TW201727843A - Sheet for forming protective film - Google Patents

Abstract

A sheet for forming a protective film 1 of the present application is formed by laminating a heat-curable resin layer 12 on a first supporting sheet 101, the heat-curable resin layer 12 is adhered to a surface having bumps of a semiconductor wafer and is cured by heat, whereby the first protective film is formed on the semiconductor wafer surface, wherein the difference between the surface free energy of a surface of the first supporting sheet 101 side of the pre-heated heat-curable resin layer 12 and that of a surface of the heat-curable resin layer 12 side of the first supporting sheet 101 is 10mJ/m2 or more.

Description

Protective film forming sheet

The present invention relates to a sheet for forming a protective film.

The present application is based on Japanese Patent Application No. 2015-217115, filed on Jan.

In the past, a multi-pin LSI (Large Scale Integration) package used in an MPU (Micro Processing Unit) or a gate array was mounted on a printing package. In the case of a wiring board, a flip chip mounting method is employed in which a bump electrode (bump) composed of eutectic solder, high-temperature solder, gold, or the like is formed as a semiconductor wafer in a connection pad portion thereof. 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 polishing a surface of a semiconductor wafer having bumps formed on a circuit surface opposite to a circuit surface, or performing dicing on a single piece. Chemical. In order to protect the circuit surface and the bump of the semiconductor wafer, the curable resin film laminated on the support sheet is attached to the bump forming surface to cure the film to the bump. The forming surface forms a protective film.

As such a curable resin film, a thermosetting component which is cured by heating is widely used, and as a film for forming a protective film having such a thermosetting resin layer, it has been disclosed that the film layer has a specific The thermoplastic resin layer having a thermoelastic modulus is a thermoplastic resin layer which is a non-plastic layer at 25 ° C in 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.

[Previous Technical Literature]

[Patent Literature]

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

However, when attempting to form a protective film on the bump forming surface by using the protective film forming sheet which is formed by supporting the on-chip laminated thermosetting resin layer, when the support sheet is peeled off, a large amount of the support sheet and the support sheet are sometimes observed. The interface of the thermosetting resin layer cannot be peeled off well, or the substrate is forcibly peeled off. The interface inside the support sheet such as the adhesive layer is peeled off, and the adhesive adheres to the side of the protective film or the like.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a sheet for forming a protective film which is excellent in easy peelability at the interface between a support sheet and a thermosetting resin layer.

The present invention relates to a sheet for forming a protective film, which is obtained by laminating a thermosetting resin layer on a first support sheet, and the sheet for forming a protective film is characterized in that the thermosetting resin layer is used for attaching to a layer of a semiconductor wafer having a surface of a bump and thermally cured to form a protective film on the surface; a surface free energy of the first support sheet side surface of the thermosetting resin layer before thermal curing, and the first support The difference in surface free energy of the side surface of the thermosetting resin layer of the sheet is 10 mJ/m ² or more.

The protective film forming sheet is preferably a water contact angle before heat curing of the first support sheet side surface of the thermosetting resin layer, and a water facing surface of the first support sheet on the thermosetting resin layer side surface. The difference in contact angle is 30° or more.

The interface between the first support sheet and the thermosetting resin layer of the sheet for forming a protective film of the present invention is excellent in easy peelability.

1, 2, 3 ‧ ‧ protective film forming sheet

11‧‧‧First substrate

11a‧‧‧The surface of the thermosetting resin layer of the first substrate

12‧‧‧ Curable resin layer

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

Top of the 911‧‧ ‧ bump

Fig. 1 is a cross-sectional view schematically showing an embodiment of a sheet for forming a protective film of the present invention.

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

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

4 is a cross-sectional view schematically showing an example of a semiconductor wafer having bumps.

Fig. 5 is a cross-sectional view schematically showing a state in which a sheet for forming a protective film of the present invention is attached to a surface of a semiconductor wafer having bumps.

FIG. 6 is a cross-sectional view schematically showing an example of a semiconductor wafer including a protective film formed using the protective film forming sheet of the present invention.

The present invention relates to a sheet for forming a protective film, which is obtained by laminating a thermosetting resin layer on a first support sheet, and the sheet for forming a protective film is characterized in that the thermosetting resin layer is used for attaching to a sheet a layer of a semiconductor wafer having a surface of a bump and thermally cured to form a protective film on the surface; a surface free energy of the first support sheet side surface of the thermosetting resin layer before thermal curing, and the first support The difference in surface free energy of the side surface of the thermosetting resin layer of the sheet is 10 mJ/m ² or more.

The surface free energy γ _s ^total of each solid can be used for the surface free energy γ _L ^{d of the} dispersive component, the surface free energy γ _L ^{p of the} polar component, and the surface free energy of the surface free energy γ _L ^h of the hydrogen bond component. For each known liquid, such as pure water, diiodomethane, or 1-bromine, the contact angle of the solid surface is measured, whereby the surface free energy γ _s ^d and polarity of the dispersing force component are solved for the following formula (2). The surface free energy γ _s ^{p of the} component and the simultaneous equation of the surface free energy γ _s ^h of the hydrogen bond component are obtained by substituting into the following formula (1).

