TW201728638A - Curable resin film and sheet for forming first protective film - Google Patents

Abstract

A curable resin film of the present application is adhered to a semiconductor wafer surface having bumps and is cured by heat, whereby a first protective film is formed on the semiconductor wafer surface, wherein the haze (h1) of the surface when cured by heating at 160 DEG C for one hour is 50 or less, or the haze (h2) of the surface when irradiated with ultraviolet rays under conditions in which the illumination intensity is 230 mW/cm2 and the amount of light is 510 mJ/cm2 is 50 or less. A sheet for forming the first protective film includes a first supporting sheet and the curable resin film on a surface of one side of the first supporting sheet.

Description

Curable resin film and first protective film forming sheet

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

The present application claims priority to Japanese Patent Application No. 2015-217095, filed on Jan.

In the past, a multi-lead LSI (Large Scale Integration) package used in an MPU (Micro Processing Unit) or a gate array has been mounted on a printed wiring board. In the case of the flip chip mounting method, a bump electrode (bump) formed of a eutectic solder, a high-temperature solder, gold, or the like is formed in the connection pad portion. In the semiconductor wafer, the bumps are faced to the corresponding terminal portions on the wafer mounting substrate by a face-down method, and are brought into contact with each other to perform fusion/diffusion bonding.

The semiconductor wafer used in the mounting method is obtained, for example, by dicing or dicing a surface of a semiconductor wafer having bumps formed on a circuit surface on the opposite side of the circuit surface. In order to protect the circuit surface and the bump of the semiconductor wafer, the curable resin film is attached to the bump forming surface, and the film is cured to form on the bump forming surface. Protective film. The curable resin film is typically attached to the bump forming surface, and the fluidity is increased by heating, whereby the upper top portion including the bump and the upper portion including the bump are penetrated. Exposed, it expands between the bumps, and is in close contact with the circuit surface, and covers the surface of the bump, particularly the surface of the portion near the circuit surface, to fill the bump. The protective film formed by curing the curable resin film in this state protects the bump in a state in which the surface of the bump is in close contact with the surface of the bump.

In the curable resin film, a sheet for forming a protective film comprising a thermosetting resin film containing a thermosetting component, a thermoplastic resin layer having a specific thermoelastic modulus laminated on the film is disclosed, and further A thermoplastic resin layer which is a non-plastic layer at 25 ° C is laminated on the uppermost layer of the thermoplastic resin layer (see Patent Document 1). Further, according to Patent Document 1, the sheet for forming a protective film is 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 in which the protective film is formed as described above is divided by the dicing together with the protective film to form a semiconductor wafer. Cutting The semiconductor wafer is cut by a specific portion, and the semiconductor wafer is viewed from the circuit surface side using a camera in the cutting device to identify the cutting line existing on the surface of the semiconductor wafer (ie, indicating that cutting is required) The position of the line of the portion or the alignment mark (that is, the mark for positioning the portion to be cut) is specified, and the cut portion of the semiconductor wafer is designated to perform cutting. Therefore, in order to cut the semiconductor wafer on which the protective film is formed on the bump forming surface at an accurate position, the camera in the cutting device must accurately identify 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 component, and the transparency is lowered. If the decrease in transparency becomes remarkable, it is difficult to recognize the cutting line or the alignment mark by the camera.

On the other hand, it is not determined whether the protective film disclosed in Patent Document 1 has high transparency.

[Previous Technical Literature] [Patent Literature]

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

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

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

A second aspect of the present invention is a curable resin film for attaching to a surface of a bump having a semiconductor wafer and curing, thereby forming a first protective film on the foregoing surface; When the curable resin film is cured by irradiation with ultraviolet rays under conditions of an illuminance of 230 mW/cm ² and a light amount of 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 further contain a filler having an average particle diameter of 250 nm or less.

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

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

1, 2, 3‧‧‧ First protective film forming sheet

11‧‧‧First substrate

11a‧‧‧ Surface of the first substrate

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

12'‧‧‧First protective film

13‧‧‧First adhesive layer

13a‧‧‧ Surface of the first adhesive layer

14‧‧‧First intermediate layer

101, 102, 103‧‧‧ first support tablets

101a, 102a, 103a‧‧‧ surface of the first support sheet

90‧‧‧Semiconductor Wafer

90a‧‧‧Circuit surface of semiconductor wafer

91‧‧‧Bumps

91a‧‧‧Bump surface

Fig. 1 is a cross-sectional view showing an example of a state in which a first protective film is formed on a bump forming surface by using the curable resin film of the present invention.

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

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

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

Further, the curable resin film of the second aspect of the present invention is used for attaching to a surface of a bump having a semiconductor wafer and curing, thereby forming a first protective film on the aforementioned surface, and borrowing When the curable resin film is cured by irradiation with ultraviolet rays under the conditions of an illuminance of 230 mW/cm ² and a light amount of 510 mJ/cm ² , the haze (h ₂ ) of the surface of the curable resin film after curing is 50 or less. . The curable resin film of the second aspect is an energy ray-curable resin film.

Further, the first protective film forming sheet of the present invention comprises the curable resin film of the first aspect or the second aspect of the present invention on one surface of the first support sheet. In the first protective film forming sheet, the "curable resin film" may be referred to as a "curable resin layer".

The first protective film forming sheet of the present invention is used by being attached to a bump-containing surface (i.e., a circuit surface) of a semiconductor wafer via a curable resin layer (curable resin film). Further, the curable resin layer after the adhesion is increased in 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 bump, particularly in the vicinity of the circuit surface. The bumps are buried in the surface of the part. The curable resin layer in this state is further cured by heating or irradiation with an energy ray, and finally a first protective film is formed, and the bump is protected in a state in which the surface of the bump is in close contact with the surface of the bump. The semiconductor wafer to which the first protective film-forming sheet is attached is polished, for example, by polishing a surface on the opposite side of the circuit surface, and then removing the first support sheet, and then heating the curable resin layer to perform bumping. The filling and the formation of the first protective film are finally incorporated into the semiconductor device in a state in which the first protective film is provided.

Further, in the present specification, the surface of the bump and the circuit surface of the semiconductor wafer may be collectively referred to as a "bump forming surface".

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

In 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 referred to simply as "cured material (α) The haze (h ₁ ) of the surface of the structure ") is 50 or less.

Further, for the second aspect of the curable resin film (energy ray-curable resin layer) of the present invention, by ^2, the light quantity of ultraviolet irradiation 510mJ / cm ² illuminance in the condition 230mW / cm and the resulting cured with ultraviolet rays The haze (h ₂ ) of the surface of the cured product (hereinafter sometimes simply referred to as "cured material (β)") is 50 or less.

Thus, the curable resin film of the present invention can form a high transparency in the form of a cured product thereof (ie, a first protective film).

Therefore, after the first protective film is formed on the bump-forming surface of the semiconductor wafer including the circuit surface using the curable resin film of the present invention, the first protective film can be interposed when the semiconductor wafer is viewed from the circuit surface side. The position and shape of the cutting lines or alignment marks present on the surface of the semiconductor wafer are accurately identified by the camera. Further, when the semiconductor wafer is cut together with the first protective film by dicing to obtain a semiconductor wafer, the cut portion of the semiconductor wafer can be accurately specified.

The haze (h ₁ ) of the surface of the cured product (α) of the present invention and the haze (h ₂ ) of the surface of the cured product (β) can be, for example, the type and amount of the component to be described later of the curable resin film. And adjust.

Fig. 1 is a cross-sectional view showing an example of a state in which a first protective film is formed on a bump forming surface by using the curable resin film of the present invention. In the drawings used in the following description, the features of the present invention may be more easily understood, and the parts which are the main parts are enlarged for the sake of convenience, and the dimensional ratios and the like of the respective constituent elements are not necessarily the same as the 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 the ball is cut by a plane, and corresponds to a plane of the portion that is cut out and exposed, and is in contact with the circuit surface 90a of the semiconductor wafer 90.

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

The above-described substantially spherical shape of the bump 91 is particularly advantageous in that the first protective film is formed using the curable resin film of the present invention.

In addition, the semiconductor wafer to be used for the curable resin film of the present invention is not limited to those shown in FIG. 1, and a part of the configuration may be changed, deleted, or added within a range that does not impair the effects of the present invention. For example, in FIG. 1, as the bump, the above-described substantially spherical shape is shown (by flat A shape in which a part of the ball is cut out, but a bump as a preferred shape is also exemplified: the substantially spherical shape is in the height direction (Fig. 1 and the semiconductor wafer) a shape obtained by stretching a circuit surface 90a perpendicular to the plane 90a, that is, a shape of a substantially spheroidal ellipsoid of a long ball (the plane of the ellipsoid of the long ball including the one end of the long axis direction is cut off by a plane) a convex shape of the formed shape; or a shape in which the substantially spherical shape as described above is flattened in the height direction, that is, a shape of a substantially spheroidal spheroid (the ellipsoid of the spheroid by a plane) A bump including a shape in which one end of the short-axis direction is cut. Similarly to the above-described substantially spherical projections, the projections having such a substantially spheroidal shape are particularly advantageous in that the first protective film is formed using the curable resin film of the present invention.

Further, the shape of the bump described so far is only an example of a case where the thermosetting resin film of the present invention is applied. In the present invention, the shape of the bump is not limited to the shape.

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

◎ first support piece

The first support sheet may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. In the case where the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

Furthermore, in the present specification, the present invention is not limited to the case of the first support sheet, and the phrase "the plurality of layers may be the same or different from each other" means "all layers can be made In the same manner, all the layers may be different, or only a part of the layers may be the same. Further, "the plural layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer are 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 a first layer is laminated on the first intermediate layer. The adhesive layer is made up of only the first substrate.

In the following, an example of the first protective film forming sheet of the present invention will be described with reference to the drawings. In the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, the parts which are the main parts are enlarged for the sake of convenience, and the dimensional ratios and the like of the respective constituent elements are not necessarily the same as the actual ones.

Fig. 2 is a cross-sectional view schematically showing an embodiment of a first protective film forming sheet of the present invention. The first protective film forming sheet 1 shown here is used as a first supporting sheet in which a first adhesive layer is laminated on a first substrate. In other words, the first protective film forming sheet 1 includes a first adhesive layer 13 on the first base material 11 and a curable resin layer (curable resin film) 12 on the first adhesive layer 13 . The first support sheet 101 is a laminate of the first substrate 11 and the first adhesive layer 13, and is provided 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 first protective film forming sheet 1, the curable resin layer 12 is cured to form a cured product (α) having a haze (h ₁ ) of 50 or less and a haze (h ₂ ) of 50 on the surface. The following cured product (β) forms a first protective film having high transparency.

Fig. 3 is a cross-sectional view schematically showing another embodiment of the first protective film forming sheet of the present invention. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals as those in FIG. 2, and detailed description thereof will be omitted. This situation is also the same in the figures of Figure 4 and later.

