunctional triols, and tetrafunctional polyhydric alcohols, and the like. In terms of ease of acquisition and excellent versatility and reactivity, the dihydric alcohol compound is preferably divalent. alcohol.

. Polyether polyol

The polyether polyol is not particularly limited, but is preferably a polyether diol. Examples of the polyether diol include compounds represented by the following general formula (1).

(In the formula, n is an integer of 2 or more; R is a divalent hydrocarbon group, and plural Rs may be the same as or different from each other.)

In the formula, n represents the number of repeating units of the group represented by the general formula "-R-O-", and is not particularly limited as long as it is an integer of 2 or more. Among them, n is preferably 10 to 250, more preferably 25 to 205, and particularly preferably 40 to 185.

In the formula, R is not particularly limited as long as it is a divalent hydrocarbon group, preferably alkylene, more preferably alkylene having 1 to 6 carbon atoms, and further preferably ethylidene, propylidene or tetramethylene , Particularly preferred is propylidene or tetramethylene.

The compound represented by the aforementioned formula (1) is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, and more preferably polypropylene glycol or polytetramethylene glycol.

By reacting the polyether diol and the polyisocyanate compound, one having an ether bond represented by the following general formula (1a) can be obtained as the terminal isocyanate urethane prepolymer. Furthermore, by using such a terminal isocyanate urethane prepolymer, the (meth)acrylic acid urethane becomes one having the ether bond, that is, having a derivative derived from the polyether diol The structural unit.

(In the formula, R and n are the same as described above.)

. Polyester polyol

The aforementioned polyester polyol is not particularly limited, and examples thereof include those obtained by performing an esterification reaction using a polybasic acid or its derivative. Furthermore, Ben said Unless otherwise specified, the so-called "derivatives" in the Mingshu refer to those in which more than one group of the original compound is substituted with other groups (substituents). The so-called "group" here is not only an atomic group formed by bonding a plurality of atoms, but also an atom.

Examples of the aforementioned polybasic acid and its derivatives include polybasic acids and their derivatives that are generally used as raw materials for polyester production.

Examples of the aforementioned polybasic acid include saturated aliphatic polybasic acids, unsaturated aliphatic polybasic acids, and aromatic polybasic acids. Dimer acids corresponding to any of these can also be used.

Examples of the saturated aliphatic polybasic acid include saturated aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Acid and so on.

Examples of the unsaturated aliphatic polybasic acid include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.

Examples of the aromatic polybasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid; and aromatic tribasic acids such as trimellitic acid. ; Aromatic tetrabasic acid such as pyromellitic acid and so on.

Examples of the derivatives of the aforementioned polybasic acids include the above-mentioned saturated aliphatic polybasic acids, anhydrides of unsaturated aliphatic polybasic acids and aromatic polybasic acids, and hydrogenated dimer acids.

Each of the aforementioned polybasic acids or their derivatives may be used alone, or two or more kinds may be used in combination. When two or more kinds are used together, the combination and ratio of these may be arbitrarily selected.

In terms of being suitable for forming a coating film having an appropriate hardness, the aforementioned polybasic acid is preferably an aromatic polybasic acid.

In the esterification reaction for obtaining the polyester polyol, a known catalyst may be used as necessary.

Examples of the catalyst include tin compounds such as dibutyltin oxide and stannous octoate; titanium alkoxides such as tetrabutyl titanate and tetrapropyl titanate; and the like.

. Polycarbonate polyol

The polycarbonate polyol is not particularly limited, and examples thereof include those obtained by reacting the same diol as the compound represented by the aforementioned formula (1) with an alkylene carbonate.

Here, each of the diol and the alkylene carbonate may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio of these may be arbitrarily selected.

The number average molecular weight calculated from the hydroxyl value of the aforementioned polyol compound is preferably 1,000 to 10,000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000. With the aforementioned number average molecular weight being 1000 or more, The excessive formation of urethane bonds is suppressed, and the control of the viscoelastic properties of the first intermediate layer becomes easier. In addition, when the aforementioned number average molecular weight is 10,000 or less, excessive softening of the first intermediate layer is suppressed.

The aforementioned number average molecular weight of the polyol compound calculated from the hydroxyl value is a value calculated from the following formula.

[Number average molecular weight of polyol compound]=[Number of functional groups of polyol compound]×56.11×1000/[Hydroxy value of polyol compound (unit: mgKOH/g)]

The aforementioned polyol compound is preferably a polyether polyol, more preferably a polyether diol.

(Polyisocyanate compound)

The polyhydric isocyanate compound that reacts with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.

One type of polyisocyanate compound may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio of these may be arbitrarily selected.

Examples of the aforementioned polyisocyanate compound include linear aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbranched Alkyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ω,ω'-diisocyanate dimethyl Cyclic aliphatic diisocyanate such as cyclohexane; 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, benzidine diisocyanate, tetramethylene xylene diisocyanate, naphthalene-1 , 5-diisocyanate and other aromatic diisocyanate.

Among these, in terms of handleability, the polyisocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate, or xylene diisocyanate.

((Meth)acrylic compound)

The (meth)acrylic compound that reacts with the terminal isocyanate urethane prepolymer is not particularly limited as long as it has at least a hydroxyl group and a (meth)acryloyl group in one molecule.

The aforementioned (meth)acrylic compound may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio of these may be arbitrarily selected.

Examples of the (meth)acrylic compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth) ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 5-hydroxy (meth)acrylate Cyclooctyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylic acid Ester and other hydroxyl-containing (meth)acrylate; N-hydroxymethyl (meth)acrylamide and other Hydroxy (meth)acrylamide; reactant obtained by reacting (meth)acrylic acid with vinyl alcohol, vinylphenol or bisphenol A diglycidyl ether, etc.

Among these, the aforementioned (meth)acrylic compound is preferably a hydroxy-containing (meth)acrylate, more preferably a hydroxy-containing alkyl (meth)acrylate, and particularly preferably (meth)acrylic acid 2 -Hydroxyethyl.

In the reaction between the terminal isocyanate urethane prepolymer and the (meth)acrylic compound, a solvent, a catalyst, etc. may be used as necessary.

The conditions for reacting the terminal isocyanate urethane prepolymer and the (meth)acrylic compound may be adjusted as appropriate. For example, the reaction temperature is preferably 60°C to 100°C, and the reaction time is preferably 1 hour. To 4 hours.

The aforementioned (meth)acrylic acid urethane may be any of oligomers, polymers, and mixtures of oligomers and polymers, preferably oligomers.

For example, the weight average molecular weight of the aforementioned (meth)acrylic acid urethane is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and particularly preferably 5,000 to 65,000. With the aforementioned weight average molecular weight of 1000 or more, in the polymer of (meth)acrylic acid urethane and a polymerizable monomer described later, due to the structure derived from the (meth)acrylic acid urethane molecules, Between the forces, it is easy to optimize the hardness of the first intermediate layer.

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

[Polymerizable monomer]

In order to further improve the film-forming property, the first intermediate layer forming composition (II-1) may contain a polymerizable monomer in addition to the aforementioned (meth)acrylate urethane.

The polymerizable monomer is preferably a compound having at least one (meth)acryloyl group in one molecule, except for oligomers and polymers having energy ray polymerizability and a weight average molecular weight of 1000 or more.

Examples of the polymerizable monomers include: alkyl (meth)acrylates having a carbon number of 1 to 30 and a chain structure constituting the alkyl ester; having a hydroxyl group, an amide group, an amine group, or a ring (Meth)acrylic compounds containing functional groups such as oxy and other functional groups; (meth)acrylates with aliphatic cyclic groups; (meth)acrylates with aromatic hydrocarbon groups; those with heterocyclic groups (Meth)acrylates; compounds with vinyl groups; compounds with allyl groups, etc.

Examples of the aforementioned (meth)acrylic acid alkyl ester having a chain alkyl group having a carbon number of 1 to 30 include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Propyl, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, Amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate Ester, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Undecyl meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate Ester (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), 17 (meth)acrylate Alkyl esters, octadecyl (meth)acrylate (stearyl (meth)acrylate), isooctadecyl (meth)acrylate (isostearyl (meth)acrylate), (A )) nonadecyl acrylate, eicosyl (meth) acrylate, etc.

Examples of the functional group-containing (meth)acrylic acid derivatives include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. , 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylate; (meth)acrylic Amine, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethylpropane (methyl (Meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide and other (meth) acrylamide and its derivatives; with amine (Meth)acrylate of a group (hereinafter sometimes referred to as "(meth)acrylate containing an amine group"); a monosubstituted amine group in which one hydrogen atom having an amine group is substituted with a group other than a hydrogen atom (Meth)acrylate (hereinafter sometimes referred to as "(meth)acrylate containing a single substituted amine group"); two hydrogen atoms with an amine group are replaced by groups other than hydrogen atoms (Meth)acrylate of disubstituted amine group (hereinafter sometimes referred to as "(meth)acrylate with disubstituted amine group"); glycidyl (meth)acrylate, (meth)acrylic acid Epoxy-containing (meth)acrylates such as methyl glycidyl ester (hereinafter sometimes referred to as "epoxy-containing (meth)acrylates") and the like.