γ _s ^total =γ _s ^d +γ _s ^p +γ _s ^h (1)

γ _L (1+cosθ)=2. (γ _s ^d .γ _L ^d ) ^1/2 +2. (γ _s ^p .γ _L ^p ) ^1/2 +2. (γ _s ^h .γ _L ^h ) ^1/2 (2)

The sheet for forming a protective film of the present invention is used by being attached to a surface of a semiconductor wafer having bumps via a thermosetting resin layer. Further, the thermosetting resin layer after the adhesion is increased in fluidity by heating, spreads between the bumps so as to cover the bumps, and is in close contact with the circuit surface, and covers the surface of the bump, particularly the aforementioned circuit surface. The bumps are buried in the surface of the nearby portion. The thermosetting resin layer in this state is further thermally cured by heating to finally form a first protective film, 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.

For example, the semiconductor wafer to which the protective film formation sheet is attached is polished to the surface opposite to the circuit surface, and then the first support sheet is removed, and then the bump is heated by heating of the thermosetting resin layer. 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.

In the sheet for forming a protective film of the present invention, the surface free energy before heat curing of the first support sheet side surface of the thermosetting resin layer and the thermosetting resin layer side of the first support sheet The difference in surface free energy of the surface is 10 mJ/m ² or more, and there is no component movement at the interface between the two. When the first support sheet is removed, the interface between the first support sheet and the thermosetting resin layer is excellent in easy peelability. The difference in surface free energy before thermal curing of the first support sheet side surface of the thermosetting resin layer and the surface free energy of the thermosetting resin layer side surface of the first support sheet is preferably 12 mJ/m ^{2 .} to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

Further, the contact angle with water of the first support sheet side surface of the thermosetting resin layer before heat curing and the contact angle with water of the thermosetting resin layer side surface of the first support sheet are When the difference is 30° or more, when the first support sheet is removed, the easy peeling property of the interface between the first support sheet and the thermosetting resin layer becomes more excellent.

Further, in the sheet for forming a protective film of the present invention, the surface of the first support sheet on the side of the thermosetting resin layer may be composed of an energy ray-curable adhesive or a non-energy ray-curable adhesive. In the case of the energy ray-curable adhesive, the value of the difference in surface free energy before the energy ray curing is in the above range, and there is no component movement at the interface between the two before the energy ray curing. That is, when the first support sheet is removed after the energy line is cured, the interface between the first support sheet and the thermosetting resin layer is easily peeled off. Sex is also excellent. Even if the value of the difference in surface free energy after the energy ray is solidified deviates from the above range, the influence on the component movement at the interface between the two before the energy ray curing is small, and the first support sheet and the heat when the first support sheet is removed The effect of the peelability of the interface of the curable resin layer is small.

Hereinafter, the sheet for forming a protective film of the present invention will be described in detail with reference to the drawings.

In addition, the pattern used in the following description may be different from the actual sheet for forming a protective film for the sake of convenience in order to easily understand the features. In addition, the materials, the conditions, and the like described in the following description are examples, and the present invention is not limited thereto, and may be appropriately modified without departing from the scope of the invention.

◎ 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 may be the same, or all layers may be different, or only a part may be made. The same layer "and 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 composed of only the first substrate.

Hereinafter, an example of the sheet for forming a protective film of the present invention will be described with reference to the drawings in accordance with the type of the first support sheet.

Fig. 1 is a cross-sectional view schematically showing an embodiment of a sheet for forming a protective film of the present invention. The sheet 1 for forming a protective film shown here is used as a first support sheet 101 by laminating a first adhesive layer 13 on a first substrate. In other words, the protective film forming sheet 1 is configured to include the first adhesive layer 13 on the first substrate 11 and the thermosetting resin layer 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 with heat on one surface 101a of the first support sheet 101, that is, on one surface 13a of the first adhesive layer 13. Curable resin layer 12. In the sheet 1 for forming a protective film, the surface free energy before heat curing of the surface of the first support sheet 101 of the thermosetting resin layer 12 and the surface of the side of the thermosetting resin layer 12 of the first adhesive layer 13 When the difference in surface free energy is 10 mJ/m ² or more, no component moves at the interface between the two, and the force is stabilized, and the interface between the first support sheet 101 and the thermosetting resin layer 12 is excellent in easy peelability. The difference between the surface free energy before heat curing of the surface of the first support sheet 101 on the side of the first support sheet 101 of the thermosetting resin layer 12 and the surface free energy of the surface of the first adhesive layer 13 on the side of the thermosetting resin layer 12 is preferably 12 mJ/ m ² to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

Fig. 2 is a cross-sectional view schematically showing another embodiment of the sheet for forming a protective film of the present invention. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof will be omitted. This situation is also the same in the figures of Figure 3 and later.