The first protective film forming sheet 2 shown here is used as a first supporting sheet in which a first intermediate layer is laminated on a first substrate and a first adhesive layer is laminated on the first intermediate layer. In other words, the first protective film forming sheet 2 includes the first intermediate layer 14 on the first substrate 11, the first adhesive layer 13 on the first intermediate layer 14, and the first adhesive layer 13 on the first adhesive layer 13 The resin layer (curable resin film) 12 is formed. The first support sheet 102 is a laminated body in which the first base material 11 , the first intermediate layer 14 and the first adhesive layer 13 are sequentially laminated, and is first adhered to one surface 102 a of the first support sheet 102 . 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 attached to 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 first protective film forming sheet 2, the curable resin layer 12 is cured to form a cured product (α) having a haze (h ₁ ) of 50 or less and a haze (h ₂ ) of 50 on the surface. The following cured product (β) forms a first protective film having high transparency.

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

The first protective film forming sheet 3 shown here uses a first support sheet as the first support sheet. In other words, the first protective film forming sheet 3 is formed by providing a curable resin layer (curable resin film) 12 on the first base material 11 . The first support sheet 103 is composed only of the first base material 11, and is provided on the one surface 103a of the first support sheet 103, that is, on one surface 11a 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 obtained by removing the first adhesive layer 13 from the first protective film forming sheet 1 shown in Fig. 2 .

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

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

○ first substrate

The first base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.

Examples of the resin include low density polyethylene (LDPE) and linear low density polyethylene (Linear). Polyethylene such as Low Density Polyethylene; LLDPE), High Density Polyethylene (HDPE); Polyethylene, Polybutene, Polybutadiene, Polymethylpentene, Decorene Resin, etc. Olefin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norbornene copolymer, etc., ethylene copolymer (using ethylene as a monomer) Copolymer); vinyl chloride resin such as polyvinyl chloride or vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polynaphthalene Ethylene formate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalate, all aromatic aromatic polyesters with structural cyclic groups Equivalent polyester; copolymer of two or more of the foregoing polyesters; poly(meth)acrylate; polyurethane; polyacrylamide; polyimine; polyamine; polycarbonate Fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polyfluorene; polyether ketone Wait.

In addition, as the resin, for example, a polymer alloy such as a mixture of the above polyester and a resin other than the above may be mentioned. The polymer of the polyester and the other resin is preferably a relatively small amount of the resin other than the polyester.

In addition, as the resin, for example, a crosslinked resin obtained by crosslinking one or two or more kinds of the resins exemplified so far, and one or more of the above-exemplified resins may be used. A modified resin such as an ionomer.

In addition, in this specification, "(meth)acrylic acid" means a package Contains the concepts of both "acrylic" and "methacrylic". The term "(meth)acrylate" is similar to that of (meth)acrylic acid. For example, "(meth)acrylate" includes the concept of "acrylate" and "methacrylate". The term "base" includes the concepts of both "acryloyl group" and "methacryloyl group".

The resin constituting the first substrate may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

The first substrate may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combinations of the plurality of layers are not Specially limited.

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

Here, the "thickness of the first base material" means the thickness of the entire first base material, for example, the thickness of the first base material composed of a plurality of layers, and the total thickness of all the layers constituting the first base material. .

The first substrate preferably has a higher precision of thickness, that is, a deviation from the thickness regardless of the portion is suppressed. Among the above-mentioned constituent materials, examples of the material which can be used for forming the first substrate having high precision of such a thickness include, for example, Polyolefins other than polyethylene and polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like.

The first base material may contain various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the resin.

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

When the first adhesive layer or the curable resin layer has energy ray curability, the first substrate preferably transmits energy rays.

The first substrate can be produced by a known method. For example, the first substrate containing a resin can be produced by molding a resin composition containing the above 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 pressure-sensitive adhesive include an acrylic resin (an adhesive composed of a resin having a (meth)acryl fluorenyl group) and a urethane resin (a resin having a urethane bond). Adhesive), a rubber-based resin (an adhesive composed of a resin having a rubber structure), an anthrone-based resin (an adhesive composed of a resin having a siloxane coupling), and an epoxy resin (having Adhesive composed of epoxy resin), polyvinyl ether, poly The adhesive resin such as carbonate is preferably an acrylic resin.

In the present invention, the term "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, not only the resin itself but also an additive, etc. A resin which exhibits adhesiveness in combination with other components, or a resin which exhibits adhesiveness by the presence of a trigger such as heat or water.

The first adhesive layer may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is There is no special limit.

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

The term "thickness of the first adhesive layer" as used herein means the thickness of the first adhesive layer as a whole, for example, the thickness of the first adhesive layer composed of a plurality of layers, which means that all of the first adhesive layers are formed. The total thickness of the layers.

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

In the present invention, the term "energy line" means an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays and radiation. Electron beam, etc.

The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, or an LED (Light Emitting Diode) lamp as an ultraviolet source. Regarding the electron beam, it can be irradiated by an electron beam accelerator or the like.

In the present invention, the term "energy ray curability" refers to a property of curing by irradiation with an energy ray. The term "non-energy ray curability" means a property that does not cure even when irradiated with an energy ray.

<<First Adhesive Composition>>

The first adhesive layer can be formed using a first adhesive composition containing an adhesive. For example, the first adhesive composition is applied to the target surface of the first adhesive layer, and if necessary, dried to form a first adhesive layer at the target portion. A more specific method of forming the first adhesive layer will be described in detail later together with the formation method of the other layers. The ratio of the content of the components which are not vaporized at normal temperature in the first adhesive composition is usually the same as the ratio of the contents of the aforementioned components of the first adhesive layer. In addition, the term "normal temperature" as used herein means a temperature which is not particularly cold or hot, that is, a normal temperature, and examples thereof include a temperature of 15 ° C to 25 ° C.

The application of the first adhesive composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll coater. , roll coater, curtain type A method of various coaters such as a coater, a pattern coater, a blade coater, a screen coater, a bar coater, and an applicator coater.

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

In the case where the first adhesive layer is in the form of energy ray curability, the first adhesive composition containing the energy ray-curable adhesive, that is, the energy ray-curable first adhesive composition, for example, the following adhesives A composition (I-1) containing a non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)"), And an energy ray-curable compound; the first adhesive composition (I-2) containing energy-line curability in which an unsaturated group is introduced into a side chain of the non-energy ray-curable adhesive resin (I-1a) Adhesive resin (I-2a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)"); and first adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) ) and energy line curable low molecular compounds.

<First Adhesive Composition (I-1)>

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

[Adhesive resin (I-1a)]

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

The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

The structural unit of the acrylic resin may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

The alkyl (meth)acrylate may, for example, be an alkyl group constituting the alkyl ester having 1 to 20 carbon atoms, and the alkyl group is preferably a linear or branched chain.

Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-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-decyl (meth)acrylate, Isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A) Tridecyl acrylate, tetradecyl (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) propylene Pentadecyl acid ester, eicosyl (meth)acrylate, and the like.

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

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

Examples of the functional group-containing monomer include a starting point for crosslinking by reaction of the functional group with a crosslinking agent described later, or a reaction of the functional group with an unsaturated group in the unsaturated group-containing compound. This can introduce an unsaturated group 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 hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxy(meth)acrylate. Propyl propyl ester, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. A hydroxyalkyl acrylate; a non-(meth)acrylic unsaturated alcohol such as vinyl alcohol or allyl alcohol (an unsaturated alcohol having no (meth) acrylonitrile skeleton).

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; fumaric acid and itaconic acid; An ethylenically unsaturated dicarboxylic acid such as maleic acid or citraconic acid (dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; 2-carboxyethyl methacrylate; Base) carboxyalkyl acrylate and the like.

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

The functional group-containing monomer constituting the acrylic polymer may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

The acrylic polymer may further have a structural unit derived from another monomer, in addition to a structural unit derived from an alkyl (meth)acrylate and a structural unit derived from a monomer having a functional group.

The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth)acrylate or the like.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The other monomers constituting the acrylic polymer may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

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

In the present invention, the term "energy ray polymerizability" refers to a property of being polymerized by irradiation of an energy ray.

The adhesive resin (I-1a) contained in the first adhesive composition (I-1) can be There are only two types, and two or more types may be used. When two or more cases are used, the combinations and ratios may be arbitrarily selected.

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

[Energy curing compound]

The energy ray-curable compound contained in the first adhesive composition (I-1) includes a monomer or oligomer which has an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray. .

In the energy ray-curable compound, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol VI (A). Poly(meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; amine (meth)acrylate Ester; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate, and the like.

In the energy ray-curable compound, examples of the oligomer include an oligomer obtained by polymerizing the above-exemplified monomers.

The energy ray-curable compound is preferably a (meth)acrylic acid urethane or a (meth)acrylic acid amine group in terms of a relatively large molecular weight and a tendency to lower the storage elastic modulus of the first adhesive layer. Formate oligomer.

The energy ray-curable compound contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily select.

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

[crosslinking agent]

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

The crosslinking agent reacts with the aforementioned functional group, for example, to crosslink the adhesive resin (I-1a) with each other.

Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of such diisocyanates; An epoxy-based crosslinking agent such as a glycol glycidyl ether (a crosslinking agent having a glycidyl group); an aziridine-based crosslinking such as hexa[1-(2-methyl)-aziridine]triphosphorazine A crosslinking agent (a crosslinking agent having an aziridine group); a metal chelate crosslinking agent such as an aluminum chelate compound (a crosslinking agent having a metal chelate structure); an isocyanurate crosslinking agent (crosslinking agent having a hetero-cyanuric acid skeleton) or the like.

The crosslinking agent is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive, improving the adhesion of the first adhesive layer, and facilitating the acquisition.

The crosslinking agent contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-1), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably 0.1%, based on 100 parts by mass of the content of the adhesive resin (I-1a). The parts by mass are preferably 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 an energy line having a relatively low energy such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compound; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzamide a mercaptophosphine oxide compound such as bisphenylphosphine oxide; a thioether compound such as benzyl phenyl sulfide or tetramethylthiuram; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; azo An azo compound such as diisobutyronitrile; a titanocene compound such as ferrocene; a thioxanthone compound such as thioxanthone; a peroxide compound; a diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone ; 2-Chloropurine and the like.

In addition, as the photopolymerization initiator, for example, an anthracene compound such as 1-chloroindole or a photosensitizer such as an amine can be used.

The photopolymerization initiator contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more cases are used, the combinations and ratios may be arbitrarily selected. .

In the first adhesive composition (I-1), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass, more preferably 0.03, based on 100 parts by mass of the content of the energy ray-curable compound. The mass fraction is preferably 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 which are not equivalent to any of the above components, within a range not impairing the effects of the present invention.

Examples of the other additives include an antistatic agent, an antioxidant, a softener (plasticizer), a filler (filler), a rust preventive, and coloring. A known additive such as a agent (pigment, dye), a sensitizer, a tackifier, a reaction retarder, and a crosslinking accelerator (catalyst).

Further, the reaction retardant is inhibited in the first adhesive composition (I-1) during storage by, for example, the action of the catalyst mixed in the first adhesive composition (I-1). It is not the target of the cross-linking reaction. The reaction retardation agent may, for example, be a chelate complex formed by a chelate against a catalyst, and more specifically, a one having two or more carbonyl groups (-C(=O)-) in one molecule.