Here, the "amine group-containing (meth)acrylate" refers to a compound in which one or more hydrogen atoms of the (meth)acrylate are substituted with an amine group (-NH ₂ ). Similarly, the so-called "(meth)acrylate containing a single substituted amine group" refers to a compound in which one or more hydrogen atoms of (meth)acrylate are substituted with a single substituted amine group. "(Meth)acrylate of a disubstituted amine" refers to a compound in which one or more hydrogen atoms of (meth)acrylate are substituted with a disubstituted amine.

Examples of the groups other than hydrogen atoms (ie, substituents) in the "monosubstituted amine group" and "disubstituted amine group" that substitute for hydrogen atoms include alkyl groups.

Examples of the (meth)acrylates having an aliphatic cyclic group include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, etc.

Examples of the (meth)acrylate having an aromatic hydrocarbon group include phenylhydroxypropyl (meth)acrylate, benzyl (meth)acrylate, and 2-hydroxy-3-phenoxy (meth)acrylate. Propyl ester and so on.

The heterocyclic group in the (meth)acrylate having a heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group.

Examples of the (meth)acrylate having a heterocyclic group include tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine and the like.

Examples of the compound having a vinyl group include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, and N-vinylcaprolactam. Amines.

Examples of the compound having an allyl group include allyl glycidyl ether.

In terms of good compatibility with the aforementioned (meth)acrylic acid urethane, the aforementioned polymerizable monomer preferably has a relatively bulky group. Examples of such polymerizable monomers include (meth)acrylates having an aliphatic cyclic group, (meth)acrylates having an aromatic hydrocarbon group, and (meth)acrylates having a heterocyclic group. It is more preferably (meth)acrylate having an aliphatic cyclic group.

The polymerizable monomer contained in the composition for forming the first intermediate layer (II-1) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these may be arbitrarily select.

In the composition (II-1) for forming the first intermediate layer, the content of the polymerizable monomer is preferably 10% by mass to 99% by mass, more preferably 15% by mass to 95% by mass, and further preferably 20% by mass to 90% by mass, particularly preferably 25% to 80% by mass.

[Photopolymerization initiator]

The composition (II-1) for forming the first intermediate layer may contain a photopolymerization initiator in addition to the (meth)acrylate urethane and the polymerizable monomer. The composition (II-1) for forming the first intermediate layer containing the photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the first intermediate layer forming composition (II-1) include the same as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator contained in the composition for forming the first intermediate layer (II-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrary Choice.

In the composition (II-1) for forming the first intermediate layer, the content of the photopolymerization initiator is preferably 100 parts by mass relative to the total content of the aforementioned (meth)acrylate carbamate and polymerizable monomers 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass Copies.

[Resin components other than (meth)acrylate urethane]

The composition (II-1) for forming the first intermediate layer may contain a resin component other than the aforementioned (meth)acrylic acid urethane as long as the effect of the present invention is not impaired.

The kind of the aforementioned resin component and its content in the first intermediate layer forming composition (II-1) may be appropriately selected according to the purpose, and are not particularly limited.

[Other additives]

The composition (II-1) for forming the first intermediate layer may contain other additives that are not equivalent to any of the above components within a range that does not impair the effect of the present invention.

Examples of the aforementioned other additives include known additives such as crosslinking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, and colorants (pigments, dyes). .

For example, as the aforementioned chain transfer agent, a thiol compound having at least one thiol group (mercapto group) in one molecule can be mentioned.

Examples of the thiol compound include nonylmercaptan, 1-dodecanemercaptan, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, and triazinedisulfide. Alcohol, triazine trithiol, 1,2,3-propanetrithiol, tetraethylene glycol-bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), quaternary Pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetramercaptoacetate, dipentaerythritol hexa(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]-isotris Polycyanate, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc.

The other additive contained in the composition for forming the first intermediate layer (II-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the composition (II-1) for forming the first intermediate layer, the content of other additives is not particularly limited as long as it is appropriately selected according to the type.

[Solvent]

The composition (II-1) for forming the first intermediate layer may contain a solvent. The composition (II-1) for forming the first intermediate layer improves the coating suitability for the surface to be coated by containing a solvent.

<<Manufacturing method of the composition for forming the first intermediate layer>>

The aforementioned first intermediate layer forming composition (II-1) and other aforementioned first intermediate layer forming composition are obtained by blending the components that constitute the composition.

The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, it can be used by: mixing the solvent with any formulation component other than the solvent to dilute the formulation component in advance; or not diluting any formulation component other than the solvent in advance, and diluting the solvent with These blending ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, as long as it is appropriately selected from known methods such as the following methods: a method of rotating a stirrer or a stirring blade to mix, a method of mixing using a mixer, and applying Ultrasonic mixing method.

The addition of each component and the temperature and time at the time of mixing are not particularly limited as long as each formulated component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15°C to 30°C.

◎Curable resin layer

The curable resin layer (curable resin film) is a layer for protecting the circuit surface of the semiconductor wafer and the bumps provided on the circuit surface. The aforementioned curable resin layer is a thermosetting resin layer (thermosetting resin film) in the first aspect, and is an energy ray curable resin layer (energy ray curable resin film) in the second aspect. The curing resin layer is cured to form a first protective film.

In the present invention, both the haze (h ₁ ) on the surface of the cured product (α) and the haze (h ₂ ) on the surface of the cured product (β) are 50 or less. The aforementioned curable resin layer with such characteristics can form a first protective film with high transparency. Therefore, the surface state of the semiconductor wafer after forming the first protective film on the bump forming surface can be observed with high precision through the first protective film, and the dicing existing on the surface of the semiconductor wafer can be accurately recognized by the camera The position and shape of the line or alignment mark.

Furthermore, both the aforementioned cured product (α) and cured product (β) can be used as the first protective film.

In addition, the aforementioned haze (h ₁ ) and haze (h ₂ ) may sometimes have the same value as each other, and may sometimes have different values.

In terms of obtaining the above-mentioned effects of the present invention more conspicuously, the smaller the aforementioned haze (h ₁ ) and (h ₂ ), the better, preferably 45 or less, such as 40 or less, 35 or less, and 30 or less, etc. Of any kind.

In addition, the lower limit values of the aforementioned hazes (h ₁ ) and (h ₂ ) are not particularly limited, but in general, it is preferably 10 in terms of easily forming the first protective film with high transparency.

In the present invention, the haze (h ₀₁ ) on the surface of the curable resin layer (curable resin film) in the first aspect before curing of the cured product (α) and the curing in the cured product (β) The haze (h ₀₂ ) on the surface of the curable resin layer (curable resin film) in the second aspect of the foregoing is not particularly limited, but the smaller the better, preferably 50 or less, more preferably 45 or less, for example It can be any of 40 or less, 35 or less, and 30 or less.

In addition, the lower limit values of the aforementioned hazes (h ₀₁ ) and (h ₀₂ ) are not particularly limited, but in general, it is preferably 10 in terms of easily forming the first protective film with high transparency.

In the present invention, the aforementioned hazes (h ₀₁ ), (h ₀₂ ), (h ₁ ) and (h ₂ ) can all be based on the use of a haze meter in accordance with JIS (Japanese Industrial Standards) K7136 (2000) Determination.

The haze (h ₁ ) and (h ₂ ) can be adjusted by adjusting the type of the curable resin layer.

In addition, the aforementioned curable resin layer can be formed using a composition for forming a curable resin layer containing its constituent material.

Therefore, the aforementioned hazes (h ₀₁ ), (h ₀₂ ), (h ₁ ), and (h ₂ ) can be adjusted by adjusting either or both of the types and amounts of the components contained in the curable resin layer forming composition Adjustment.

Among the components contained in the composition for forming a curable resin layer, in particular, granular components such as a filler (D), which will be described later, tend to cause cloudiness of the cured product. In the present invention, by reducing the use amount of the granular components such as filler (D) or selecting suitable ones as the granular components, the aforementioned haze (h ₁ ) and (h ₂ ) can be reduced, and high transparency can be obtained Of the cured product.

The composition for forming a curable resin layer (a composition for forming a thermosetting resin layer, a composition for forming an energy ray curable resin layer) and a method for manufacturing the same will be described in detail below.

○Thermosetting resin layer

Examples of preferred thermosetting resin layers include those containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is considered A component formed by a polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as a trigger of the reaction. Furthermore, in the present invention, the polycondensation reaction is also included in the polymerization reaction.

The aforementioned thermosetting resin layer may be only one layer (single layer) or plural layers of more than two layers. In the case of plural layers, the plural layers may be the same as or different from each other, and the combination of the plural layers There is no particular limitation.