The protective film forming sheet 2 shown here is used for laminating the first intermediate layer 14 on the first substrate 11 and laminating the first adhesive layer 13 on the first intermediate layer 14 as the first supporting sheet. 102. In other words, the protective film forming sheet 2 is configured to include the first intermediate layer 14 on the first base material 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 thermosetting resin layer 12 is used. 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 formed on one surface 102 a of the first support sheet 102 , that is, the first layer. A thermosetting resin layer 12 is provided on one surface 13a of the adhesive layer 13.

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

In the sheet 2 for forming a protective film, the surface free energy before heat curing of the surface of the first support sheet 102 of the thermosetting resin layer 12 and the surface of the side of the thermosetting resin layer 12 of the first adhesive layer 13 When the difference in surface free energy is 10 mJ/m ² or more, no component moves at the interface between the two, and the force is stabilized, and the interface between the first support sheet 102 and the thermosetting resin layer 12 is excellent in easy peelability. The surface free energy before the heat curing of the side surface of the first support sheet 102 of the thermosetting resin layer 12 and the surface free energy of the surface of the first adhesive layer 13 on the side of the thermosetting resin layer 12 are preferably 12 mJ/ m ² to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

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

The sheet 3 for forming a protective film shown here is a first support sheet 103 using only the first base material 11. In other words, the protective film forming sheet 3 is configured to include the thermosetting resin layer 12 on the first base material 11. The first support sheet 103 is composed only of the first base material 11, and is provided with a thermosetting resin layer 12 on one surface 103a of the first support sheet 103, that is, on one surface 11a of the first base material 11 .

In other words, the protective film forming sheet 3 is obtained by removing the first adhesive layer 13 from the protective film forming sheet 1 shown in Fig. 1 . In the sheet for forming a protective film 3, the surface free energy before the surface of the first support sheet 103 on the side of the first support sheet 103 of the thermosetting resin layer 12 and the surface of the side surface of the thermosetting resin layer 12 of the first support sheet 103. When the difference in free energy is 10 mJ/m ² or more, there is no component movement at the interface between the two, and the force is stabilized, and the interface between the first support sheet 103 and the thermosetting resin layer 12 is excellent in easy peelability. The difference between the surface free energy before thermal curing of the surface of the first support sheet 103 on the side of the first support sheet 103 of the thermosetting resin layer 12 and the surface free energy of the surface of the first support sheet 103 on the side of the thermosetting resin layer 12 is preferably 12 mJ/m. ² to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, more preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

4 is a cross-sectional view schematically showing an example of a semiconductor wafer 90 having bumps 91. The circuit surface 90a of the semiconductor wafer 90 shown here is provided with a plurality of bumps 91.

The bump 91 has, for example, a shape in which one portion 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 shape of the bump is not limited to the shape as shown in the figure, and the effect of the present invention (easily peelable at the interface between the first support sheet and the thermosetting resin layer) includes elliptical spherical bumps on the projection surface. Especially effective.

FIG. 5 is a cross-sectional view schematically showing a state in which the protective film forming sheet of the present invention is attached to the surface of the semiconductor wafer 90 having the bumps 91. The heat-curable resin layer 12 after being attached is increased in fluidity by heating, spreads between the bumps so as to cover the bumps, and is in close contact with the circuit surface, and covers the surface of the bump, particularly the vicinity of the circuit surface. The bumps are buried in the surface of the part.

The thickness of the thermosetting resin layer 12 is set to be thinner than the height of the bumps 91, and the thermosetting resin layer 12 and the first adhesive layer 13 are combined. The thickness is set to be thicker than the height of the bump 91, and the entire bump 91 is covered with the thermosetting resin layer 12 and the first adhesive layer 13.

The semiconductor wafer to which the protective film formation sheet is attached is polished, for example, on the surface opposite to the surface of the circuit surface, and then the first support sheet 101 is removed, and then heated by the thermosetting resin layer 12 A protective film 12' is formed, and finally, a wafer cut into a predetermined size in a state in which the first protective film 12' is provided is incorporated in a semiconductor device.

FIG. 6 is a cross-sectional view showing an example of a semiconductor wafer 90 including a first protective film 12' formed using the protective film forming sheet 1 of the present invention. The first protective film 12' is formed using the thermosetting resin film of the present invention, and the circuit surface 90a of the semiconductor wafer 90 is covered, and the upper top 911 of the bump 91 in the surface 91a of the bump 91 and Covered by areas other nearby.

In the sheet for forming a protective film 1 of the present invention, the easy peeling property of the interface between the first support sheet 101 and the thermosetting resin layer 12, that is, the interface between the first adhesive layer 13 and the thermosetting resin layer 12 is easily peeled off. Since the first support sheet 101 is peeled off and removed, peeling failure does not occur. As shown in FIG. 6, the thermosetting resin layer 12 which becomes the first protective film 12' remains after curing, and the circuit surface and the convex are protected. Piece.