The other additives contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-1), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

[solvent]

The first adhesive composition (I-1) may also contain a solvent. When the first adhesive composition (I-1) contains a solvent, the coating suitability to the surface to be coated is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include a ketone such as methyl ethyl ketone or acetone; an ester such as ethyl acetate (carboxylate); an ether such as tetrahydrofuran or dioxane; and cyclohexane. An aliphatic hydrocarbon such as n-hexane; an aromatic hydrocarbon such as toluene or xylene; an alcohol such as 1-propanol or 2-propanol; or the like.

The solvent can be directly used in the first adhesive composition (I-1), for example, without removing the adhesive resin (I-1a) from the adhesive resin (I-1a). When the first adhesive composition (I-1) is produced, a solvent which is the same as or different from that used in the production of the adhesive resin (I-1a) may be separately added.

The solvent contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<First Adhesive Composition (I-2)>

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

[Adhesive resin (I-2a)]

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

The unsaturated group-containing compound is further bonded to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the above-mentioned energy ray polymerizable unsaturated group. a compound of the group.

Examples of the energy ray polymerizable unsaturated group include a (meth) acryl fluorenyl group, an ethenyl group, an allyl group (2-propenyl group), and the like, and a (meth) acrylonitrile group is preferable.

Examples of the group bondable to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group which may be bonded to a hydroxyl group or an amine group, and a bond with a carboxyl group or an epoxy group. The hydroxyl group and the amine group of the knot.

Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl decyl isocyanate, and (meth)acrylic acid glycidyl ester.

The adhesive resin (I-2a) contained in the first adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be Choose arbitrarily.

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

[crosslinking agent]

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

The crosslinking agent in the first adhesive composition (I-2) may be the same as the crosslinking agent in the first adhesive composition (I-1).

The crosslinking agent contained in the first adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-2), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably 0.1%, based on 100 parts by mass of the adhesive resin (I-2a). The parts by mass are preferably 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 a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy line having a relatively low energy such as ultraviolet rays.

The photopolymerization initiator in the first adhesive composition (I-2) is 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 one type or two or more types. When two or more cases are used, the combinations and ratios may be arbitrarily selected. .

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

[Other additives]

The first adhesive composition (I-2) may contain other additives which are not equivalent to any of the above components, within a range not impairing the effects of the present invention.

The other additives mentioned in the first adhesive composition (I-2) are the same as those of the other additives in the first adhesive composition (I-1).

The other additives contained in the first adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-2), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

[solvent]

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

The solvent in the first adhesive composition (I-2) is the same as the solvent in the first adhesive composition (I-1).

The solvent contained in the first adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<First Adhesive Composition (I-3)>

As described above, the first adhesive composition (I-3) contains the above-mentioned 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 from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, particularly preferably 15% by mass. % to 90% by mass.

[Energy ray curable low molecular compound]

The energy ray-curable low molecular compound contained in the first adhesive composition (I-3) includes a monomer having an energy ray polymerizable unsaturated group and which can be cured by irradiation with an energy ray. The polymer is the same as the energy ray-curable compound contained in the first adhesive composition (I-1).

The energy ray-curable low molecular compound contained in the first adhesive composition (I-3) may be one type or two or more types. In the case of the above, the 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 from 0.01 part by mass to 300 parts by mass based on 100 parts by mass of the content of the adhesive resin (I-2a). More preferably, it is 0.03 part by mass to 200 parts by mass, and particularly preferably from 0.05 part by mass 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 an energy line having a relatively low energy such as ultraviolet rays.

The photopolymerization initiator in the first adhesive composition (I-3) is 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 one type or two or more types. When two or more cases are used, the combinations and ratios 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 energy ray-curable low molecular compound. The mass fraction is 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 which are not equivalent to any of the above components, within a range not impairing the effects of the present invention.

The other additives mentioned above are 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 one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-3), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

[solvent]

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

The solvent in the first adhesive composition (I-3) is the same as the solvent in the first adhesive composition (I-1).

The solvent contained in the first adhesive composition (I-3) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<First Adhesive Composition Other than First Adhesive Compositions (I-1) to (I-3)>

Heretofore, the first adhesive composition (I-1), the first adhesive composition (I-2), and the first adhesive composition (I-3) have been mainly described, but as such All of the first adhesive compositions other than the three first adhesive compositions are included in the specification (in the present specification, referred to as "first adhesive compositions (I-1) to (I-3)) The same can be used in the first adhesive composition ").

As the first adhesive composition other than the first adhesive composition (I-1) to (I-3), in addition to the energy ray-curable adhesive composition, a non-energy ray-curable adhesive may be mentioned. Composition.

Examples of the non-energy ray-curable adhesive composition include an acrylic resin (resin having a (meth) acrylonitrile group) and an urethane resin (a resin having a urethane bond). ), rubber-based resin (resin having a rubber structure), anthrone-based resin (resin having a siloxane coupling), epoxy resin (a resin having an epoxy group), and adhesion such as polyvinyl ether or polycarbonate The resin is preferably one containing an acrylic resin.

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

<<Method of Manufacturing First Adhesive Composition>>

The first adhesive composition such as the first adhesive composition (I-1) to (I-3) can be used to form the first adhesive by using the adhesive, and optionally the above-mentioned adhesive. It is obtained by blending the components of the agent composition.

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

When a solvent is used, it can be used by mixing a solvent with any compounding component other than the solvent to pre-dilute the compounding component, or by pre-diluting any of the formulating components other than the solvent, and These formulated ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from a known method such as the following method: a method in which a stirrer or a stirring blade is rotated and mixed; a method in which mixing is performed using a mixer; Ultrasonic method of mixing.

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

○ first intermediate layer

The first intermediate layer is in the form of a sheet or a film, and the constituent material thereof is appropriately selected depending on the purpose, and is not particularly limited.

For example, in order to suppress the case where the shape of the bump existing on the surface of the semiconductor is reflected on the protective film covering the surface of the semiconductor to deform the protective film, as the preferred constituent material of the first intermediate layer, the first intermediate layer For the further improvement of the adhesion, (meth) propyl Alkyl amide or the like.

The first intermediate layer may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combinations of the plurality of layers are not Specially limited.

The thickness of the first intermediate layer can be appropriately adjusted according to the height of the bump of the semiconductor surface to be protected, and it is also preferably 50 μm to 600 μm in terms of easily absorbing the influence of the bump having a relatively high height. More preferably, it is 70 μm to 500 μm, and particularly preferably 80 μm to 400 μm.

Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer, for example, the thickness of the first intermediate layer composed of a plurality of layers, and the total thickness of all the layers constituting the first intermediate layer. .

<<First intermediate layer forming composition>>

The first intermediate layer can be formed using a composition for forming a first intermediate layer containing a constituent material thereof. For example, the first intermediate layer forming composition is applied to the surface to be formed of the first intermediate layer, and if necessary, it is dried or cured by irradiation with an energy ray, whereby the first intermediate layer can be formed at the target portion. A more specific method of forming the first intermediate layer will be described in detail later together with the formation method of the other layers. The ratio of the content of the components which are not vaporized at normal temperature in the composition for forming the first intermediate layer is usually the same as the ratio of the content of the components of the first intermediate layer. The term "normal temperature" as used herein is as explained above.

The application of the first intermediate layer forming composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll coat. Method for various coating machines such as cloth machine, roll coater, curtain coater, pattern coater, blade coater, screen coater, wire bar coater, and staple coater .

The drying conditions of the first intermediate layer forming composition are not particularly limited. For example, the first intermediate layer-forming composition containing a solvent to be described later 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.

When the composition for forming the first intermediate layer has energy ray curability, it is preferably cured by irradiation with an energy ray after drying.

The first intermediate layer-forming composition (II-1) or the like containing (meth)acrylic acid urethane is exemplified as the first intermediate layer-forming composition.

<First intermediate layer forming composition (II-1)>

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

[(Meth)acrylic acid urethane]

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

The (meth)acrylic acid urethane may be monofunctional (having only one (meth) acrylonitrile group in one molecule), or may be difunctional or more (more than two in one molecule) Base) A polyacrylic acid group. Among them, in the present invention, the (meth)acrylic acid urethane is preferably at least monofunctional.

The (meth)acrylic acid urethane contained in the first intermediate layer forming product may, for example, be a reaction between a polyol compound and a polyvalent isocyanate compound to obtain a terminal isocyanate urethane prepolymer. Further, a (meth)acrylic compound having a hydroxyl group and a (meth)acrylinyl group is reacted with the terminal isocyanate urethane prepolymer. The term "terminal isocyanate urethane prepolymer" as used herein refers to a prepolymer having a urethane bond and having an isocyanate group at a terminal portion of the molecule.

The (meth)acrylic acid urethane contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When two or more types are used, the Combinations and ratios can be arbitrarily selected.

(polyol compound)

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

These polyol compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

Examples of the polyol compound include an alkylene glycol, a polyether polyol, a polyester polyol, and a polycarbonate polyol.

The polyol compound may be any one of a difunctional diol, a trifunctional triol, and a tetrafunctional or higher polyhydric alcohol, and is preferably two in terms of availability, versatility, reactivity, and the like. alcohol.

. Polyether polyol

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

(wherein n is an integer of 2 or more; R is a divalent hydrocarbon group, and a plurality of R may be the same or different from each other.)

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

In the formula, R is not particularly limited as long as it is a divalent hydrocarbon group, and is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and further preferably an exoethyl group, a propyl group or a tetramethylene group. It is especially preferred to be a propyl or tetramethylene group.

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

By reacting the above polyether diol with the above polyvalent isocyanate compound, an ether bond having the ether bond represented by the following formula (1a) can be obtained as the terminal isocyanate urethane prepolymer. Further, by using such a terminal isocyanate urethane prepolymer, the (meth)acrylic acid urethane has the above-mentioned ether bond portion, that is, has a polyether type diol derived therefrom. Structural unit.

(wherein R and n are the same as described above.)

. Polyester polyol

The polyester polyol is not particularly limited, and examples thereof include those obtained by subjecting an esterification reaction using a polybasic acid or a derivative thereof. Furthermore, this is said The term "derivative" as used in the specification means that one or more groups of the original compound are substituted by a group other than the substituent (substituent) unless otherwise specified. Here, the "group" is not only an atomic group in which a plurality of atoms are bonded, but also an atom.

Examples of the polybasic acid and the derivative thereof include polybasic acids and derivatives thereof which are generally used as a raw material for the production of polyester.

Examples of the polybasic acid include a saturated aliphatic polybasic acid, an unsaturated aliphatic polybasic acid, and an aromatic polybasic acid, and a dimer acid corresponding to any of these may be used.

Examples of the saturated aliphatic polybasic acid include saturated aliphatic binary compounds such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and sebacic acid. Acid, etc.

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-naphthalene dicarboxylic acid; and aromatic tribasic acids such as trimellitic acid. An aromatic tetrabasic acid such as pyromellitic acid.

Examples of the derivative of the polybasic acid include an acid anhydride of the above saturated aliphatic polybasic acid, an unsaturated aliphatic polybasic acid, and an aromatic polybasic acid, and a hydrogenated dimer acid.