The thickness of the aforementioned thermosetting resin layer is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the thermosetting resin layer is equal to or greater than the aforementioned lower limit, the first protective film with higher protection ability can be formed. In addition, when the thickness of the thermosetting resin layer is equal to or less than the above upper limit value, the excessive thickness is suppressed.

Here, the "thickness of the thermosetting resin layer" refers to the thickness of the entire thermosetting resin layer, for example, the thickness of the thermosetting resin layer composed of a plurality of layers refers to all the constituents of the thermosetting resin layer The total thickness of the layers.

The curing conditions when the aforementioned thermosetting resin layer is attached to the bump forming surface of the semiconductor wafer and cured to form the first protective film, as long as the first protective film fully exhibits its function It is not particularly limited as long as it is appropriately selected according to the type of thermosetting resin layer.

For example, the heating temperature during curing of the thermosetting resin layer is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. Moreover, the heating time during the curing is preferably 0.5 hours to 5 hours, more preferably 0.5 hours to 3 hours, and particularly preferably 1 hour to 2 hours.

<<Composition for Forming Thermosetting Resin Layer>>

The thermosetting resin layer can be formed using a composition for forming a thermosetting resin layer containing its constituent material. For example, the composition for forming a thermosetting resin layer is applied to the surface to be formed of the thermosetting resin layer, and drying is performed as necessary, whereby the thermosetting resin layer can be formed at the target site. The ratio of the contents of the components in the thermosetting resin layer forming composition that do not vaporize at normal temperature is generally the same as the ratio of the contents of the aforementioned components of the thermosetting resin layer. The so-called "normal temperature" here is as explained above.

The application of the composition for forming a thermosetting resin layer may be performed by a known method, and examples include air knife coater, blade coater, bar coater, gravure coater, and roll type. Coaters, roll coaters, curtain coaters, pattern coaters, blade coaters, screen coaters, wire bar coaters, stapling coaters, etc. method.

The drying conditions of the composition for forming a thermosetting resin layer are not particularly limited, and when the composition for forming a thermosetting resin layer contains a solvent described later, it is preferable to perform heat drying. The composition for forming a thermosetting resin layer containing a solvent is preferably, for example, 70°C to 130°C and 10 seconds to 5 minutes Dry under conditions.

<Composition for forming a resin layer (III-1)>

Examples of the composition for forming a thermosetting resin layer include, for example, a composition (III-1) for forming a thermosetting resin layer containing a polymer component (A) and a thermosetting component (B) (in this specification, there are It is simply referred to as "resin layer forming composition (III-1)") and so on.

[Polymer component (A)]

The polymer component (A) is a polymer compound for imparting film-forming properties or flexibility to the thermosetting resin layer.

The composition (III-1) for forming a resin layer and the polymer component (A) contained in the thermosetting resin layer may be only one kind, or may be two or more kinds. In the case of two or more kinds, The combination and ratio can be arbitrarily selected.

Examples of the polymer component (A) include acrylic resins (resins having a (meth)acryloyl group), polyesters, and urethane resins (resins having a urethane bond), Acrylic urethane resin, silicone resin (resin with siloxane bond), rubber resin (resin with rubber structure), phenoxy resin, thermosetting polyimide, etc., preferably Acrylic resin.

Examples of the acrylic resin as the polymer component (A) include known acrylic polymers.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit, the shape stability (temporal stability during storage) of the thermosetting resin layer is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above upper limit, the thermosetting resin layer easily follows the uneven surface of the adherend, and further suppresses the occurrence of voids and the like between the adherend and the thermosetting resin layer.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is equal to or greater than the above lower limit value, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved. In addition, when the Tg of the acrylic resin is equal to or lower than the above upper limit value, the adhesion between the thermosetting resin layer and the first protective film and the adherend is improved.

Examples of the acrylic resin include: one or more than two (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxyl Copolymers of two or more monomers such as methacrylamide.

Examples of the aforementioned (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, (meth) Third butyl acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate , N-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (meth) ) Dodecyl acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, myristyl (meth) acrylate (myristyl (meth) acrylate), ( Pentadecyl meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate Ester (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon (meth)acrylic acid alkyl ester; (meth)acrylic acid isobutyl ester, ( Cycloalkyl (meth)acrylate such as dicyclopentyl methacrylate; aralkyl (meth)acrylate such as benzyl (meth)acrylate; dicyclopentenyl (meth)acrylate etc. Group) cycloalkenyl acrylate; dicyclopentenyloxyethyl (meth)acrylate and other cyclomethoxyalkyl (meth)acrylate; (meth)acrylamide; (meth)acrylic acid shrink Glyceryl esters and other (meth)acrylates containing glycidyl groups; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; (Meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate containing substituted amine groups. The "substituted amine group" herein refers to a group in which one or two hydrogen atoms of the amine group are substituted with groups other than hydrogen atoms.

The acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide in addition to the aforementioned (meth)acrylate. One or more than two monomers are copolymerized.

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

The acrylic resin may also have functional groups such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds. The aforementioned functional group of the acrylic resin may be bonded to other compounds via a cross-linking agent (F) described below, or may be directly bonded to other compounds without a cross-linking agent (F). By bonding the acrylic resin to other compounds through the aforementioned functional groups, the reliability of the package obtained by using the first protective film forming sheet tends to be improved.

In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter, sometimes simply referred to as "thermoplastic resin") may be used alone without using an acrylic resin, or the thermoplastic resin and acrylic The resin is used together. By using the aforementioned thermoplastic resin, the releasability of the first protective film from the first support sheet may be improved, or the thermosetting resin layer may easily follow the uneven surface of the adherend, thereby further suppressing the adherend and the thermosetting resin There are gaps between layers.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, and more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The aforementioned thermoplastic resin contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these Can be chosen arbitrarily.

In the composition (III-1) for forming a resin layer, regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (ie, thermosetting property) The content of the polymer component (A) of the resin layer) is preferably 5% by mass to 85% by mass, more preferably 5% by mass to 80% by mass, for example, 5% by mass to 70% by mass, and 5% by mass to 60% by mass Any one of mass%, 5 mass% to 50 mass%, 5 mass% to 40 mass%, and 5 mass% to 30 mass%. However, these contents in the composition (III-1) for resin layer formation are an example.

The polymer component (A) sometimes corresponds to the thermosetting component (B). Benfa In the Ming Dynasty, when the composition (III-1) for forming a resin layer contains components corresponding to both the polymer component (A) and the thermosetting component (B), it is regarded as a composition for forming a resin layer (III-1) Contains the polymer component (A) and the thermosetting component (B).

[Thermosetting component (B)]

The thermosetting component (B) is a component for curing the thermosetting resin layer to form a hard first protective film.

The composition (III-1) for forming a resin layer and the thermosetting component (B) contained in the thermosetting resin layer may be only one kind, or may be two or more kinds. In the case of two or more kinds, The combination and ratio can be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., preferably cyclic Oxygen thermosetting resin.

(Epoxy thermosetting resin)

The epoxy-based thermosetting resin system is composed of an epoxy resin (B1) and a thermosetting agent (B2).

The composition (III-1) for forming a resin layer and the epoxy-based thermosetting resin contained in the thermosetting resin layer may be only one kind, or may be two or more kinds. In the case of two or more kinds, these The combination and ratio can be arbitrarily selected.

. Epoxy resin (B1)

Examples of the epoxy resin (B1) include known epoxy resins, and examples include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resin. Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Oxygen compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the first protective film forming sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of the multifunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting (meth)acrylic acid or its derivative to an epoxy group addition reaction.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include vinyl (ethenyl), 2-propenyl (allyl), (meth)acryloyl, and (meth)acryloyl. The amine group and the like are preferably acryl.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, and it is preferably 300 to 30,000 in terms of the curability of the thermosetting resin layer and the strength and heat resistance of the first protective film after curing. More preferably, it is 400 to 10,000, and particularly preferably 500 to 3000.

The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1000 g/eq, more preferably 300 g/eq to 800 g/eq.

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

. Heat curing agent (B2)

The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

Examples of the thermosetting agent (B2) include compounds having two or more functional groups that can react with epoxy groups in one molecule. Examples of the aforementioned functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amine groups, carboxyl groups, acid groups, and the like. Preferably, phenolic hydroxyl groups, amine groups, or acid groups are anhydrideized. The formed group is more preferably a phenolic hydroxyl group or an amine group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type Phenol resin etc.

Among the thermosetting agent (B2), examples of the amine-based curing agent having an amine group include dicyanodiamide (hereinafter sometimes simply referred to as "DICY").

The thermal curing agent (B2) may have an unsaturated hydrocarbon group.

As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound in which a part of hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the phenol resin Compounds formed on aromatic rings.

The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.

In the case of using a phenolic curing agent as the thermosetting agent (B2), the softening point or glass of the thermosetting agent (B2) is preferred in terms of improving the peelability of the first protective film from the first support sheet The transfer temperature is high.