○ first substrate

The first substrate may be composed of only one layer (single layer), or may be composed of a plurality of layers of two or more layers. In the case where the substrate 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.

Further, in the present specification, the present invention is not limited to the case of the substrate, and the phrase "the plurality of layers may be the same or different from each other" means that "all the layers may be the same, or all the layers may be different, or only a part of the layers may be the same. Further, the phrase "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".

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 polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, and poly Polyolefin other than polyethylene such as methylpentene or norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-northene An ethylene-based copolymer such as an olefin copolymer (a copolymer obtained by using ethylene as a monomer); a vinyl chloride-based resin such as a polyvinyl chloride or a vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; Cycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene isophthalate, polyethylene 2,6-naphthalenedicarboxylate, All structural units have an aromatic cyclic group of wholly aromatic polyester Ester; a copolymer of two or more of the foregoing polyesters; poly(meth)acrylate; polyurethane; polyacrylamide; polyimine; polyamine; polycarbonate; Resin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polyfluorene; polyether ketone.

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 ionic polymer.

In the present specification, the term "(meth)acrylic acid" means a concept including both "acrylic acid" and "methacrylic acid". The term similar to (meth)acrylic acid is also the same. For example, the term "(meth)acrylate" includes both the concept of "acrylate" and "methacrylate", and the so-called "(meth)acryloyl group. The concept of both "acrylic sulfhydryl" and "methacryl fluorenyl" is included.

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 plural 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 not particularly 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 means 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. Among the above-mentioned constituent materials, examples of the material which can be used for forming the first base material having such a high precision include polyethylene, polyethylene, polyethylene terephthalate, and ethylene-acetic acid. Vinyl ester 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 An adhesive resin such as an epoxy group resin, or an adhesive resin such as polyvinyl ether or polycarbonate 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 has adhesiveness but also other additives and the like. A resin which exhibits adhesiveness in combination with a component, 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, and refers to all the layers constituting the first adhesive layer. Total thickness.

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 ion beam, and examples thereof include ultraviolet rays, electron beams, and the like.

The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a husion 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, "energy ray curability" refers to a property of curing by irradiation with an energy ray, and "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 composed of a first adhesive containing an adhesive Formed by matter. For example, by applying a first adhesive composition on the surface of the first adhesive layer, and drying as needed, a more specific method of forming the first adhesive layer with respect to the first adhesive layer can be formed at the target portion. The method of forming the other layers will be described in detail later. 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 the present specification, the term "normal temperature" 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. A method of various coaters such as a roll coater, a curtain coater, a pattern coater, a blade coater, a screen coater, a bar coater, and a staple coater.

The drying condition of the first adhesive composition is not particularly limited. When the first adhesive composition contains a solvent to be described later, it is preferably heated and dried. In this case, for example, it is preferably at 70 ° C to 130 ° C. Drying is carried out for 10 seconds to 5 minutes.

When 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 Agent composition And the first adhesive composition (I-1) containing a non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)"), and energy The line-curable compound; the first adhesive composition (I-2), which contains an energy-line-curable adhesive in which an unsaturated group is introduced into a side chain of the non-energy ray-curable adhesive resin (I-1a). Resin (I-2a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)"); and first adhesive composition (I-3) containing the above-mentioned 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 (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (methyl) Cetyl acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (meth) acrylate Stearyl ester), decyl (meth) acrylate Ester, (meth) acrylate, eicosyl acrylate.

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 aforementioned acrylic polymer is preferably derived from (meth)acrylic acid In addition to the structural unit of the alkyl ester, there is further a structural unit derived from a monomer having a functional group.

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, 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; Ethylene unsaturated dicarboxylic acid such as maleic acid or citraconic acid (dicarboxylic acid having an ethylenically unsaturated bond); An anhydride of a dicarboxylic acid; a carboxyalkyl (meth)acrylate such as 2-carboxyethyl methacrylate;

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 the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group-containing monomer.

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 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.

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, "energy ray polymerizability" means a property of being polymerized by irradiation of an energy ray.

The adhesive resin (I-1a) 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 arbitrary. Ground selection.

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 based on the total mass of the first adhesive composition (I-1). % is more preferably 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 selected. .

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 based on the total mass of the first adhesive composition (I-1). More preferably, it is 5% by mass to 90% by mass, and particularly preferably 10% by mass to 85% by 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. a ketone compound; a fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide; a thioether compound such as phenyl thioether or thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; ferrocene; Ferrocene compound; thioxanthone compound such as thioxanthone; peroxide compound; diketone compound such as diethyl hydrazine; benzoin, diphenyl fluorene, benzophenone, 2,4-diethyl thioxanthone 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2-chloroindole, 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 types 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 also contain other additives which are not equivalent to any of the above components, within a range not detracting from the effects of the present invention.

Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. A known additive such as a reaction retarder or 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. Examples of the reaction retardation agent include those in which a chelate complex is formed by a chelate compound, and more specifically, two or more carbonyl groups in one molecule. (-C(=O)-).

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 a ring; An aliphatic hydrocarbon such as hexane or 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 used as the solvent (I-1a), for example, without being removed from the adhesive (I-1a), and can be used directly in the first adhesive composition (I-1), or 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 arbitrary. Ground selection.

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 based on the total mass of the first adhesive composition (I-2). % is more preferably 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 aforementioned crosslinking agent in the first adhesive composition (I-2) can be enumerated 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 types 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 based on 100 parts by mass of the adhesive resin (I-2a). The amount 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-2) may also contain other additives which are not equivalent to any of the above components, within a range not detracting from 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. As long as it is appropriate to adjust.

<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 based on the total mass of the first adhesive composition (I-3). % is more preferably 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 monomers and oligomers which have an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray. 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. When two or more types are used, the combinations and ratios may be arbitrary. Ground selection.

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 0.03 The mass portion is preferably 200 parts by mass, particularly preferably 0.05 parts 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 types 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 100 parts by mass based on the total content of the adhesive resin (I-2a) and the energy ray-curable low molecular compound. From 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass to 10 parts by mass, even more preferably from 0.05 part by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-3) may also contain other additives which are not equivalent to any of the above components, within a range not detracting from the effects of the present invention.

As the other additives mentioned above, the first adhesive composition can be cited The other additives in (I-1) are the same.

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 (I-1) to first adhesive composition other than the first adhesive composition (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 Containing ingredients and describing the composition of the three first adhesives All of the first adhesive compositions other than the materials (referred to as "the first adhesive composition (I-1) to the first adhesive composition (I-3) in the present specification" ) can also be used in the same way.

As the first adhesive composition other than the first adhesive composition (I-1) to the first adhesive composition (I-3), in addition to the energy ray-curable adhesive composition, non-energy may be cited. A line curable adhesive 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 composition (I-1) to the first adhesive composition (I-3) preferably contains one or two or more kinds of crosslinking agents, and the content thereof can be set to It is the same as the above-described first adhesive composition (I-1).

<<Method of Manufacturing First Adhesive Composition>>

The first adhesive composition such as the first adhesive composition (I-1) to the first adhesive composition (I-3) may be composed of the above-mentioned adhesive, and optionally the above-mentioned adhesive. It is obtained by formulating the components constituting the first adhesive 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 blending 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 is not particularly limited as long as it is appropriately selected according to the purpose.

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 cause deformation of the protective film, as a preferable constituent material of the first intermediate layer, the first intermediate layer is The aspect of further improving the adhesion is exemplified by (meth)acrylic acid urethane or the like.

The first intermediate layer may be only one layer (single layer), or may be more than two 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 not particularly 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 refers to 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 formation target surface of the first intermediate layer, dried as necessary, 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 coating of the first intermediate layer forming composition is performed by using a known method. The method may be carried out, for example, using an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, a roll coater, and a curtain coater. A method of various coaters such as a pattern coater, a blade coater, a screen coater, a bar coater, and a staple coater.

The drying condition of the first intermediate layer-forming composition is not particularly limited. When the first intermediate layer-forming composition contains a solvent to be described later, it is preferably heated and dried. In this case, for example, it is preferably 70. Dry at °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) Any of those which are polyfunctional, preferably at least monofunctional.

The (meth)acrylic acid urethane contained in the composition for forming the first intermediate layer 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 combination may be used. And the ratio 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.

The above polyol compounds 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.

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 of a difunctional diol, a trifunctional triol, and a tetrafunctional or higher polyhydric alcohol, and is preferably a diol in terms of availability, versatility, and reactivity. .

. 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 aforementioned (meth)acrylic acid urethane has the above-mentioned ether bond portion, that is, has a polyether type diol derived therefrom. The 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. In the present specification, the term "derivative" means that one or more groups of the original compound are substituted with a group other than the above (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 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.

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 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. When the number average molecular weight is 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 Cyclic aliphatic diisocyanate such as alkane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ω,ω'-diisocyanate dimethylcyclohexane 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, tolidine diisocyanate, tetramethylene xylene diisocyanate, naphthalene-1,5-diisocyanate and other aromatic diisocyanates Wait.

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 above-mentioned (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; a hydroxyl group-containing (meth) acrylamide such as N-methylol (meth) acrylamide; or a (meth)acrylic acid with vinyl alcohol or vinyl phenol or The reactant obtained by the reaction of 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.

The reaction of the terminal isocyanate urethane prepolymer and the (meth)acrylic compound can be carried out by using a solvent, a catalyst or the like as necessary.

The conditions for reacting the terminal isocyanate urethane prepolymer with the (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 Force, and it is easy to optimize the hardness of the first intermediate layer.