The polybasic acid or a derivative thereof may be used singly or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

The polybasic acid is preferably an aromatic polybasic acid in terms of being suitable for forming a coating film having a moderate hardness.

In the esterification reaction for obtaining a polyester polyol, a known catalyst can also be used as needed.

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

. Polycarbonate polyol

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

Here, the diol and the alkylene carbonate may be used singly or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

The number average molecular weight of the polyol compound calculated based on the hydroxyl value is preferably from 1,000 to 10,000, more preferably from 2,000 to 9000, still more preferably from 3,000 to 7,000. By the aforementioned number average molecular weight of 1000 or more, The excessive formation of the urethane bond is suppressed, and the control of the viscoelastic property of the first intermediate layer becomes easier. Further, by the aforementioned number average molecular weight being 10,000 or less, excessive softening of the first intermediate layer is suppressed.

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

[A number average molecular weight of the polyol compound] = [number of functional groups of the polyol compound] × 56.11 × 1000 / [hydroxy group value of the polyol compound (unit: mgKOH / g)]

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

(polyisocyanate compound)

The polyvalent isocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.

The polyisocyanate compound may be used alone or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

Examples of the polyvalent isocyanate compound include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate and hail Alkyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ω,ω'-diisocyanate dimethyl a cyclic aliphatic diisocyanate such as cyclohexane; 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, tolidine diisocyanate, tetramethylene xylene diisocyanate, naphthalene-1 An aromatic diisocyanate such as 5-diisocyanate.

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

((meth)acrylic compound)

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

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

Examples of the (meth)acrylic compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). ) 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) acrylate a hydroxyl group-containing (meth) acrylate such as an ester; N-hydroxymethyl (meth) acrylamide or the like a (meth) acrylamide of a hydroxyl group; a reactant obtained by reacting (meth)acrylic acid with vinyl alcohol, vinyl phenol or bisphenol A diglycidyl ether, and the like.

Among these, the (meth)acrylic compound is preferably a hydroxyl group-containing (meth)acrylate, more preferably a hydroxyl group-containing (meth)acrylic acid alkyl ester, and particularly preferably (meth)acrylic acid 2 - hydroxyethyl ester.

In the reaction between the terminal isocyanate urethane prepolymer and the (meth)acrylic compound, a solvent, a catalyst, or the like can be used as needed.

The conditions for reacting the terminal isocyanate urethane prepolymer with the above (meth)acrylic compound may be appropriately adjusted, for example, the reaction temperature is preferably from 60 ° C to 100 ° C, and the reaction time is preferably one hour. Up to 4 hours.

The aforementioned (meth)acrylic acid urethane may be any of an oligomer, a polymer, and a mixture of an oligomer and a polymer, and is preferably an oligomer.

For example, the weight average molecular weight of the aforementioned (meth)acrylic acid urethane is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000, still more preferably from 5,000 to 65,000. By the weight average molecular weight of 1,000 or more, in the polymer of the (meth)acrylic acid urethane and the polymerizable monomer described later, the molecules derived from the structure of the (meth)acrylic acid urethane are The force is applied, and the hardness of the first intermediate layer is easily optimized.

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

[Polymerizable monomer]

In the aspect of further improving the film formability, the first intermediate layer-forming composition (II-1) may contain a polymerizable monomer in addition to the (meth)acrylic acid urethane.

The polymerizable monomer is preferably a compound having at least one (meth) acrylonitrile group in one molecule, except for an oligomer and a polymer having energy ray polymerizability and a weight average molecular weight of 1,000 or more.

The polymerizable monomer may, for example, be an alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms and having a chain shape; and having a hydroxyl group, a mercaptoamine group, an amine group or a ring. (meth)acrylic compound containing a functional group such as an oxy group; (meth) acrylate having an aliphatic cyclic group; (meth) acrylate having an aromatic hydrocarbon group; having a heterocyclic group (Meth) acrylate; a compound having a vinyl group; a compound having an allyl group; and the like.

Examples of the alkyl (meth)acrylate having a chain alkyl group having 1 to 30 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-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-decyl (meth)acrylate, isodecyl (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), (meth)acrylic acid Alkyl ester, octadecyl (meth) acrylate (stearyl (meth) acrylate), isostearyl (meth) acrylate (isostearyl (meth) acrylate), (A) Base) hexadecyl acrylate, eicosyl (meth) acrylate, and the like.

Examples of the functional group-containing (meth)acrylic acid derivative include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. a hydroxyl group-containing (meth) acrylate such as 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; (meth) acrylonitrile Amine, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methylolpropane (A) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. (meth) acrylamide and its derivatives; a (meth) acrylate (hereinafter sometimes referred to as "amino group-containing (meth) acrylate"); a monosubstituted amino group having a hydrogen atom of an amine group substituted with a group other than a hydrogen atom (meth) acrylate (hereinafter sometimes referred to as "monosubstituted amino group-containing (meth) acrylate"); two hydrogen atoms having an amine group are replaced by a group other than a hydrogen atom A disubstituted amino group (meth) acrylate (hereinafter sometimes referred to as "disubstituted amine group-containing (meth) acrylate"); (meth) acrylate glycidyl ester, (meth) acrylate An epoxy group-containing (meth) acrylate such as methyl glycidyl ester (hereinafter sometimes referred to as "epoxy group-containing (meth) acrylate)" or the like.

Here, the "amino group-containing (meth) acrylate" means a compound in which one or two or more hydrogen atoms of a (meth) acrylate are substituted with an amine group (-NH ₂ ). Similarly, the term "monosubstituted amino group-containing (meth) acrylate" refers to a compound in which one or two or more hydrogen atoms of a (meth) acrylate are substituted with a monosubstituted amino group, so-called "including The (di)amino group (meth) acrylate refers to a compound in which one or two or more hydrogen atoms of a (meth) acrylate are substituted with a disubstituted amino group.

Examples of the group other than the hydrogen atom of the substituted hydrogen atom in the "monosubstituted amine group" and the "disubstituted amine group" (that is, the substituent) include an alkyl group and the like.

Examples of the (meth) acrylate having an aliphatic cyclic group include isodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, and the like.

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 the like.

The heterocyclic group in the (meth) acrylate having a heterocyclic group may be any of an aromatic heterocyclic group and an aliphatic heterocyclic group.

Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryl hydrazino morpholine.

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

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

The polymerizable monomer is preferably a group having a relatively large volume in terms of compatibility with the aforementioned (meth)acrylic acid urethane. Examples of such a polymerizable monomer include (meth) acrylate having an aliphatic cyclic group, (meth) acrylate having an aromatic hydrocarbon group, and (meth) acrylate having a heterocyclic group. More preferably, it is an (meth) acrylate having an aliphatic cyclic group.

The polymerizable monomer contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily select.

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

[Photopolymerization initiator]

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

The photopolymerization initiator in the first intermediate layer-forming composition (II-1) is the same as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrary. Ground selection.

In the first intermediate layer-forming composition (II-1), the content of the photopolymerization initiator is preferably 100 parts by mass based on the total content of the (meth)acrylic acid urethane and the polymerizable monomer. 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 Share.

[Resin component other than (meth)acrylic acid urethane]

The first intermediate layer-forming composition (II-1) may contain a resin component other than the above-mentioned (meth)acrylic acid urethane, within a range not impairing the effects of the present invention.

The type of the resin component and the content in the first intermediate layer-forming composition (II-1) are not particularly limited as long as they are appropriately selected depending on the purpose.

[Other additives]

The first intermediate layer-forming composition (II-1) may contain other additives which are not equivalent to any of the above components, within a range not impairing the effects of the present invention.

Examples of the other additives include known additives such as a crosslinking agent, an antistatic agent, an antioxidant, a chain transfer agent, a softener (plasticizer), a filler, a rust preventive, and a colorant (pigment, dye). .

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

Examples of the thiol compound include mercapto mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, and triazine disulfide. Alcohol, triazine trithiol, 1,2,3-propanetrithiol, tetraethylene glycol-bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), season Pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetradecyl acetate, dipentaerythritol hexa(3-mercaptopropionate), tris[(3-mercaptopropoxy)-ethyl]-isotrid Polycyanate, 1,4-bis(3-mercaptobutoxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like.

The other additives contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the first intermediate layer-forming composition (II-1), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

[solvent]

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

<<Method for Producing Composition for First Intermediate Layer Formation>>

The first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) is obtained by blending the components constituting the composition.

The order of addition of the components is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used by mixing a solvent with any of the components other than the solvent to pre-dilute the formulation; or not pre-diluting any of the components other than the solvent, and These formulated ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from a known method such as the following method: a method in which a stirrer or a stirring blade is rotated and mixed; a method in which mixing is performed using a mixer; Ultrasonic method of mixing.

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

◎ Curable resin layer

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

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

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

Further, the haze (h ₁ ) and the haze (h ₂ ) may be the same value or may be different values.

In view of obtaining the effects of the present invention more significantly, the haze (h ₁ ) and (h ₂ ) are preferably as small as possible, preferably 45 or less, and for example, 40 or less, 35 or less, and 30 or less. Any of them.

In addition, the lower limit of the haze (h ₁ ) and (h ₂ ) is not particularly limited, and is usually preferably 10 in terms of easily forming a first protective film having high transparency.

In the present invention, the haze (h ₀₁ ) of the surface of the curable resin layer (curable resin film) of the first aspect before curing of the cured product (α) and the curing of the cured product (β) The haze (h ₀₂ ) of the surface of the curable resin layer (curable resin film) of the second embodiment is not particularly limited, but is preferably as small as possible, preferably 50 or less, more preferably 45 or less. Any one of 40 or less, 35 or less, and 30 or less may be used.

In addition, the lower limit of the haze (h ₀₁ ) and (h ₀₂ ) is not particularly limited, and is usually preferably 10 in terms of easily forming a first protective film having high transparency.

In the present invention, the haze (h ₀₁ ), (h ₀₂ ), (h ₁ ), and (h ₂ ) may be in accordance with JIS (Japanese Industrial Standards) K7136 (2000) by using a haze meter. Determination.

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

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

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

Among the components contained in the composition for forming a curable resin layer, in particular, the particulate component such as the filler (D) described later tends to cause white turbidity of the cured product. In the present invention, by reducing the amount of the particulate component such as the filler (D) or selecting the appropriate one as the particulate component, the haze (h ₁ ) and (h ₂ ) can be reduced, and transparency can be obtained. Cured product.

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

○Hot curable resin layer

As a preferable thermosetting resin layer, the polymer component (A) and the thermosetting component (B) are mentioned, for example. Polymer component (A) is considered A component formed by a polymerization reaction of a polymerizable compound. Further, the thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction with heat as a trigger for the reaction. Further, in the present invention, a polycondensation reaction is also included in the polymerization reaction.

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

The thickness of the aforementioned thermosetting resin layer is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, still more preferably from 5 μm to 50 μm. When the thickness of the thermosetting resin layer is at least the above lower limit value, a first protective film having a higher protective ability can be formed. In addition, the thickness of the thermosetting resin layer is equal to or less than the above upper limit value, and the excess thickness is suppressed.