In the thermosetting agent (B2), for example, the number average molecular weight of the resin components such as polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is preferably 300 to 30,000, more It is preferably 400 to 10000, and particularly preferably 500 to 3000.

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

The thermosetting agent (B2) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio of these may be arbitrarily selected Select.

In the composition (III-1) for forming a resin layer and the thermosetting resin layer, the content of the thermosetting agent (B2) is preferably 0.1 part by mass to 500 parts by mass with respect to the content of the epoxy resin (B1) by 100 parts by mass. The part is more preferably 1 part by mass to 200 parts by mass, for example, any one of 5 parts by mass to 100 parts by mass, 10 parts by mass to 80 parts by mass, and 15 parts by mass to 60 parts by mass. When the content of the thermosetting agent (B2) is equal to or higher than the lower limit, the thermosetting resin layer can be more easily cured. In addition, when the content of the thermosetting agent (B2) is equal to or less than the upper limit value, the moisture absorption rate of the thermosetting resin layer is reduced, and the reliability of the package obtained by using the first protective film forming sheet is further improved.

In the composition (III-1) for forming a resin layer and the thermosetting resin layer, the content of the thermosetting component (B) relative to the content of the polymer component (A) is 100 parts by mass (for example, the epoxy resin (B1) ) And the total content of the thermosetting agent (B2)) is preferably 50 parts by mass to 1000 parts by mass, more preferably 100 parts by mass to 900 parts by mass, particularly preferably 150 parts by mass to 800 parts by mass, for example, 200 parts by mass Any one of parts to 700 parts by mass, 300 parts by mass to 700 parts by mass, and 400 parts by mass to 700 parts by mass. When the aforementioned content of the thermosetting component (B) is in such a range, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[Curing accelerator (C)]

The composition for forming a resin layer (III-1) and the thermosetting resin layer may also be used Contains curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the resin layer forming composition (III-1).

Preferred curing accelerators (C) include, for example, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. Tertiary amine; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl 5-imidazoles such as methyl-5-hydroxymethylimidazole (imidazoles with more than one hydrogen atom substituted with groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (more than one) (Phosphine in which the hydrogen atom is substituted by an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate and other tetraphenylboron salts.

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

When the curing accelerator (C) is used, the curing accelerator is contained in the resin layer forming composition (III-1) and the thermosetting resin layer with respect to the content of the thermosetting component (B) of 100 parts by mass. The content of (C) is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the curing accelerator (C) is equal to or higher than the aforementioned lower limit value, the effect brought about by the use of the curing accelerator (C) can be obtained more remarkably. In addition, when the content of the curing accelerator (C) is equal to or less than the above upper limit, for example, the curing of the highly polar curing accelerator (C) under high temperature and high humidity conditions in the thermosetting tree The efficiency of segregation by moving to the interface side with the adherend in the fat layer is improved, and the reliability of the package obtained by using the first protective film forming sheet is further improved.

[Filling material (D)]

The composition for forming a resin layer (III-1) and the thermosetting resin layer may contain a filler (D). Since the thermosetting resin layer contains the filler (D), it is easy to adjust the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin layer. Furthermore, by optimizing the thermal expansion coefficient of the object to be formed of the first protective film, the reliability of the package obtained by using the sheet for forming the first protective film is further improved. In addition, by containing the filler (D) in the thermosetting resin layer, the moisture absorption rate of the first protective film can be reduced or the heat dissipation property can be improved.

The filler (D) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium white, red lead, silicon carbide, and boron nitride; these inorganic fillers are formed into spherical shapes Beads; surface modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

Among these, the inorganic filler material is preferably silica or alumina.

The average particle diameter of the filler (D) is not particularly limited, but is preferably 250 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and particularly preferably 100 nm or less. When the average particle diameter of the filler (D) is equal to or lower than the upper limit value, the haze (h ₁ ) on the surface of the cured product (α) becomes smaller, and the transparency of the first protective film becomes higher.

On the other hand, the lower limit value of the average particle diameter of the filler (D) is not particularly limited, but it is usually preferably 10 nm.

Furthermore, the present specification, the term "average particle diameter" unless otherwise specified, refers to the cumulative value of 50% by a laser diffraction scattering method particle size distribution curve of determined diameter (D ₅₀₎ of value.

The composition for forming a resin layer (III-1) and the filler (D) contained in the thermosetting resin layer may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination of these And the ratio can be arbitrarily selected.

When the filler (D) is used, the composition for forming a resin layer (III-1) and the thermosetting resin layer (curable resin film) preferably contain the filler (D) having an average particle diameter of 250 nm or less In terms of easily forming the first protective film with high transparency, it is more preferable to contain the filler (D) having an average particle diameter of 10 nm to 250 nm.

When the composition (III-1) for forming a resin layer and the thermosetting resin layer contain the filler (D) having an average particle diameter of 250 nm or less as described above, the filler (D) may contain only average particles The filler material (D) with a diameter of 250 nm or less may also contain the filler material (D) with an average particle size of 250 nm or less and other filler materials (D) (that is, the average particle size is greater than 250nm filler material (D)).

When the average particle diameter of the filler (D) is greater than 250 nm, the average particle diameter is preferably 1200 nm or less, and more preferably 1050 nm or less.

In the case where the composition for forming a resin layer (III-1) and the thermosetting resin layer contain a filler (D), the average particle size in the composition for forming a resin layer (III-1) and the thermosetting resin layer The ratio of the content of the filler material (D) having a diameter of 250 nm or less to the total content of the filler material (D) (sometimes referred to as "ratio (w1)" in this specification) is preferably 35% by mass to 100% by mass, More preferably, it is 45% by mass to 100% by mass, for example, any of 55% by mass to 100% by mass, 65% by mass to 100% by mass, 75% by mass to 100% by mass, and 85% by mass to 100% by mass. With the aforementioned ratio (w1) within such a range, the haze (h ₁ ) on the surface of the cured product (α) becomes smaller, and the transparency of the first protective film becomes higher.

Moreover, in the case where the aforementioned ratio (w1) is within the above range, the average particle diameter of the filler (D) having an average particle diameter greater than 250 nm is preferable in terms of achieving the effect of the present invention more significantly It is 1200 nm or less, more preferably 1050 nm or less.

In the case of using the filler (D), in the composition (III-1) for forming a resin layer, the ratio of the content of the filler (D) to the total content of all components other than the solvent (ie, thermosetting resin) The content of the filler material (D) of the layer) is preferably 5% by mass to 80% by mass, more preferably 7% by mass to 60% by mass, for example, 7% by mass to 50% by mass, and 7% by mass to 40% Any one of mass% and 7 mass% to 30 mass%. When the content of the filler (D) is in this range, the adjustment of the aforementioned thermal expansion coefficient becomes easier.

[Coupling agent (E)]

The composition for forming a resin layer (III-1) and the thermosetting resin layer may contain a coupling agent (E). By using a functional group capable of reacting with an inorganic compound or an organic compound as a coupling agent (E), the adhesion and adhesion of the thermosetting resin layer to the adherend can be improved. In addition, by using the coupling agent (E), the first protective film obtained by curing the thermosetting resin layer improves water resistance without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A), the thermosetting component (B), etc., and more preferably is a silane coupling agent.

Preferred examples of the aforementioned silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrioxide. Ethoxysilane, 3-glycidoxymethyl diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldi Ethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Based silane, 3- Mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, Vinyl triethoxysilane, imidazole silane, etc.

The composition (III-1) for forming a resin layer and the coupling agent (E) contained in the thermosetting resin layer may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination of these And the ratio can be arbitrarily selected.

When the coupling agent (E) is used, the total content of the polymer component (A) and the thermosetting component (B) in the resin layer forming composition (III-1) and the thermosetting resin layer 100 parts by mass, the content of the coupling agent (E) is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. By the aforementioned content of the coupling agent (E) being at least the aforementioned lower limit value, the dispersibility of the filler (D) in the resin is improved significantly, or the adhesion between the thermosetting resin layer and the adherend is obtained Improve the effect brought by the use of coupling agent (E). In addition, when the content of the coupling agent (E) is equal to or less than the upper limit, the generation of outgassing is further suppressed.

[Crosslinking agent (F)]

When using the acrylic resin or the like having a functional group such as a vinyl group, (meth)acryloyl group, amine group, hydroxyl group, carboxyl group, and isocyanate group that can be bonded to another compound as the polymer component (A), The composition for forming a resin layer (III-1) and the thermosetting resin layer may contain a crosslinking agent (F). The cross-linking agent (F) is a component for bonding the aforementioned functional groups in the polymer component (A) to other compounds and cross-linking. By cross-linking in this way, the initial stage of the thermosetting resin layer can be adjusted Then force and cohesion.

Examples of the crosslinking agent (F) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine-based crosslinking. Agent (crosslinking agent with aziridine group), etc.