In addition, the weight average molecular weight in this specification is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method, unless otherwise indicated.

[Polymerizable monomer]

In the aspect of further improving the film-forming property, 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, isooctyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester N-decyl acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate ((methyl) Lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, (A) Cetyl hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (meth) acrylate Ester), isostearyl (meth)acrylate (isostearyl (meth)acrylate), nonadecyl (meth)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"); disubstituted with two hydrogen atoms having an amine group substituted with a group other than a hydrogen atom Amino (meth) acrylate (hereinafter sometimes referred to as "including two a (meth) acrylate having a substituted amino group; a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate or methyl glycidyl (meth) acrylate (hereinafter sometimes referred to as "Epoxy group-containing (meth) acrylate").

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 "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, and the so-called "containing two The substituted (meth) acrylate group means 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 (meth)acrylic acid urethane, and examples of such a polymerizable monomer include : (meth) acrylate having an aliphatic cyclic group, (meth) acrylate having an aromatic hydrocarbon group, (meth) acrylate having a heterocyclic group, etc., more preferably having an aliphatic cyclic group (meth) acrylate.

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 selected. .

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 based on the total mass of the first intermediate layer-forming composition (II-1). % is more preferably 15% by mass to 95% by mass, further preferably 20% by mass to 90% by mass, particularly preferably 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 arbitrarily select.

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 It is preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[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), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetradecyl acetate, dipentaerythritol hexa(3-indenyl) Propionate), tris[(3-mercaptopropoxy)-ethyl]-isocyanate, 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, etc. .

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 in the composition for forming the first intermediate layer, it may be used by mixing the solvent with any of the components other than the solvent to preliminarily dilute the compounding component; or The formulated ingredients are pre-diluted and the solvent is mixed with the formulated ingredients.

The method of mixing the components at the time of blending 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.

◎Hot curable resin layer

The thermosetting resin layer is used to protect a circuit surface of a semiconductor wafer and a layer of bumps provided on the circuit surface, and to form a first protective film by curing.

As a preferable thermosetting resin layer, the polymer component (A) and the thermosetting component (B) are mentioned, for example. The polymer component (A) is considered to be a component formed by a polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is capable of curing (polymerization) by triggering heat as a reaction. The ingredients should be. 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, when the thickness of the thermosetting resin layer is equal to or less than the above upper limit value, the effect of suppressing the inclusion of bubbles in the first protective film is further improved.

Here, the "thickness of the thermosetting resin layer" 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 the layers constituting the thermosetting resin layer. Total thickness.

<<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 component which is not vaporized at normal temperature in the composition for forming a thermosetting resin layer The ratio of the content of this is usually the same as the ratio of the contents of the aforementioned 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. In this case, for example, it is preferably Drying is carried out at 70 ° C to 130 ° C for 10 seconds to 5 minutes.

<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 combination may be two or more. And the ratio 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 at most the above upper limit value, the thermosetting resin layer easily follows the uneven surface of the adherend.

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, by acrylic resin When the Tg 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, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (A) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, (meth) acrylate A hexadecyl ester (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc. The alkyl group has a carbon number of 1 18-chain alkyl (meth)acrylate; isodecyl (meth)acrylate, cycloalkyl (meth)acrylate such as dicyclopentanyl (meth)acrylate; benzyl (meth)acrylate ester An arylalkyl (meth)acrylate; a cycloalkylenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; a dicyclopentenyloxyethyl (meth)acrylate; Cycloalkenyloxyalkyl acrylate; (meth) acrylimide; glycidyl-containing (meth) acrylate such as glycidyl (meth) acrylate; hydroxymethyl (meth) acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate a hydroxyl group-containing (meth) acrylate such as a butyl ester or a 4-hydroxybutyl (meth)acrylate; a (meth)acrylic acid having a substituted amino group such as N-methylaminoethyl (meth)acrylate Ester and 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 aforementioned functional group of the acrylic resin can be via a crosslinking agent (F) described later Further, it may be bonded to other compounds or may be directly bonded to other compounds without passing through the crosslinking agent (F). When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the sheet for forming a protective film 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.

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 may be Choose arbitrarily.

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 (that is, the content of the polymer component (A) of the thermosetting resin layer) It does not depend on the kind of the polymer component (A), and is preferably 5% by mass to 85% by mass, more preferably 5% by mass to 80% by mass.

The polymer component (A) sometimes also corresponds to the thermosetting component (B). In the present invention, when 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. The substance (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, 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, the above-mentioned 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 sheet for forming a protective film is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include converting a part of an epoxy group of a polyfunctional epoxy resin into an unsaturated hydrocarbon. a compound formed from a 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.

In the present specification, the "number average molecular weight" means a number average molecular weight expressed by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

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.

In the present specification, the term "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be based on JIS (Japanese Jdustrial Standards) K 7236:2001. Method determination.

The epoxy resin (B1) 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.