The term "thickness of the thermosetting resin layer" as used herein means the thickness of the entire thermosetting resin layer. For example, the thickness of the thermosetting resin layer composed of a plurality of layers means all of the thermosetting resin layers. The total thickness of the layers.

The curing condition when the thermosetting resin layer is adhered to the bump forming surface of the semiconductor wafer and cured to form the first protective film is a degree of curing that is sufficient for the first protective film to sufficiently exhibit its function. In addition, it is not particularly limited, and may be appropriately selected depending on the type of the thermosetting resin layer.

For example, the heating temperature at the time of curing the thermosetting resin layer is preferably from 100 ° C to 200 ° C, more preferably from 110 ° C to 180 ° C, still more preferably from 120 ° C to 170 ° C. Further, the heating time in the above curing is preferably from 0.5 to 5 hours, more preferably from 0.5 to 3 hours, still more preferably from 1 hour to 2 hours.

<<Composition for forming a thermosetting resin layer>>

The thermosetting resin layer can be formed using a composition for forming a thermosetting resin layer containing the constituent material. For example, a composition for forming a thermosetting resin layer is applied to a surface to be formed of a thermosetting resin layer, and if necessary, drying can be performed to form a thermosetting resin layer at a target portion. The ratio of the content of the components which are not vaporized at normal temperature in the thermosetting resin layer-forming composition is usually the same as the ratio of the components of the thermosetting resin layer. The term "normal temperature" as used herein is as explained above.

The coating of the thermosetting resin layer-forming composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll type. Coating machine, roll coater, curtain coater, pattern coater, blade coater, screen coater, bar coater, staple coater, etc. method.

The drying condition of the thermosetting resin layer-forming composition is not particularly limited. When the thermosetting resin layer-forming composition contains a solvent to be described later, it is preferably heated and dried. 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 the conditions.

<Resin layer forming composition (III-1)>

The thermosetting resin layer-forming composition (III-1) containing the polymer component (A) and the thermosetting component (B) is exemplified as the thermosetting resin layer-forming composition (in the present specification, The time is simply referred to as "the composition for forming a resin layer (III-1)").

[Polymer component (A)]

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

The polymer component (A) contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, the Combinations and ratios can be arbitrarily selected.

Examples of the polymer component (A) include an acrylic resin (a resin having a (meth)acrylonitrile group), a polyester, and a urethane resin (a resin having a urethane bond). An urethane urethane resin, an oxime ketone resin (a resin having a decane bond), a rubber resin (a resin having a rubber structure), a phenoxy resin, a thermosetting polyimide, etc., preferably Acrylic resin.

The acrylic resin as the polymer component (A) includes a known acrylic polymer.

The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (chronological 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-described upper limit, the thermosetting resin layer easily follows the uneven surface of the adherend, and further suppresses generation of voids between the adherend and the thermosetting resin layer.

The glass transition temperature (Tg) of the acrylic resin is preferably from -60 ° C to 70 ° C, more preferably from -30 ° C to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, the adhesion 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 less than the above upper limit, the adhesion between the thermosetting resin layer and the first protective film and the adherend is improved.

Examples of the acrylic resin include a polymer of one or two or more (meth) acrylates selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxyl. A copolymer of two or more kinds of monomers such as methacrylamide or the like.

Examples of the (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, dibutyl (meth)acrylate, (methyl) Tert-butyl acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate , n-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (methyl) ) lauryl acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), ( Pentadecyl methyl methacrylate, cetyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate An alkyl (meth)acrylate having a chain structure of an alkyl group having an alkyl group having a carbon number of from 1 to 18, such as an ester (stearyl (meth) acrylate); isodecyl (meth)acrylate; (cyclo) (meth) acrylate such as dicyclopentanyl methacrylate; aralkyl (meth) acrylate such as benzyl (meth) acrylate; dicyclopentenyl (meth) acrylate; (meth)acrylic acid (meth)acrylic acid cycloalkyloxyalkyl ester such as cyclopentenyloxyethyl ester; (meth) acrylonitrile imine; glycidyl group-containing (meth) acrylate such as glycidyl (meth)acrylate ; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-(meth) acrylate a hydroxyl group-containing (meth) acrylate such as hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; N-methylaminoethyl (meth)acrylate; A (meth) acrylate containing a substituted amino group or the like. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of an amine group are substituted with a group other than a hydrogen atom.

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

The monomers constituting the acrylic resin may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

The acrylic resin may have a functional group which may be bonded to another compound such as a vinyl group, a (meth) acrylonitrile group, an amine group, a hydroxyl group, a carboxyl group or an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) to be described later, or may be directly bonded to another compound without passing through the crosslinking agent (F). When the acrylic resin is bonded to another compound by the above functional group, 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, and the thermoplastic resin and acrylic acid may be used. Resin and use. By using the thermoplastic resin, the peeling property 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. A gap or the like is formed between the layers.

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

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

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

The thermoplastic resin contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, the combinations and ratios thereof Can be arbitrarily chosen.

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

The polymer component (A) sometimes also corresponds to the thermosetting component (B). This hair In the case where the resin layer-forming composition (III-1) contains a component corresponding to both the polymer component (A) and the thermosetting component (B), it is considered to be a resin layer-forming composition. (III-1) contains a polymer component (A) and a thermosetting component (B).

[Thermal curable component (B)]

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

The thermosetting component (B) contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, these are The combinations and ratios can be arbitrarily selected.

Examples of the thermosetting component (B) include an epoxy-based thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, an anthrone resin, and the like, and preferably a ring. Oxygen-based thermosetting resin.

(epoxy thermosetting resin)

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

The epoxy-based thermosetting resin contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, these types may be used. The combinations and ratios can be arbitrarily selected.

. Epoxy resin (B1)

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

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. 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 a compound obtained by converting a part of an epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth)acrylic acid or a derivative thereof.

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

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl, 2-propenyl (allyl), (meth)acrylonitrile, and (meth)acryl oxime. An amine group or the like is preferably an acrylonitrile group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, and is preferably from 300 to 30,000 in terms of curability of the thermosetting resin layer and strength and heat resistance of the first protective film after curing. More preferably from 400 to 10,000, and particularly preferably from 500 to 3,000.

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

The epoxy resin (B1) may be used singly or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

. Heat curing agent (B2)

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

The thermosetting agent (B2) may, for example, be a compound having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a group in which an acid group is anhydride-formed. Preferably, the phenolic hydroxyl group, the amine group or the acid group is anhydride-treated. The group formed is more preferably a phenolic hydroxyl group or an amine group.

In the thermosetting agent (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a dicyclopentadiene type phenol resin, and an aralkyl type. Phenolic resin, etc.

In the thermosetting agent (B2), examples of the amine-based curing agent having an amine group include dicyanodicimide (hereinafter sometimes abbreviated as "DICY").

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

The thermosetting agent (B2) having an unsaturated hydrocarbon group may, for example, be a compound in which a part of a hydroxyl group 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 a phenol resin. a compound formed on an aromatic ring.

The aforementioned unsaturated hydrocarbon group in the heat curing agent (B2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used 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 supporting sheet. The transfer temperature is high.

In the thermosetting agent (B2), for example, the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene type phenol resin, or an aralkyl type phenol resin preferably has a number average molecular weight of 300 to 30,000, more preferably Good for 400 to 10,000, especially for 500 to 3000.

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

The heat curing agent (B2) may be used singly or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected. Choose.

In the resin layer-forming composition (III-1) and the thermosetting resin layer, the content of the thermosetting agent (B2) is preferably from 0.1 part by mass to 500% by mass based on 100 parts by mass of the epoxy resin (B1). The portion is more preferably from 1 part by mass to 200 parts by mass, and may be, for example, from 5 parts by mass to 100 parts by mass, from 10 parts by mass to 80 parts by mass, and from 15 parts by mass to 60 parts by mass. When the content of the heat curing agent (B2) is at least the above lower limit value, curing of the thermosetting resin layer is more easily performed. In addition, when the content of the thermosetting agent (B2) is at most the above upper limit value, the moisture absorption rate of the thermosetting resin layer is lowered, and the reliability of the package obtained by using the first protective film forming sheet is further improved.

In the resin layer-forming composition (III-1) and the thermosetting resin layer, the content of the thermosetting component (B) is 100 parts by mass based on the content of the polymer component (A) (for example, epoxy resin (B1) And the total content of the heat curing agent (B2) is preferably from 50 parts by mass to 1000 parts by mass, more preferably from 100 parts by mass to 900 parts by mass, even more preferably from 150 parts by mass to 800 parts by mass, for example, 200 parts by mass 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 content of the thermosetting component (B) is in such a range, the adhesion 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 resin layer-forming composition (III-1) and the thermosetting resin layer may also be used. Contains a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the resin layer-forming composition (III-1).

Preferred examples of the curing accelerator (C) include tri-ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. Tertiary amine; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl An imidazole such as a 5-hydroxymethylimidazole (an imidazole in which one or more hydrogen atoms are substituted by a group other than a hydrogen atom); an organic phosphine such as tributylphosphine, diphenylphosphine or triphenylphosphine (more than one) a phosphine in which a hydrogen atom is substituted with an organic group; a tetraphenylborate such as tetraphenylphosphonium tetraphenylborate or triphenylphosphine tetraphenylborate; and the like.

The curing accelerator (C) contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, the Combinations and ratios can be arbitrarily selected.

In the case of using the curing accelerator (C), in the resin layer-forming composition (III-1) and the thermosetting resin layer, the curing accelerator is contained in an amount of 100 parts by mass based on the content of the thermosetting component (B). The content of (C) is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass. When the content of the curing accelerator (C) is at least the above lower limit value, the effect by using the curing accelerator (C) can be more remarkably obtained. In addition, when the content of the curing accelerator (C) is equal to or less than the above upper limit, for example, the curing accelerator (C) having high polarity is suppressed in a thermosetting tree under high temperature and high humidity conditions. The efficiency of segregation in the lipid layer to the interface side with the adherend is improved, and the reliability of the package obtained by using the first protective film forming sheet is further improved.

[Filling material (D)]

The resin layer-forming composition (III-1) and the thermosetting resin layer may further contain a filler (D). The thermosetting resin layer contains the filler (D), and the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin layer is easily adjusted. Further, 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 first protective film forming sheet is further improved. Further, by including the filler (D) in the thermosetting resin layer, the moisture absorption rate of the first protective film can be lowered 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 cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, red dan, tantalum carbide, and boron nitride; and the inorganic fillers are spherical. Beads; surface modifiers of such inorganic fillers; single crystal fibers of such inorganic fillers; glass fibers, and the like.

Among these, the inorganic filler is preferably cerium oxide or aluminum oxide.

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 less than the above upper limit value, the haze (h ₁ ) of 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 of the average particle diameter of the filler (D) is not particularly limited, but is usually preferably 10 nm.

In addition, the "average particle diameter" in the present specification means a particle diameter (D ₅₀ ) of 50% of the integrated value in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified. value.

The filler (D) contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, the combination may be two or more. And the ratio can be arbitrarily selected.