Examples of the aforementioned organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); Terpolymers, isocyanurate bodies and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyisocyanate compounds etc. with polyol compounds . The aforementioned "adduct" means that the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. A reactant of a molecularly active hydrogen compound. Examples of the aforementioned adducts include xylene diisocyanate adducts of trimethylolpropane as described later. The so-called "terminal isocyanate urethane prepolymer" is as described above.

As the organic polyisocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate ; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Toluene diisocyanate, hexamethylene are added to all or part of the hydroxyl groups of trimethylolpropane and other polyols Methyl diisocyanate and xylene diisocyanate, one or more than two compounds; diamine diisocyanate, etc.

Examples of the aforementioned organic polyimine compounds include N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxyamide), trimethylolpropane-tri-β-nitrogen Propyridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylene Based on melamine.

In the case of using an organic polyisocyanate compound as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, it can be contained in the thermosetting resin layer by the reaction of the cross-linking agent (F) and the polymer component (A) Easy to import cross-linked structure.

Included in the resin layer forming composition (III-1) and thermosetting resin layer There may be only one type of crosslinking agent (F), or two or more types. In the case of more than two types, the combination and ratio of these may be arbitrarily selected.

When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the resin layer forming composition (III-1) is preferably 100 parts by mass relative to the content of the polymer component (A). It is 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (F) is equal to or higher than the aforementioned lower limit, the effect brought about by the use of the cross-linking agent (F) can be obtained more remarkably. In addition, when the content of the cross-linking agent (F) is equal to or less than the upper limit, the excessive use of the cross-linking agent (F) is suppressed.

[Energy Ray Curable Resin (G)]

The composition (III-1) for forming a resin layer may contain an energy ray-curable resin (G). Since the thermosetting resin layer contains the energy ray-curable resin (G), the characteristics can be changed by the irradiation of the energy ray.

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound.

Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and preferably acrylate compounds having a (meth)acryloyl group.

Examples of the aforementioned acrylate-based compound include trimethylol Propane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate Esters, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. containing chain aliphatic skeleton ( (Meth)acrylate; (meth)acrylate containing cyclic aliphatic skeleton such as dicyclopentyl di(meth)acrylate; polyalkylene glycol such as polyethylene glycol di(meth)acrylate ( Meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modified (meth)acrylate; the aforementioned polyalkylene glycol (meth) Group) polyether (meth)acrylate other than acrylate; itaconic acid oligomer, etc.

The weight average molecular weight of the aforementioned energy ray curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

The aforementioned energy ray curable compound used for polymerization may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

The energy ray curable resin (G) contained in the resin layer forming composition (III-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be Choose arbitrarily.

When using energy ray-curable resin (G), in the resin layer shape In the composition for use (III-1), the content of the energy ray-curable resin (G) is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 85% by mass.

[Photopolymerization initiator (H)]

When the composition (III-1) for forming a resin layer contains an energy ray curable resin (G), in order to efficiently perform the polymerization reaction of the energy ray curable resin (G), a photopolymerization initiator may be included (H).

Examples of the photopolymerization initiator (H) in the resin layer forming composition (III-1) include the same as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator (H) contained in the resin layer forming composition (III-1) may be only one kind, or may be two or more kinds. In the case of two or more kinds, the combination and ratio of these may be Choose arbitrarily.

In the case of using a photopolymerization initiator (H), in the resin layer forming composition (III-1), the photopolymerization initiator ( The content of H) 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.

[General Additive (I)]

The composition (III-1) for forming a resin layer and the thermosetting resin layer may contain a general-purpose additive (I) within a range that does not impair the effect of the present invention.

The general-purpose additive (I) may be a well-known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include plasticizers, antistatic agents, antioxidants, and colorants (dyes, pigments). , Gettering agent (gettering agent), etc.

The composition for forming a resin layer (III-1) and the general additive (I) contained in the thermosetting resin layer may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination of these And the ratio can be arbitrarily selected.

The content of the resin layer forming composition (III-1) and the general-purpose additive (I) of the thermosetting resin layer is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent]

The composition (III-1) for forming a resin layer preferably further contains a solvent. The solvent-containing composition for forming a resin layer (III-1) is easy to handle.

The solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol Alcohols such as alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with an amide bond), etc. .

The solvent for the resin layer forming composition (III-1) may be only one There may be two or more species, and in the case of two or more species, the combination and ratio of these may be arbitrarily selected.

The solvent contained in the resin layer forming composition (III-1) is preferably methyl ethyl ketone in that the components contained in the resin layer forming composition (III-1) can be more uniformly mixed. Wait.

<<Method for manufacturing composition for forming thermosetting resin layer>>

The composition for thermosetting resin layer formation, such as the composition for resin layer formation (III-1), can be obtained by mixing each component which comprises this composition.

The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, it can be used by mixing the solvent with any formulation component other than the solvent and diluting the formulation component in advance; or without diluting any formulation component other than the solvent in advance, and combining the solvent with These blending ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, and can be appropriately selected from known methods such as the following methods: a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; applying ultrasonic waves The method of mixing, etc.

The addition of each component and the temperature and time at the time of mixing are not particularly limited as long as each formulated component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15°C to 30°C.

○Energy line curable resin layer

The aforementioned energy ray-curable resin layer contains an energy ray-curable component (a).

The energy ray-curable component (a) is preferably uncured and preferably adhesive, and more preferably uncured and adhesive. Here, the so-called "energy ray" and "energy ray curability" are as described above.

The aforementioned energy ray-curable resin layer may be only one layer (single layer) or plural layers of more than two layers. In the case of plural layers, the plural layers may be the same as or different from each other. The combination is not particularly limited.

The thickness of the aforementioned energy ray-curable resin layer is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the energy ray-curable resin layer is equal to or greater than the above lower limit value, a first protective film with higher protection ability can be formed. In addition, when the thickness of the energy ray-curable resin layer is equal to or less than the above upper limit value, the excessive thickness is suppressed.

Here, the "thickness of the energy ray-curable resin layer" refers to the thickness of the entire energy ray-curable resin layer, for example, the thickness of the energy ray-curable resin layer composed of a plurality of layers refers to the composition of the energy ray-curable resin The total thickness of all layers of the resin layer.

The curing conditions for attaching the aforementioned energy ray-curable resin layer to the bump forming surface of the semiconductor wafer and curing it to form the first protective film, as long as the first protective film fully cures its function The degree is not particularly limited, as long as it is appropriately selected according to the type of thermosetting resin layer.

For example, the illuminance of the energy ray during curing of the energy ray-curable resin layer is preferably 180 mW/cm ² to 280 mW/cm ² . Moreover, the light quantity of the energy rays during the curing is preferably 450 mW/cm ² to 1000 mJ/cm ² .

<<Composition for Forming Energy Ray Curable Resin Layer>>

The energy ray-curable resin layer can be formed using a composition for forming an energy ray-curable resin layer containing its constituent material. For example, by applying the composition for forming an energy ray-curable resin layer on the surface to be formed of the energy ray-curable resin layer, and drying if necessary, the energy ray-curable resin layer can be formed on the target portion. The ratio of the contents of the components that do not vaporize at ordinary temperature in the composition for forming an energy ray-curable resin layer is generally the same as the ratio of the contents of the aforementioned components of the energy-ray-curable resin layer. The so-called "normal temperature" here is as explained above.

The application of the composition for forming an energy ray-curable resin layer may be carried out by a known method, and examples include air knife coaters, blade coaters, bar coaters, gravure coaters, and rolls. Coater, roll coater, curtain coater, pattern coater, blade coater, screen coater, wire bar coater, stapling coater, etc. Method.

The drying conditions of the composition for forming an energy ray curable resin layer are not particularly limited, and the composition for forming an energy ray curable resin layer contains In the case of a solvent, it is preferably dried by heating. The composition for forming an energy ray-curable resin layer containing a solvent is preferably dried at 70° C. to 130° C. for 10 seconds to 5 minutes, for example.

<Composition for Forming Resin Layer (IV-1)>

Examples of the composition for forming an energy ray-curable resin layer include, for example, the composition for forming an energy ray-curable resin layer (IV-1) containing the aforementioned energy ray-curable component (a) (in this specification, it may only be abbreviated as It is "the composition for resin layer formation (IV-1)"), etc.

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation of energy ray, and is a component for imparting film-forming properties, flexibility, or the like to the energy ray-curable resin layer.

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 80,000 to 2,000,000, and a compound having an energy ray-curable group and a molecular weight of 100 to 80,000 (a2). The aforementioned polymer (a1) may be crosslinked by at least a part of it with a crosslinking agent, or may not be crosslinked.

(Polymer (a1) with an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000)

Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 include: The acrylic polymer (a11) having a functional group that reacts with a group possessed by other compounds, and an energy ray-curable compound having an energy ray-curable group having an energy ray-curable group such as a group that reacts with the aforementioned functional group and an energy ray-curable double bond ( a12) Acrylic resin (a1-1) obtained by polymerization.

Examples of the aforementioned functional groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amine groups, and substituted amine groups (one or two hydrogen atoms of an amine group are substituted with groups other than hydrogen atoms. Group), epoxy, etc. Among these, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxyl group.