. 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 aralkylphenol. 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 hydrocarbon 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 number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin is preferably from 300 to 30,000, more preferably It is 400 to 10,000, and particularly preferably 500 to 3,000.

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 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.

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). More preferably, it is 1 part by mass to 200 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, thermal curability is lowered. The moisture absorption rate of the resin layer is further improved by the reliability of the package obtained by using the sheet for forming a protective film.

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) 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, still more preferably from 150 parts by mass to 800 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 further contain 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 combination may be two or more. And the ratio 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) which suppresses high polarity is moved to the adherend in the thermosetting resin layer under high temperature and high humidity conditions. The efficiency of segregation on the interface side is improved, and the reliability of the package obtained by using the sheet for forming a protective film is further improved.

[Filling material (D)]

The resin layer-forming composition (III-1) and the thermosetting resin layer may further contain a filler (D). By including the filler (D) in the thermosetting resin layer, the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin layer is easily adjusted, and the thermal expansion coefficient is obtained by forming the object of the first protective film. Optimum, the package obtained by using the protective film forming sheet The reliability 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, iron oxide, 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 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 combinations and The ratio can be arbitrarily selected.

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, thermosetting property) The content of the filler (D) of the resin layer is preferably from 5% by mass to 35% by mass, more preferably from 7% by mass to 25% by mass.

[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. Further, by using the coupling agent (E), the first protective film obtained by curing the thermosetting resin layer improves water resistance without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group 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 Baseline, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, methyltriethoxydecane, vinyl Trimethoxy decane, 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 combinations 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) for bonding and crosslinking the functional group with another compound. The initial adhesion and cohesive force of the thermosetting resin layer can be adjusted by crosslinking using the crosslinking agent (F).

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. The reaction product of the compound of the molecularly active hydrogen may, for example, be 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; Mercapone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of toluene diisocyanate to all or a portion of the hydroxyl groups of a polyol such as trimethylolpropane Any one or more of hexamethylene diisocyanate and xylene diisocyanate; or a diisocyanate diisocyanate.

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 crosslinking agent (F) 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 crosslinking agent (F), in the resin layer-forming composition (III-1), cross-linking is carried out in an amount of 100 parts by mass based on the content of the polymer component (A). The content of the agent (F) is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass, still 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 trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(a). Acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (Methyl) propylene containing a chain aliphatic skeleton such as (meth) acrylate (meth)acrylate containing a cyclic aliphatic skeleton such as dicyclopentanyl (meth)acrylate; polyalkylene glycol (methyl) such as polyethylene glycol di(meth)acrylate Acrylate; oligoester (meth) acrylate; (meth) acrylate urethane oligomer; epoxy modified (meth) acrylate; the aforementioned polyalkylene glycol (meth) acrylate Polyether (meth) acrylate other than ester; 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 polymerized 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 arbitrary. Ground selection.

In the resin layer-forming composition (III-1), the content of the energy ray-curable resin (G) is preferably from 1% by mass to 95% based on the total mass of the resin layer-forming composition (III-1). The mass% is more preferably from 5% by mass to 90% by mass, particularly preferably from 10% by mass to 85% by 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 used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrary. Ground selection.

In the resin layer-forming composition (III-1), the content of the photopolymerization initiator (H) is preferably from 0.1 part by mass to 20 parts by mass based on 100 parts by mass of the energy ray-curable resin (G). More preferably, it is 1 part by mass to 10 parts by mass, and particularly preferably 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 the 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) 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 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 one type or two or more types. When two or more types are used, 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 blending is not particularly limited, and can 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.

Method for producing ruthenium protective film forming sheet

The sheet for forming a protective film 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, when manufacturing the first support sheet, when the first adhesive layer or the first intermediate layer is laminated on the first substrate, by coating on the first substrate The first adhesive composition or the first intermediate layer forming composition may be dried as needed or irradiated with an energy ray to laminate a first adhesive layer or a first intermediate layer.

On the other hand, for example, when a thermosetting resin layer is further laminated on the first adhesive layer which has been laminated on the first substrate, the composition for forming a thermosetting resin layer may be applied to the first adhesive layer. The material directly forms a thermosetting 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. As described above, in the case where a laminate structure of two consecutive layers is formed using any of the compositions, the composition can be further coated on the layer formed of the above composition to newly 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 surface of the formed layer on the side opposite to the side in contact with the release film is The exposed faces of the remaining layers formed 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 sheet for forming a protective film formed by laminating a first adhesive layer on a first substrate and laminating a thermosetting resin layer on the first adhesive layer (the first support sheet is the first substrate and the first substrate) In the case of a sheet for forming a protective film of a laminate of an adhesive layer, the first adhesive composition is applied onto the first substrate, and dried as needed, thereby preliminarily layering on the first substrate. The first adhesive layer is coated with a thermosetting resin layer-forming composition on the release film, and if necessary, dried to form a thermosetting resin layer on the release film to expose the thermosetting resin layer. The surface is bonded to the exposed surface of the first adhesive layer which has been laminated on the first substrate, and the thermosetting resin layer is laminated on the first adhesive layer, whereby a sheet for forming a protective film can be obtained.