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

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

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

When the resin layer-forming composition (III-1) and the thermosetting resin layer contain the filler (D), the resin layer-forming composition (III-1) and the thermosetting resin layer have an average particle size. The ratio of the content of the filler (D) having a diameter of 250 nm or less to the total content of the filler (D) (sometimes referred to as "proportion (w1)" in the present specification) is preferably from 35% by mass to 100% by mass. More preferably, it is 45% by mass to 100% by mass, and for example, it may be 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. By the above ratio (w1) being such a range, the haze (h ₁ ) of the surface of the cured product (α) becomes smaller, and the transparency of the first protective film becomes higher.

Further, in the case where the above ratio (w1) is in the above range, the average particle diameter of the filler (D) having an average particle diameter of more than 250 nm is preferable in that the effect of the present invention is more remarkably obtained. It is 1200 nm or less, more preferably 1050 nm or less.

In the case of using the filler (D), in the resin layer-forming composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the thermosetting resin) The content of the filler (D) of the layer is preferably from 5% by mass to 80% by mass, more preferably from 7% by mass to 60% by mass, and for example, may also be from 7% by mass to 50% by mass, and from 7% by mass to 40% by mass. % by mass and any of 7 mass% to 30 mass%. By the content of the filler (D) being such a range, the adjustment of the above thermal expansion coefficient becomes easier.

[coupler (E)]

The resin layer-forming composition (III-1) and the thermosetting resin layer may further 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 of the thermosetting resin layer to the adherend and the adhesion can be improved. Moreover, the first protective film obtained by curing the thermosetting resin layer by using the coupling agent (E) improves the water resistance without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group reactive with a functional group possessed by the polymer component (A) or the thermosetting component (B), and more preferably a decane coupling agent.

Preferred examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl III. Ethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propylmethyldi Ethoxy decane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethoxy Base decane, 3- Mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, methyltriethoxydecane, vinyltrimethoxydecane, Vinyl triethoxy decane, imidazolium, and the like.

The coupler (E) contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, the combination may be two or more. And the ratio can be arbitrarily selected.

In the case of using the coupling agent (E), 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. The content of the coupling agent (E) is preferably from 0.03 parts by mass to 20 parts by mass, more preferably from 0.05 parts by mass to 10 parts by mass, even more preferably from 0.1 part by mass to 5 parts by mass, per 100 parts by mass. When the content of the coupling agent (E) is at least the above lower limit value, the dispersibility of the filler (D) in the resin or the adhesion of the thermosetting resin layer to the adherend is more remarkably obtained. Improve the efficacy brought about by the use of the coupling agent (E). In addition, when the content of the coupling agent (E) is at most the above upper limit value, generation of outgas is further suppressed.

[crosslinking agent (F)]

When a functional group such as a vinyl group, a (meth) acrylonitrile group, an amine group, a hydroxyl group, a carboxyl group or an isocyanate group which can be bonded to another compound such as the above acrylic resin is used as the polymer component (A), The resin layer-forming composition (III-1) and the thermosetting resin layer may further contain a crosslinking agent. (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (A) with another compound, and crosslinking is carried out in such a manner that the initial stage of the thermosetting resin layer can be adjusted. Then force and cohesion.

Examples of the crosslinking agent (F) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking. A reagent (a cross-linking agent having an aziridine group) or the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"); a trimer such as an aromatic polyvalent isocyanate compound, an isocyanurate or an adduct, a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound or the like with a polyol compound, and the like . The term "adduct" means a low content of the above aromatic polyvalent isocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. A reactant of a compound of molecularly active hydrogen. Examples of the adducts include a xylene diisocyanate adduct of trimethylolpropane described later. Further, the "terminal isocyanate urethane prepolymer" is as described above.

More specifically, the organic polyvalent isocyanate compound may, for example, be 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; addition of toluene diisocyanate to six or all of the hydroxyl groups of polyols such as trimethylolpropane A compound obtained by any one or two or more kinds of methyl diisocyanate and xylene diisocyanate; an isocyanuric acid diisocyanate or the like.

Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyguanamine), and trimethylolpropane-tri-β-nitrogen. Propidyl propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxylamine) Based on melamine and the like.

In the case where an organic polyvalent isocyanate compound is used as the crosslinking agent (F), as the polymer component (A), a hydroxyl group-containing polymer is preferably used. When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, it can be reacted in the thermosetting resin layer by reacting the crosslinking agent (F) with the polymer component (A). It is easy to introduce a crosslinked structure.

The resin layer-forming composition (III-1) and the thermosetting resin layer are contained The crosslinking agent (F) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the case of using the crosslinking agent (F), in the resin layer-forming composition (III-1), the content of the crosslinking agent (F) is preferably 100 parts by mass based on the content of the polymer component (A). It is from 0.01 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass, even more preferably from 0.5 part by mass to 5 parts by mass. When the content of the crosslinking agent (F) is at least the above lower limit value, the effect by the use of the crosslinking agent (F) is more remarkably obtained. In addition, when the content of the crosslinking agent (F) is at most the above upper limit value, excessive use of the crosslinking agent (F) is suppressed.

[Energy Curing Resin (G)]

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

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

The energy ray-curable compound may, for example, be a compound having at least one polymerizable double bond in the molecule, and is preferably an acrylate-based compound having a (meth) acrylonitrile group.

Examples of the acrylate-based compound include a trimethylol group. Propane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate a chain-like aliphatic skeleton such as ester, dipentaerythritol hexa(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate or the like ( (meth) acrylate; (meth) acrylate containing a cyclic aliphatic skeleton such as dicyclopentanyl (meth) acrylate; and a polyalkylene glycol such as polyethylene glycol di(meth) acrylate ( Methyl) acrylate; oligoester (meth) acrylate; (meth) acrylate urethane oligomer; epoxy modified (meth) acrylate; the aforementioned polyalkylene glycol (A) Polyether (meth) acrylate other than acrylate; itaconic acid oligomer and the like.

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

The energy ray-curable compound to be used for the polymerization may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

The energy ray-curable resin (G) contained in the resin layer-forming composition (III-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be Choose arbitrarily.

In the case of using the energy ray curable resin (G), in the form of a resin layer In the composition (III-1), the content of the energy ray-curable resin (G) is preferably from 1% by mass to 95% by mass, more preferably from 5% by mass to 90% by mass, even more preferably from 10% by mass to 85 mass%.

[Photopolymerization initiator (H)]

In the case where the energy ray-curable resin (G) is contained in the resin layer-forming composition (III-1), the photopolymerization initiator (G) may be efficiently polymerized, and a photopolymerization initiator may be contained. (H).

The photopolymerization initiator (H) in the resin layer-forming composition (III-1) is the same as the photopolymerization initiator in the first binder composition (I-1).

The photopolymerization initiator (H) contained in the resin layer-forming composition (III-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be Choose arbitrarily.

In the case of using the photopolymerization initiator (H), in the resin layer-forming composition (III-1), the photopolymerization initiator (100 parts by mass) based on the content of the energy ray-curable resin (G) The content of H) is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, still more preferably from 2 parts by mass to 5 parts by mass.

[General Additives (I)]

The resin layer-forming composition (III-1) and the thermosetting resin layer may contain a general-purpose additive (I) within a range not impairing the effects of the present invention.

The general-purpose additive (I) can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye, pigment). , gettering agent, etc.

The general additive (I) to be contained in the resin layer-forming composition (III-1) and the thermosetting resin layer may be one type or two or more types. When two or more types are used, the combination may be two or more. And the ratio can be arbitrarily selected.

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

[solvent]

The resin layer-forming composition (III-1) preferably further contains a solvent. The composition (III-1) for forming a resin layer containing a solvent is excellent in handleability.

The solvent is not particularly limited, and examples thereof include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butyl. An alcohol such as an alcohol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; a decylamine such as dimethylformamide or N-methylpyrrolidone (a compound having a guanamine bond); .

The solvent contained in the resin layer-forming composition (III-1) may be only one Alternatively, two or more kinds may be used, and in the case of two or more types, the combinations and ratios may be arbitrarily selected.

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

<<Method for Producing Composition for Forming Thermosetting Resin Layer>>

The composition for forming a thermosetting resin layer such as the resin layer-forming composition (III-1) can be obtained by blending the components constituting the composition.

The order of addition of the components is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used by mixing a solvent with any of the components other than the solvent to pre-dilute the formulation; or not pre-diluting any of the components other than the solvent, and These formulated ingredients are mixed.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from a known method such as a method in which a stirrer or a stirring blade is rotated and mixed; a method of mixing using a mixer; and applying ultrasonic waves The method of mixing, etc.

The temperature and time during the addition and mixing of the respective components are not particularly limited as long as the respective components do not deteriorate, and the temperature is preferably from 15 ° C to 30 ° C as long as it is appropriately adjusted.

○ Energy line curable resin layer

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

The energy ray curable component (a) is preferably uncured, and preferably has adhesiveness, more preferably uncured and adhesive. Here, "energy line" and "energy line curability" are as described above.

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

The thickness of the energy ray-curable resin layer is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, still more preferably from 5 μm to 50 μm. When the thickness of the energy ray-curable resin layer is at least the above lower limit value, a first protective film having higher protection ability can be formed. In addition, the thickness of the energy ray-curable resin layer is equal to or less than the above upper limit value, and the excess thickness is suppressed.

Here, the "thickness of the energy ray-curable resin layer" means 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 means the energy ray curability. The total thickness of all layers of the resin layer.

The curing condition when the energy ray-curable resin layer is adhered to the bump forming surface of the semiconductor wafer and cured to form the first protective film is cured as long as the first protective film sufficiently exhibits its function. The degree is not particularly limited, and may be appropriately selected depending on the type of the thermosetting resin layer.

For example, the illuminance of the energy ray at the time of curing the energy ray-curable resin layer is preferably from 180 mW/cm ² to 280 mW/cm ² . Further, the amount of light of the energy ray at the time of curing is preferably from 450 mW/cm ² to 1000 mJ/cm ² .

<<Energy line curable resin layer forming composition>>

The energy ray-curable resin layer can be formed using a composition for forming an energy ray-curable resin layer containing the constituent material. For example, a composition for forming an energy ray-curable resin layer is applied to a surface to be formed of the energy ray-curable resin layer, and if necessary, drying is performed to form an energy ray-curable resin layer at a target portion. The ratio of the content of the components which are not vaporized at normal temperature in the energy ray-curable resin layer-forming composition is usually the same as the ratio of the components of the energy ray-curable resin layer. The term "normal temperature" as used herein is as explained above.

The application of the energy ray-curable resin layer-forming composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll. Coating machine, roll coater, curtain coater, pattern coater, blade coater, screen coater, bar coater, staple coater, etc. The method.

The drying condition of the energy ray-curable resin layer-forming composition is not particularly limited, and the energy ray-curable resin layer-forming composition contains the following. In the case of a solvent, it is preferred to carry out heat drying. 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.

<Resin layer forming composition (IV-1)>

For example, the energy ray-curable resin layer-forming composition (IV-1) containing the energy ray-curable component (a) may be used. It is "the composition (IV-1) for resin layer formation").