Among these, the aforementioned functional group is preferably a hydroxyl group.

. Acrylic polymer with functional groups (a11)

As the acrylic polymer (a11) having the aforementioned functional group, for example, an acrylic monomer having the aforementioned functional group and an acrylic monomer not having the aforementioned functional group are copolymerized, or other than A monomer other than an acrylic monomer (non-acrylic monomer) is further copolymerized.

In addition, the acrylic polymer (a11) may be a random copolymer or a block copolymer.

Examples of the acrylic monomer having the aforementioned functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and a substituted amine Monomer, epoxy-containing monomer, etc.

Examples of the aforementioned hydroxyl group-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-(meth)acrylic acid. Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylate; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylene unsaturated dicarboxylic acids such as maleic acid and citraconic acid (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. ( Meth)acrylic acid carboxyalkyl ester, etc.

The acrylic monomer having the aforementioned functional group is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

The acrylic monomer having the aforementioned functional group constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected .

Examples of the acrylic monomer that does not have the aforementioned functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), ( Tridecyl meth)acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetane (meth)acrylate Alkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. It is an alkyl (meth)acrylate having a chain structure of 1 to 18 carbon atoms.

In addition, examples of the acrylic monomer that does not have the aforementioned functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate. (Meth)acrylates containing alkoxyalkyl groups such as esters and ethoxyethyl (meth)acrylate; containing aromatic groups such as aryl (meth)acrylates such as phenyl (meth)acrylate (Meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N -Dimethylaminopropyl ester and other non-crosslinking (meth)acrylates with tertiary amino groups Wait.

The acrylic monomer that does not have the aforementioned functional group constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily select.

Examples of the non-acrylic monomers include olefins such as ethylene and camphene; vinyl acetate; and styrene.

The non-acrylic monomer constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the functional group to the total amount of structural units constituting the polymer is preferably 0.1% by mass To 50% by mass, more preferably 1% to 40% by mass, particularly preferably 3% to 30% by mass. With the aforementioned ratio in this range, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12), the energy ray curability The content of the base can easily adjust the curing degree of the first protective film to a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected .

In the composition (IV-1) for forming a resin layer, the content of the acrylic resin (a1-1) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 3 to 20.

. Energy ray curable compound (a12)

The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as a function that can be possessed by the acrylic polymer (a11) It is more preferable that the group reacting with a group has an isocyanate group as the aforementioned group. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The energy ray curable compound (a12) preferably has 1 to 5 energy ray curable groups in one molecule, and more preferably has 1 to 2 energy ray curable groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryloyl isocyanate. , Allyl isocyanate, 1,1-(bisacryloyloxymethyl) ethyl isocyanate; acryl monoisocyanate obtained by the reaction of a diisocyanate compound or polyisocyanate compound and hydroxyethyl (meth)acrylate Compounds; by diisocyanate compounds or polyisocyanate compounds, polyol compounds and (methyl) Acryloyl monoisocyanate compound obtained by the reaction of hydroxyethyl acrylate, etc.

Among these, the energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The energy ray curable compound (a12) constituting the acrylic resin (a1-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these may be arbitrarily select.

In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%. With the aforementioned content ratio being in this range, the adhesion of the first protective film after curing becomes greater. Furthermore, when the energy ray-curable compound (a12) is a monofunctional (having one of the aforementioned groups in one molecule) compound, the upper limit of the content ratio becomes 100 mol%. When the compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol%.

The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.

Here, the "weight average molecular weight" is as described above.

In the case where the polymer (a1) is a product obtained by crosslinking at least a part of it with a crosslinking agent, the polymer (a1) may not be equivalent to those described as constituting the acrylic polymer (a11) Any one of the above monomers and a monomer having a group that reacts with a cross-linking agent may be polymerized and cross-linked on the group that reacts with the cross-linking agent. It is formed by crosslinking the group that reacts with the aforementioned functional group of the sexual compound (a12).

The composition (IV-1) for forming a resin layer and the aforementioned polymer (a1) contained in the energy ray-curable resin layer may be only one kind, or may be two or more kinds. In the case of two or more kinds, The combination and ratio can be arbitrarily selected.

(Compound (a2) with an energy ray-curable group and a molecular weight of 100 to 80,000)

Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred examples include (methyl ) Acryloyl, vinyl, etc.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof 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. .

Among the aforementioned compound (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers and oligomers, and preferably an acrylate compound having a (meth)acryloyl group.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylate. Bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth) Group) acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy) phenyl] stilbene, 2,2-bis[4-((meth)acryloyloxypolypropyloxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate Base) 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)acryloyloxyethoxy)phenyl]propane , Neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyl propane and other difunctional (meth Group) acrylate; tris(2-(meth)acryloyloxyethyl) isocyanurate, ε-caprolactone modified tri-(2-(meth)acryloyloxyethyl) Isocyanurate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylol Propane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate And other multifunctional (meth)acrylates; (meth)acrylate urethane oligomers and other multifunctional (meth)acrylate oligomers.

Among the aforementioned compound (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, those described in paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102" can be used. . Such a resin also corresponds to a resin constituting a thermosetting component described later, and is treated as the aforementioned compound (a2) in the present invention.

The weight average molecular weight of the aforementioned compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

The aforementioned compound (a2) contained in the resin layer forming composition (IV-1) and the energy ray-curable resin layer may be only one kind, or may be two or more kinds. In the case of two or more kinds, The combination and ratio can be arbitrarily selected.

[Polymer (b) without energy ray-curable group]

When the composition for forming a resin layer (IV-1) and the energy ray-curable resin layer contain the compound (a2) as the energy ray-curable component (a), it is preferable to further contain no energy ray-curable Sex-based polymer (b).

The aforementioned polymer (b) may be crosslinked by at least a part of it with a crosslinking agent, or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. Wait.

Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes simply referred to as "acrylic polymer (b-1)").

The acrylic polymer (b-1) may also be well-known, for example, it may be a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers, or one or two A copolymer of the above acrylic monomer and a monomer (non-acrylic monomer) other than one or two or more acrylic monomers.

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth)acrylate, (meth)acrylate having a cyclic skeleton, and glycidyl group-containing (meth) Group) acrylate, hydroxyl-containing (meth)acrylate, substituted amine-containing (meth)acrylate, etc. Here, the so-called "substituted amine group" is as described above.

Examples of the aforementioned (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isopropyl (meth)acrylate Butyl ester, second butyl (meth) acrylate, third butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) ) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylic acid Decyl ester, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, (meth)acrylic acid Myristyl (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), (methyl ) Heptadecyl acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc. Group) alkyl acrylate.

Examples of the (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (methyl ) Aralkyl alkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate etc. (Meth)acrylic acid cycloalkenyloxyalkyl ester and the like.

Examples of the glycidyl group-containing (meth)acrylate include glycidyl (meth)acrylate.

Examples of the hydroxyl-containing (meth)acrylates include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (meth) 2-Hydroxypropyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Wait.

Examples of the substituted amine group-containing (meth)acrylates include N-methylaminoethyl (meth)acrylate.

Examples of the non-acrylic monomers that constitute the acrylic polymer (b-1) include olefins such as ethylene and camphene; vinyl acetate; and styrene.

Examples of the polymer (b) that does not have the aforementioned energy ray-curable group and is cross-linked by a cross-linking agent include, for example, those obtained by reacting the reactive functional group in the polymer (b) with a cross-linking agent .

The aforementioned reactive functional group is not particularly limited as long as it is appropriately selected according to the type of crosslinking agent and the like. For example, in the case where the crosslinking agent is a polyisocyanate compound, the reactive functional group may include a hydroxyl group, a carboxyl group, an amine group, and the like. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent is an epoxy-based compound, examples of the above-mentioned reactive functional group include a carboxyl group, an amine group, and an amide group. Among these, the one having a high reactivity with an epoxy group is preferred. carboxyl. Among them, in terms of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

As having the aforementioned reactive functional group and not having energy ray curability Examples of the group-based polymer (b) include those obtained by polymerizing at least a monomer having the above-mentioned reactive functional group. In the case of the acrylic polymer (b-1), as long as the above-mentioned acrylic monomer and the monomer having the aforementioned reactive functional group are exemplified as the monomer constituting the acrylic polymer (b-1), Either or both of non-acrylic monomers are sufficient. Examples of the aforementioned polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing hydroxyl-containing (meth)acrylates. In addition, the above-mentioned acrylic system A monomer or non-acrylic monomer in which one or two or more hydrogen atoms are substituted by the aforementioned reactive functional group is obtained by polymerization of the monomer.

In the aforementioned polymer (b) having a reactive functional group, relative to the total amount of structural units constituting the polymer, the ratio (content) of the amount of structural units derived from the monomer having a reactive functional group is It is preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 10% by mass. With the aforementioned ratio being such a range, the degree of crosslinking in the aforementioned polymer (b) becomes a better range.