[Energy curing component (a)]

The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and is a component for imparting film-forming property or flexibility 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 having a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray-curable group and having a molecular weight of 100 to 80,000. (a2). The polymer (a1) may be obtained by crosslinking at least a part thereof with a crosslinking agent or may be not crosslinked.

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

As the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, for example, it is possible to An acrylic polymer (a11) having a functional group reactive with a group of another compound, and an energy ray-curable compound having an energy ray-curable group such as a group reactive with the functional group and an energy ray-curable double bond ( A12) An acrylic resin (a1-1) obtained by polymerization.

Examples of the functional group reactive with a group of another compound include a hydroxyl group, a carboxyl group, an amine group, and a substituted amine group (one or two hydrogen atoms of the amine group are substituted by a group other than a hydrogen atom) a group), an epoxy group, and the like. Among them, in order to prevent corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the functional group is preferably a group other than a carboxyl group.

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

. Acrylic polymer having functional groups (a11)

The acrylic polymer (a11) having the functional group may, for example, be copolymerized with an acrylic monomer having the functional group and an acrylic monomer having no functional group, or may be A monomer other than the monomer other than the acrylic monomer (non-acrylic monomer) is further copolymerized.

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

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylate; vinyl alcohol, A non-(meth)acrylic unsaturated alcohol such as allyl alcohol (an unsaturated alcohol having no (meth) acrylonitrile skeleton) or the like.

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; fumaric acid and itaconic acid; An ethylenically unsaturated dicarboxylic acid such as maleic acid or citraconic acid (dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; 2-carboxyethyl methacrylate; a carboxyalkyl acrylate or the like.

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

The acrylic monomer having the functional group of the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

Examples of the acrylic monomer having no such functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (methyl) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate , isodecyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate (lauryl (meth) acrylate), ( Tridecyl methyl methacrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecane (meth) acrylate Alkyl ester (alkyl palmitate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate) The base carbon number is 1 to 18 (Meth) acrylic acid alkyl ester-like structure.

Further, examples of the acrylic monomer having no such functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxylated (meth)acrylate. An alkoxyalkyl group-containing (meth) acrylate such as an ester or ethoxyethyl (meth) acrylate; or an aromatic group such as an aryl (meth) acrylate such as phenyl (meth) acrylate (meth) acrylate; non-crosslinkable (meth) acrylamide and its derivatives; N,N-dimethylaminoethyl (meth) acrylate, N, N (meth) acrylate a non-crosslinkable (meth) acrylate having a tertiary amino group such as dimethylaminopropyl propyl ester Wait.

The acrylic monomer constituting the acrylic polymer (a11) having no such functional group may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily select.

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

The non-acrylic monomers constituting the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural unit constituting the polymer is preferably 0.1% by mass. It is 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 3% by mass to 30% by mass. 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 is obtained by the above-mentioned ratio in the above range. The content of the base can easily adjust the degree of curing of the first protective film to a preferred range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the resin layer-forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably from 1 to 40, more preferably from 2 to 30, still more preferably from 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 an isocyanate group, an epoxy group, and a carboxyl group as a functional group capable of reacting with the acrylic polymer (a11). The group reactive group, more preferably has an isocyanate group as the aforementioned group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the above group, 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 one to five energy-ray-curable groups in one molecule, and more preferably has one to two energy-ray-curable groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and methacryl oxime isocyanate. , allyl isocyanate, 1,1-(bispropenyloxymethyl)ethyl isocyanate; propylene decyl monoisocyanate obtained by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate a compound; a diisocyanate compound or a polyisocyanate compound, a polyol compound, and (meth) An acrylonitrile monoisocyanate compound obtained by the reaction of hydroxyethyl acrylate.

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

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, the combinations and ratios 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 from 20 mol% to 120 mol%, more preferably from 35 mol% to 100 mol%, still more preferably from 50 mol% to 100 mol%. By the ratio of the above content being such a range, the adhesion force of the first protective film after curing becomes larger. In the case where the energy ray-curable compound (a12) is a monofunctional (one group having one group in one molecule) compound, the upper limit of the ratio of the content is 100 mol%, and the energy ray curability is When the compound (a12) is a compound having a polyfunctionality (having two or more of the above groups in one molecule), the upper limit of the ratio of the above content may exceed 100 mol%.

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

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

In the case where the polymer (a1) is at least partially crosslinked by a crosslinking agent, the polymer (a1) may not be equivalent to those constituting the acrylic polymer (a11). The monomer having any of the above monomers and having a group reactive with the crosslinking agent is polymerized, and is crosslinked on a group reactive with the crosslinking agent, or may be derived from the aforementioned energy ray curing. The compound (a12) is crosslinked with a group reactive with the aforementioned functional group.

The polymer (a1) to be contained in the resin layer-forming composition (IV-1) and the energy ray-curable resin layer may be one type or two or more types. When two or more types are used, these The combinations and ratios can be arbitrarily selected.

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

The energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of from 100 to 80,000 is a group containing an energy ray-curable double bond, and preferably, it is a methyl group. ) acryl oxime, vinyl, and the like.

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. .

In the compound (a2), the low molecular weight compound having an energy ray-curable group may, for example, be a polyfunctional monomer or oligomer, and is preferably an acrylate compound having a (meth) acrylonitrile group.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylate. Bisphenol bis(meth)acrylate, 2,2-bis[4-((meth)propenyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(A) Acrylate, 2,2-bis[4-((meth)propenyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl)propene oxime) Ethyloxy)phenyl]anthracene, 2,2-bis[4-((meth)propenyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(a) Acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane Difunctional (methyl) such as neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis(methyl)propenyloxypropane Acrylate; tris(2-(methyl)propenyloxyethyl)isocyanate, ε-caprolactone modified tris-(2-(methyl)propenyloxyethyl) Cyanuric acid ester, 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 A polyfunctional (meth) acrylate oligomer such as a polyfunctional (meth) acrylate or a (meth) acrylate urethane oligomer.

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

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

The compound (a2) to be contained in the resin layer-forming composition (IV-1) and the energy ray-curable resin layer may be one type or two or more types. When two or more types are used, the Combinations and ratios can be arbitrarily selected.

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

When the resin layer-forming composition (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 curing. A base based polymer (b).

The polymer (b) may be at least partially crosslinked by a crosslinking agent or may be uncrosslinked.

Examples of the polymer (b) having no energy ray-curable group include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, and an urethane urethane resin. Wait.

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

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include an alkyl (meth)acrylate, a (meth)acrylate having a cyclic skeleton, and a glycidyl group (A). Acrylate, hydroxyl group-containing (meth) acrylate, substituted amino group-containing (meth) acrylate, and the like. The "substituted amine group" herein is as described above.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl acrylate, (meth) acrylate Butyl ester, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (methyl) ) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Anthracene ester, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, (meth)acrylic acid Tetradecyl ester (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), (methyl) a heptadecyl acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc., which constitutes an alkyl ester having an alkyl group having a chain structure of 1 to 18 (A) Alkyl acrylate.

Examples of the (meth) acrylate having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isodecyl (meth)acrylate and dicyclopentanyl (meth)acrylate; Arylalkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth) acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate (meth)acrylic cycloalkenyloxyalkyl ester and the like.

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

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

Examples of the (meth) acrylate containing a substituted amino group include N-methylaminoethyl (meth) acrylate and the like.

The non-acrylic monomer constituting the acrylic polymer (b-1) may, for example, be an olefin such as ethylene or decene; vinyl acetate; styrene or the like.

The polymer (b) which does not have the energy ray-curable group which is crosslinked by at least a part of the crosslinking agent, for example, may be a reaction between a reactive functional group and a crosslinking agent in the polymer (b). .

The reactive functional group is not particularly limited as long as it is appropriately selected depending on the type of the crosslinking agent and the like. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group may, for example, be a hydroxyl group, a carboxyl group or an amine group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In the case where the crosslinking agent is an epoxy compound, the reactive functional group may, for example, be a carboxyl group, an amine group or a guanamine group, and among these, it is preferred to have high reactivity with an epoxy group. carboxyl. Among them, in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

As having the aforementioned reactive functional group and having no energy ray curability The polymer (b) based on the base may, for example, be obtained by polymerizing at least a monomer having the aforementioned reactive functional group. In the case of the acrylic polymer (b-1), the acrylic functional monomer exemplified as the monomer constituting the acrylic polymer (b-1) and the reactive functional group are used. Either or both of the non-acrylic monomers may be used. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and the above-mentioned acrylic acid may be mentioned. A monomer obtained by polymerizing a monomer or a non-acrylic monomer in which one or two or more hydrogen atoms are substituted with the aforementioned reactive functional group.

In the above polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group is relatively larger than the total amount of the structural unit constituting the polymer. It is preferably from 1% by mass to 20% by mass, more preferably from 2% by mass to 10% by mass. By the above ratio being such a range, in the above polymer (b), the degree of crosslinking becomes a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to the viewpoint that the film forming property of the resin layer-forming composition (IV-1) is further improved. 2000000, more preferably 100000 to 1.500000. Here, the "weight average molecular weight" is as described above.

The polymer (b) having no energy ray-curable group contained in the resin layer-forming composition (IV-1) and the energy ray-curable resin layer may be used alone or in combination of two or more kinds. In the above case, the combinations and ratios can be arbitrarily selected.

The composition (IV-1) for forming a resin layer includes a composition containing either or both of the polymer (a1) and the compound (a2). In the case where the resin layer-forming composition (IV-1) contains the compound (a2), it is preferred to further contain the polymer (b) having no energy ray-curable group, and in this case, It is preferable to further contain the aforementioned (a1). In addition, the resin layer-forming composition (IV-1) may not contain the compound (a2), and may contain the polymer (a1) and the polymer (b) having no energy ray-curable group.

When the resin layer-forming composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the resin layer-forming composition In the above (IV-1), the content of the compound (a2) is preferably 10 parts by mass based on 100 parts by mass of the total 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 resin layer-forming composition (IV-1), the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group is relative to the total content of components other than the solvent. Ratio (ie, energy line curing) The energy-line curable component (a) of the resin layer and the total content of the polymer (b) having no energy ray-curable group are preferably from 5% by mass to 90% by mass, more preferably from 10% by mass to 80% by weight. The mass% is particularly preferably from 20% by mass to 70% by mass. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray curability of the energy ray-curable resin layer is further improved.

The resin layer-forming composition (IV-1) may contain, in addition to the energy ray-curable component, a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, and a general-purpose additive, depending on the purpose. One or more of the group consisting of. For example, by using the resin layer-forming composition (IV-1) containing the energy ray-curable component and the thermosetting component, the energy ray-curable resin layer formed is improved in adhesion to the adherend by heating. The strength of the first protective film formed of the energy ray-curable resin layer is also improved.

The thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, and the general-purpose additive in the resin layer-forming composition (IV-1) are each a resin layer-forming composition ( 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) in III-1) are the same.

In the resin layer-forming composition (IV-1), 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. , use both together In the case of the above, the combinations and ratios can be arbitrarily selected.

The content of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, and the general-purpose additive in the resin layer-forming composition (IV-1) may be appropriately adjusted according to the purpose, and may not be appropriately adjusted. Specially limited.

Since the resin layer-forming composition (IV-1) is improved in handleability by dilution, it is preferred to further contain a solvent.

The solvent contained in the resin layer-forming composition (III-1) is the same as the solvent in the resin layer-forming composition (III-1).

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

<<Method for Producing Composition for Energy-Line Curable Resin Layer Formation>>

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

The order of addition of the components is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used by mixing a solvent with any of the components other than the solvent to pre-dilute the formulation; or not pre-diluting any of the components other than the solvent, and These formulated 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: rotating the agitator or the stirring blade A method of mixing by mixing; a method of mixing using a mixer; a method of applying ultrasonic waves for mixing, and the like.

The temperature and time during the addition and mixing of the respective components are not particularly limited as long as the respective components do not deteriorate, and the temperature is preferably from 15 ° C to 30 ° C as long as it is appropriately adjusted.

◇First protective film forming sheet manufacturing method

The first protective film forming sheet can be produced by sequentially laminating the above layers in a corresponding positional relationship. The formation method of each layer is as described above.

For example, in the case of manufacturing the first support sheet, when the first adhesive layer or the first intermediate layer is laminated on the first substrate, the first adhesive composition or the first coating is applied on the first substrate. The intermediate layer forming composition may be dried or irradiated with an energy ray as needed, and a first adhesive layer or a first intermediate layer may be laminated.

On the other hand, for example, when a curable resin layer is further laminated on the first adhesive layer which has been laminated on the first substrate, the thermosetting resin layer forming composition can be applied onto the first adhesive layer. Or a composition for forming an energy ray-curable resin layer, and directly forming a curable resin layer. Similarly, when the first adhesive layer is further laminated on the first intermediate layer which has been laminated on the first substrate, the first adhesive composition may be applied on the first intermediate layer to directly form the first adhesive. Agent layer. Thus, in the case of using any composition to form a laminated structure of two consecutive layers, it can be composed of the foregoing A layer is further coated on the layer formed by the object to form a layer. Preferably, the layer of the back layer in the two layers is formed in advance on the other release film by using the composition, and the exposed side of the formed layer on the side opposite to the side of the release film is formed and formed. The exposed faces of the remaining layers are bonded to each other, thereby forming a laminated structure of two consecutive layers. In this case, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as needed after forming a laminated structure.

For example, a first protective film forming sheet in which a first adhesive layer is laminated on a first substrate and a curable resin layer is laminated on the first adhesive layer (the first support sheet is a 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 onto the first substrate, and dried as needed, thereby preliminarily laminating on the first substrate. The first adhesive layer is coated with a thermosetting resin layer-forming composition or an energy-ray-curable resin layer-forming composition on the release film, and if necessary, dried to form a curable resin layer on the release film. The exposed surface of the curable resin layer is bonded to the exposed surface of the first adhesive layer 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, when a first intermediate layer is laminated on a first substrate, and a first support sheet is formed by laminating a first adhesive layer on the first intermediate layer, a first coating is applied to the first substrate. The intermediate layer forming composition is dried or irradiated with an energy ray as needed, thereby preliminarily laminating the first intermediate layer on the first substrate, and applying the first adhesive composition on the release film, Drying is required to form a first adhesive layer on the release film, and the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer laminated on the first substrate. An adhesive layer is laminated on the first intermediate layer, whereby the first support sheet can be obtained. 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 applied to the release film, and if necessary, drying is performed to form a curable resin on the release film in advance. The layer is formed by bonding the exposed surface of the curable resin layer to the exposed surface of the first adhesive layer laminated on the first intermediate layer, and laminating the curable resin layer on the first adhesive layer. The sheet for forming a first protective film.

Furthermore, in the case where the first adhesive layer or the first intermediate layer is laminated on the first substrate, the first adhesive composition or the first intermediate layer may be formed on the first substrate instead of the above. By using the composition method, the first adhesive composition or the first intermediate layer forming composition is applied onto the release film, and if necessary, drying or irradiating the energy ray, thereby preliminarily forming the first adhesive layer on the release film. Or the first intermediate layer, the exposed surface of the layers is bonded to one surface of the first substrate, thereby laminating the first adhesive layer or the first intermediate layer on the first substrate.

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

In this manner, the layer other than the first base material constituting the first protective film forming sheet can be formed on the surface of the target layer by being formed on the release film in advance. In the method of laminating, the first protective film-forming sheet can be produced by appropriately selecting a layer using such a step as needed.

In addition, the first protective film forming sheet is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a curable resin layer) on the opposite side of the first support sheet. Therefore, the composition for forming the outermost layer is formed by applying a composition for forming a thermosetting resin layer or a composition for forming an energy ray-curable resin layer to the release film (preferably as a release-treated surface). Drying is carried out as needed, whereby a layer constituting the outermost layer is formed on the release film in advance, and the remaining layers are laminated on the exposed surface on the side opposite to the side where the release film is in contact with the release film, and the remaining layers are not removed by any of the above methods. While maintaining the bonding state, the first protective film forming sheet can also be obtained.

[Examples]

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

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

. Polymer composition

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

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

. Curing accelerator

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

. Filler

Filler (D)-1: spherical cerium oxide modified by an epoxy group ("Admanano YA050C-MKK", Admatechs Co., Ltd., average particle diameter: 50 nm).

Filler (D)-2: spherical cerium oxide modified by an epoxy group ("SC1050-MA" manufactured by Admatechs Co., Ltd., average particle diameter: 300 nm).

Filler (D)-3: spherical cerium oxide modified by an epoxy group ("SC2050-MA" manufactured by Admatechs Co., Ltd., average particle diameter: 500 nm).

Filler (D)-4: spherical cerium oxide modified by an epoxy group ("SC4050-MA" manufactured by Admatech Co., Ltd., average particle diameter: 1000 nm).

Filler (D)-5: spherical cerium oxide modified by an epoxy group (manufactured by Admatechs, "YC100C-MJK", average particle diameter: 100 nm).

[Manufacturing Example 1]

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

2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (80 parts by mass) and HEA (20 parts by mass) were used as a raw material of the copolymer to carry out a polymerization reaction, thereby obtaining an acrylic polymer.

To the acrylic polymer, 2-methacryloxyethyl isocyanate (hereinafter abbreviated as "MOI") (22 parts by mass, about 80 mol% based on HEA) was added to the acrylic polymer at 50 ° C in an air stream. A 48-hour addition reaction was carried out, whereby the target adhesive resin (I-2a) was obtained.

[Example 1]

<Manufacture of Sheet for Forming First Protective Film>

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

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

(Manufacture of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 1, a toluene diisocyanate trimer adduct of trimethylolpropane (manufactured by Tosoh Corporation, "Coronate L" was added. (0.5 parts by mass) As an isocyanate-based crosslinking agent, the mixture was stirred at 23 ° C to obtain a first adhesive composition (I-2) having a solid content concentration of 30% by mass as a first adhesive composition. In addition, the number of the preparation parts in the "manufacture of the first adhesive composition" is all a solid content conversion value.

(Manufacture of sheet for forming a first protective film)

The release treatment surface of the release film ("SP-PET381031", thickness: 38 μm, manufactured by Lintec Co., Ltd.) obtained by peeling off one side of the polyethylene terephthalate film by an oxime treatment is applied. The first adhesive composition obtained above was dried by heating at 120 ° C for 2 minutes to form a first adhesive layer having 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 are bonded together as a first substrate. Thickness of 50 μm), adhesive layer (thickness 2.5 μm) and polyolefin film (thickness 25 μm) sequentially laminated A laminate film of 105 μm was obtained, whereby a first support sheet was obtained.

The release treatment surface of the release film ("SP-PET381031", thickness: 38 μm, manufactured by Lintec Co., Ltd.) obtained by peeling off one side of the polyethylene terephthalate film by an oxime treatment is applied. The thermosetting resin layer-forming composition obtained above was dried at 100 ° C for 2 minutes to prepare a thermosetting resin film (thermosetting resin layer) having a thickness of 40 μm.

Then, the release film is removed from the first adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin film obtained above is bonded to the exposed surface of the first adhesive layer to obtain the first The first protective film forming sheet in which the base material, the first adhesive layer, the thermosetting resin layer, and the release film are sequentially laminated in the thickness direction.

<Evaluation of Cured Product of Thermosetting Resin Film>

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

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

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

(Evaluation of Optical Properties of Cured Product of Thermosetting Resin Film)

The release treatment surface of the release film ("SP-PET381031", thickness: 38 μm, manufactured by Lintec Co., Ltd.) obtained by peeling off one side of the polyethylene terephthalate film by an oxime treatment is applied. The thermosetting resin layer-forming composition obtained above was dried at 100 ° C for 2 minutes to prepare a thermosetting resin film having a thickness of 40 μm. Then, the thermosetting resin film was heated at 160 ° C for 1 hour to be thermally cured to obtain a cured product (that is, a first protective film).

The cured product of the thermosetting resin film obtained above was placed on a high-quality paper having a blue "+" mark of 1 mm in length and 1 mm in width, and the camera provided above the cured product was used in accordance with the following. The evaluation criteria were evaluated for the visibility of the "+" mark on the surface of the high-quality paper interposed between the cured products. The results are shown in Table 1.

○: The mark can be clearly recognized.

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

<Production of First Protective Film Forming Sheet and Evaluation of Cured Product of Thermosetting Resin Film>

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

The composition for forming a thermosetting resin layer was set as shown in Table 1. A sheet for forming a first protective film was produced in the same manner as in Example 1 except that the content and the content of the material were contained, 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 product of the thermosetting resin films of Examples 1 to 3 had a haze (h ₁ ) of the surface as small as 25.6 to 43.8, and was excellent in optical characteristics.

On the other hand, in the cured product of the thermosetting resin film of Comparative Examples 1 to 5, the haze (h ₁ ) of the surface was as large as 55.1 or more, and the optical characteristics were inferior.

(industry availability)

The present invention can be used for manufacturing a semiconductor wafer or the like having bumps in a connection pad portion used in a flip chip mounting method.

1‧‧‧First protective film forming sheet

11‧‧‧First substrate

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

13‧‧‧First adhesive layer

13a‧‧‧ Surface of the first adhesive layer

101‧‧‧First Support

101a‧‧‧ Surface of the first support sheet

Claims (4)

A curable resin film for adhering to a surface of a bump having a semiconductor wafer and curing, thereby forming a first protective film on the surface; and, by using the curable resin film When it is heated at 160 ° C for 1 hour to be cured, the surface of the curable resin film after curing has a haze (h ₁ ) of 50 or less. A curable resin film for attaching to a surface of a bump having a semiconductor wafer and curing, thereby forming a first protective film on the surface; and by using the curable resin film When the ultraviolet ray is irradiated under the conditions of an illuminance of 230 mW/cm ² and a light amount of 510 mJ/cm ² , the surface of the curable resin film after curing has a haze (h ₂ ) of 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. A sheet for forming a first protective film, comprising a curable resin film according to any one of claims 1 to 3, which is provided on one surface of the first support sheet.