From the viewpoint that the film-forming property of the resin layer forming composition (IV-1) becomes better, the weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to 2000000, preferably 100,000 to 1.500000. Here, the "weight average molecular weight" is as described above.

The resin layer forming composition (IV-1) and the energy ray-curable resin layer containing the polymer (b) that does not have an energy ray-curable group may be only one kind, or two or more kinds, and two kinds In the above cases, these combinations and ratios can be arbitrarily selected.

Examples of the composition (IV-1) for forming a resin layer include a composition containing either or both of the polymer (a1) and the compound (a2). In addition, when the composition (IV-1) for forming a resin layer contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy ray-curable group, and in this case, also It is preferable to further contain the aforementioned (a1). Moreover, the composition (IV-1) for resin layer formation may not contain the said compound (a2), and may contain the said polymer (a1) and the polymer (b) which does not have an energy ray curable group.

When the composition (IV-1) for forming a resin layer contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group, the composition for forming a resin layer In (IV-1), the content of the compound (a2) is preferably 10 parts by mass to 100 parts by mass relative to the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. 400 parts by mass, more preferably 30 parts by mass to 350 parts by mass.

In the composition (IV-1) for forming a resin layer, the total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group relative to the total content of components other than the solvent Proportion (ie, energy line curing The total content of the aforementioned energy ray-curable component (a) and the polymer (b) having no energy ray-curable group of the reactive resin layer) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80 % By mass, particularly preferably 20% to 70% by mass. With the aforementioned ratio of the content of the energy ray-curable component being in such a range, the energy ray-curable resin layer becomes more energy-curable.

The composition (IV-1) for forming a resin layer contains, in addition to the aforementioned energy ray-curable components, depending on the purpose, it may be selected from the group consisting of thermosetting components, photopolymerization initiators, fillers, coupling agents, crosslinking agents, and general additives One or more than two of the formed group. For example, by using the composition (IV-1) for forming a resin layer containing the aforementioned energy ray curable component and thermosetting component, the energy ray curable resin layer formed by heating increases the adhesion to the adherend The strength of the first protective film formed by the energy ray-curable resin layer is also improved.

Examples of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, and general-purpose additives in the composition (IV-1) for resin layer formation include the composition for resin layer formation ( In III-1), the thermosetting component (B), the photopolymerization initiator (H), the filler (D), the coupling agent (E), the crosslinking agent (F), and the general-purpose additive (I) are the same.

In the composition (IV-1) for forming a resin layer, the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, and the general-purpose additive may be used alone or in combination of two or more. , Combined with two In more than one case, the combination and ratio of these can be arbitrarily selected.

The content of the aforementioned thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, and general-purpose additives in the composition (IV-1) for forming a resin layer may be appropriately adjusted according to the purpose. Specially limited.

The composition for forming a resin layer (IV-1) improves its handleability by dilution, so it is preferable to further contain a solvent.

Examples of the solvent contained in the composition (IV-1) for forming a resin layer include the same as the solvent in the composition (III-1) for forming a resin layer.

The solvent contained in the resin layer forming composition (IV-1) may be only one kind or two or more kinds.

<<Manufacturing method of energy ray curable resin layer forming composition>>

The composition for forming an energy ray-curable resin layer such as the composition for forming a resin layer (IV-1) can be obtained by blending the components constituting the composition.

The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, it can be used by mixing the solvent with any formulation component other than the solvent and diluting the formulation component in advance; or without diluting any formulation component other than the solvent in advance, and combining the solvent with These blending ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, and can be appropriately selected from known methods such as the following methods: agitating a stirrer or stirring blade, etc. The method of switching to mixing; the method of mixing using a mixer; the method of mixing using ultrasonic waves, etc.

The addition of each component and the temperature and time at the time of mixing are not particularly limited as long as each formulated component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15°C to 30°C.

◇Manufacturing method of the first protective film forming sheet

The above-mentioned first protective film forming sheet can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

For example, when manufacturing the first support sheet, when the first adhesive layer or the first intermediate layer is stacked on the first substrate, by applying the first adhesive composition or the first on the first substrate The composition for forming the intermediate layer may be dried or irradiated with energy rays as needed, and the first adhesive layer or the first intermediate layer may be laminated.

On the other hand, for example, in the case where a curable resin layer is further laminated on the first adhesive layer that has been laminated on the first substrate, a composition for forming a thermosetting resin layer may be applied on the first adhesive layer Or a composition for forming an energy ray-curable resin layer to directly form a curable resin layer. Similarly, when the first adhesive layer is further laminated on the first intermediate layer that has been laminated on the first substrate, the first adhesive composition can be applied on the first intermediate layer to directly form the first adhesive剂层。 Agent layer. As such, in the case of using any composition to form a layered structure of two consecutive layers, The layer formed by the object is further coated with a composition to form a new layer. Among them, it is preferable to form the post-lamination layer of the two layers in advance using the aforementioned composition on another release film, and the exposed surface of the formed layer on the opposite side to the side in contact with the release film and the formed The exposed surfaces of the remaining layers are bonded together, thereby forming a layered structure of two consecutive layers. At this time, the aforementioned composition is preferably applied to the peeling treatment surface of the peeling film. The release film may be removed as needed after forming the laminated structure.

For example, a sheet for forming a first protective film formed by stacking a first adhesive layer on a first substrate and a curable resin layer on the first adhesive layer (the first support sheet is the first substrate and In the case of the first protective film forming sheet of the laminate of the first adhesive layer), the first adhesive composition is applied on the first substrate and dried as necessary, thereby pre-stacking on the first substrate The first adhesive layer is additionally coated with a composition for forming a thermosetting resin layer or a composition for forming an energy ray curable resin layer on the release film, and if necessary, dried to form a curable resin layer on the release film in advance , The exposed surface of the curable resin layer is bonded to the exposed surface of the first adhesive layer that has been laminated on the first substrate, and the curable resin layer is laminated on the first adhesive layer, thereby obtaining the first A sheet for forming a protective film.

In addition, for example, in the case of manufacturing a first support layer formed by stacking a first intermediate layer on the first substrate and a first adhesive layer stacked on the first intermediate layer, the first substrate is coated on the first substrate The composition for forming the intermediate layer may be dried or irradiated with energy rays as needed, thereby preliminarily depositing the first intermediate layer on the first substrate, and coating the first adhesive composition on the release film, depending on Drying is required, so that a first adhesive layer is formed on the release film in advance, and the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer that has been laminated on the first substrate, and the first An adhesive is laminated on the first intermediate layer, thereby obtaining the first support sheet. In this case, for example, a composition for forming a thermosetting resin layer or a composition for forming an energy ray curable resin layer is further coated on the release film, and if necessary, dried to form a curable resin in advance on the release film Layer, the exposed surface of the curable resin layer is bonded to the exposed surface of the first adhesive layer that has been laminated on the first intermediate layer, and the curable resin layer is laminated on the first adhesive layer to obtain The first protective film forming sheet.

Furthermore, in the case of laminating the first adhesive layer or the first intermediate layer on the first substrate, it may be formed instead of applying the first adhesive composition or the first intermediate layer on the first substrate as described above Using the method of composition, the first adhesive composition or the first intermediate layer forming composition is coated on the release film, and drying or irradiating energy rays as necessary, thereby forming the first adhesive layer on the release film in advance Or a first intermediate layer, the exposed surfaces of these layers are bonded to one surface of the first substrate, thereby laminating the first adhesive layer or the first intermediate layer on the first substrate.

In either method, the release film may be removed at any timing after the formation of the target laminate structure.

In this way, layers other than the first base material constituting the sheet for forming the first protective film can be formed on the release film in advance and bonded to the surface of the target layer The method is to build up the layer, so it is only necessary to appropriately select the layer adopting such steps as needed to manufacture the first protective film forming sheet.

In addition, the sheet for forming the first protective film is usually stored in a state where a release film is stuck on the surface of the outermost layer (for example, curable resin layer) on the side opposite to the first support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting resin layer or a composition for forming an energy ray curable resin layer, is coated on the release film (preferably its peeling surface), If necessary, dry to form a layer that constitutes the outermost layer on the release film in advance. On the exposed side of the layer that is in contact with the release film on the opposite side, stack the remaining layers by any of the above methods without removing the release film. While maintaining the bonded state, the sheet for forming the first protective film can also be obtained.

[Example]

Hereinafter, the present invention will be described in more detail with specific examples. However, the present invention is not limited to the embodiments shown below.

The components for producing the composition for forming a thermosetting resin layer are shown below.

. Polymer composition

Polymer component (A)-1: butyl acrylate (hereinafter referred to as "BA") (55 parts by mass), methyl acrylate (hereinafter referred to as "MA") (10 parts by mass), glycidyl methacrylate (Hereinafter referred to as "GMA") (20 Acrylic resin (weight average molecular weight 800,000, glass transition temperature -28°C) obtained by copolymerization of 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass).

. Epoxy resin

Epoxy resin (B1)-1: Liquid bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "YL983U").

Epoxy resin (B1)-2: Multifunctional aromatic epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "EPPN-502H").

Epoxy resin (B1)-3: Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, "EPICLON HP-7200").

. Heat curing agent

Thermosetting agent (B2)-1: Novolac type phenol resin (manufactured by Showa Denko Corporation, "BRG-556").

. Curing accelerator

Curing accelerator (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., "Curezole 2PHZ-PW").

. Filler

Filling material (D)-1: epoxy-modified spherical silica (made by Admatechs, "Admanano YA050C-MKK", average particle diameter 50 nm).

Filling material (D)-2: Spherical silica modified with epoxy groups (Admatechs, "SC1050-MA", average particle diameter 300 nm).

Filling material (D)-3: spherical silica modified with epoxy group (manufactured by Admatechs, "SC2050-MA", average particle diameter 500 nm).

Filling material (D)-4: epoxy-modified spherical silica (manufactured by Admatechs, "SC4050-MA", average particle diameter 1000 nm).

Filling material (D)-5: epoxy-modified spherical silica (made by Admatechs, "YC100C-MJK", average particle diameter 100 nm).

[Production Example 1]

(Manufacture of adhesive resin (I-2a))

Acrylic polymer was obtained by using 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (80 parts by mass) and HEA (20 parts by mass) as a raw material of the copolymer and performing a polymerization reaction.

To this acrylic polymer, 2-methacryloxyethyl isocyanate (hereinafter abbreviated as "MOI") (22 parts by mass, about 80 mol% relative to HEA) was added, and the air flow was at 50°C The addition reaction was carried out for 48 hours, thereby obtaining the target adhesive resin (I-2a).

[Example 1]

<Manufacture of the sheet for forming the first protective film>

(Manufacture of a composition for forming a thermosetting resin layer)

The polymer component (A)-1, epoxy resin (B1)-1, epoxy resin (B1)-2, epoxy resin (B1)-3, thermosetting agent (B2)-1, curing accelerator ( C)-1 and filler (D)-1 are dissolved or dispersed in methyl ethyl ketone so that the ratio of these contents becomes the value shown in Table 1, and stirred at 23°C By mixing, a composition (III-1) for forming a resin layer having a solid content concentration of 55% by mass was obtained as a composition for forming a thermosetting resin layer. In addition, the description of "-" in the column containing a component in Table 1 means that the composition for forming a thermosetting resin layer does not contain the component.

(Manufacture of the first adhesive composition)

Toluene diisocyanate trimer adduct (manufactured by Tosoh Corporation, "Coronate L") was added to the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 1 by adding trimethylolpropane (0.5 parts by mass) as an isocyanate-based crosslinking agent, and stirred at 23° C., thereby obtaining a first adhesive composition (I-2) having a solid content concentration of 30% by mass as a first adhesive composition. In addition, all the preparation parts in this "production of a 1st adhesive composition" are solid content conversion values.

(Manufacture of the first protective film forming sheet)

Apply to the aforementioned peeled surface of a peeling film (manufactured by Lintec, "SP-PET381031", thickness 38 μm) obtained by peeling one side of the polyethylene terephthalate film by silicone treatment The first adhesive composition obtained above was heated and dried at 120° C. for 2 minutes, thereby forming a first adhesive layer with a thickness of 60 μm.

Then, on the exposed surface of the first adhesive layer, a polyolefin film (thickness 25 μm), an adhesive layer (thickness 2.5 μm), and a polyethylene terephthalate film (which is the first substrate) were bonded together. Thickness of 50μm), adhesive layer (thickness of 2.5μm) and polyolefin film (thickness of 25μm) in order A 105 μm laminated film, thereby obtaining a first support sheet.

Apply to the aforementioned peeled surface of a peeling film (manufactured by Lintec, "SP-PET381031", thickness 38 μm) obtained by peeling one side of the polyethylene terephthalate film by silicone treatment The composition for forming a thermosetting resin layer obtained above was dried at 100° C. for 2 minutes to prepare a thermosetting resin film (thermosetting resin layer) with a thickness of 40 μm.

Then, the release film was removed from the first adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin film obtained above was bonded to the exposed surface of the first adhesive layer to obtain the first A sheet for forming a first protective film formed by sequentially stacking a base material, a first adhesive layer, a thermosetting resin layer, and a release film in these thickness directions.

<Evaluation of cured product of thermosetting resin film>

(Measurement of the haze (h ₁ ) on the surface of the cured product of the thermosetting resin film)

After removing the release film from the first protective film forming sheet obtained above, the exposed thermosetting resin film (thermosetting resin layer) is attached to the glass plate. Next, the first support sheet was peeled from the thermosetting resin film, and the thermosetting resin film remaining on the glass plate was heated at 160° C. for 1 hour, thereby thermally curing it. Then, using a haze meter ("NDH 5000" manufactured by Nippon Denshoku Industries Co., Ltd.), the haze on the surface of the cured thermosetting resin film (that is, the first protective film) was measured.

The above operation was performed three times, and the average value of the measured values of the obtained haze was obtained, and this average value was used as the haze (h ₁ ) on the surface of the curable resin film after curing. The results are shown in Table 1.

(Evaluation of the optical characteristics of the cured product of the thermosetting resin film)

Apply to the aforementioned peeled surface of a peeling film (manufactured by Lintec, "SP-PET381031", thickness 38 μm) obtained by peeling one side of the polyethylene terephthalate film by silicone treatment The thermosetting resin layer-forming composition obtained above was dried at 100° C. for 2 minutes, thereby producing a thermosetting resin film having a thickness of 40 μm. Next, this thermosetting resin film was heated at 160° C. for 1 hour, thereby thermally curing it to obtain a cured product (that is, a first protective film).

Place the cured product of the thermosetting resin film obtained above on a high-quality paper with a blue "+" mark with a size of 1 mm in length and 1 mm in width printed on the surface, using the camera provided above the cured material, according to the following The evaluation criterion evaluates the visibility of the "+" mark on the surface of the high-quality paper that sandwiches the cured product. The results are shown in Table 1.

○: The mark can be clearly recognized.

×: The mark is blurred and cannot be clearly recognized.

<Manufacture of the sheet for forming the first protective film, evaluation of the cured product of the thermosetting resin film>

[Examples 2 to 3, Comparative Examples 1 to 5]

Except for setting the composition for thermosetting resin layer formation as shown in Table 1 The first protective film forming sheet was produced in the same manner as in Example 1 except for the content and content of the substance, and the cured product of the thermosetting resin film was evaluated. The results are shown in Table 1.

As shown by the above results, the cured products of the thermosetting resin films of Examples 1 to 3 have a surface haze (h ₁ ) as small as 25.6 to 43.8, and are excellent in optical characteristics.

On the other hand, the cured products of the thermosetting resin films of Comparative Examples 1 to 5 had a surface haze (h ₁ ) of 55.1 or more, and had poor optical characteristics.

(Industry availability)

The present invention can be used to manufacture semiconductor wafers having bumps in connection pads used in flip chip mounting methods.

Claims (7)

A curable resin film for attaching and curing a bumped surface of a semiconductor wafer, thereby forming a first protective film on the surface; and, by applying the curable resin film When heated at 160° C. for 1 hour to cure, the haze (h ₁ ) of the surface of the curable resin film after curing is 50 or less. A curable resin film for attaching and curing a bumped surface of a semiconductor wafer, thereby forming a first protective film on the surface; and, by applying the above curable resin film when the illuminance at 230mW / cm ^2, light quantity irradiated with ultraviolet rays at 510mJ / cm ² of the cured condition, the haze (h ₂₎ of the surface of the resin film after curing is 50 or less. The curable resin film according to claim 1 or 2, wherein the curable resin film contains a filler having an average particle diameter of 250 nm or less. The curable resin film according to claim 1 or 2, wherein the curable resin film is used to cover the top of the bump of the semiconductor wafer and a region other than the vicinity of the top of the top of the semiconductor wafer and closely adhere to the bump The top and the surface other than the vicinity of the top and the circuit surface of the semiconductor wafer to form the first protective film. The curable resin film as described in claim 1 or 2, wherein the curable resin film is such that the haze is determined so that the position and shape of the scribe line or alignment mark existing on the surface of the semiconductor wafer can be recognized ( h ₁ ) or the aforementioned haze (h ₂ ) is set to 50 or less. A sheet for forming a first protective film is provided with a curable resin film according to any one of claims 1 to 5 on one surface of a first support sheet. A first method for forming a protective film, comprising: attaching a curable resin film as described in any one of claims 1 to 5 to a surface of a semiconductor wafer having bumps; the curable resin film is heated, By this, the top of the bump of the semiconductor wafer and the area other than the vicinity of the top are covered and tightly adhered to the surface of the top of the bump and the vicinity of the top and the circuit surface of the semiconductor wafer; And curing the curable resin film.