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 as needed or irradiated with an energy ray, whereby a first intermediate layer is preliminarily laminated on the first substrate, and the first adhesive composition is applied onto the release film, and dried as needed. Thereby, a first adhesive layer is formed on the release film in advance, and the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer laminated on the first substrate to bond the first adhesive layer. The first intermediate layer is obtained by laminating on the first intermediate layer. In this case, for example, a composition for forming a thermosetting resin layer is applied onto the release film, and if necessary, drying is performed to form a thermosetting resin layer on the release film in advance, and the thermosetting resin layer is formed. The exposed surface is bonded to the exposed surface of the first adhesive layer which has been laminated on the first intermediate layer, and the thermosetting resin layer is laminated on the first adhesive layer, whereby a sheet for forming a protective film can be obtained.

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. Coating the first adhesive composition or the first intermediate layer forming composition on the release film by the method of the composition Drying or irradiating the energy ray as needed, thereby preliminarily forming a first adhesive layer or a first intermediate layer on the release film, and bonding the exposed faces of the layers to one surface of the first substrate, This laminates the first adhesive layer or the first intermediate layer onto the first substrate.

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

In this manner, the layer other than the first base material constituting the sheet for forming a protective film can be laminated by being formed on the release film in advance and bonded to the surface of the target layer. Therefore, it is necessary to appropriately select such a step as needed. It is sufficient to form a sheet for forming a protective film.

In addition, the sheet for forming a protective film is usually stored in a state in which a peeling film is bonded to the surface of the outermost layer (for example, a thermosetting resin layer) on the opposite side of the first support sheet. Therefore, a composition for forming a layer forming the outermost layer is applied to the release film (preferably as a release-treated surface), and a composition for forming a layer of the outermost layer is formed, and dried on the release film. The layer constituting the outermost layer is formed in advance, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the above methods, and the release film is removed without being removed. A sheet for forming a protective film can 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 parts by mass) and acrylic acid 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) copolymerized acrylic resin (weight average molecular weight 800,000, glass transfer) Temperature -28 ° C).

. 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", manufactured by Admatechs Co., Ltd.).

[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.

[Manufacturing Example 2]

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

Butyl acrylate (hereinafter abbreviated as "BA") (52 parts by mass), methyl methacrylate (hereinafter abbreviated as "MMA") (20 parts by mass), and HEA (28 parts by mass) were used as raw materials of the copolymer. The polymerization reaction was carried out, whereby an acrylic polymer was obtained.

To the acrylic polymer, 2-methacryloxyethyl isocyanate (hereinafter abbreviated as "MOI") (28 parts by mass, relative to HEA) was added. On the other hand, about 90 mol%), a 48-hour addition reaction was carried out at 50 ° C in an air stream to obtain a target adhesive resin (I-2a).

[Manufacturing Example 3]

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

A lauryl acrylate (hereinafter abbreviated as "LA") (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.

The MOI was added to the acrylic polymer in a manner of 0.8 times the total mole number of the isocyanate group in the MOI relative to the total number of moles of the hydroxyl group in the HEA, and was carried out in an air stream at 50 ° C for 48 hours. The reaction was carried out, whereby the target adhesive resin (I-2a) was obtained.

[Manufacturing Example 4]

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

2EHA (40 parts by mass), vinyl acetate (hereinafter sometimes abbreviated as "VAc") (40 parts by mass), and HEA (20 parts by mass) are used as raw materials of the copolymer to carry out a polymerization reaction, thereby obtaining an acrylic polymer. .

The MOI was added to the acrylic polymer in a manner of 0.8 times the total mole number of the isocyanate group in the MOI relative to the total number of moles of the hydroxyl group in the HEA, and was carried out in an air stream at 50 ° C for 48 hours. The reaction was carried out, whereby the target adhesive resin (I-2a) was obtained.

[Manufacturing Example 5]

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

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.

The MOI was added to the acrylic polymer in a manner of 0.8 times the total mole number of the isocyanate group in the MOI relative to the total number of moles of the hydroxyl group in the HEA, and was carried out in an air stream at 50 ° C for 48 hours. The reaction was carried out, whereby the target adhesive resin (I-2a) was obtained.

[Example 1]

<Manufacture of Sheet for Forming Protective Film>

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

Polymer component (A)-1 (100 parts by mass), epoxy resin (B1)-1 (135 parts by mass), epoxy resin (B1)-2 (90 parts by mass), epoxy resin (B1)- 3 (150 parts by mass), a curing accelerator (C)-1 (180 parts by mass), a curing accelerator (G)-1 (1 part by mass), and a filler (D)-1 (160 parts by mass) were dissolved in The methyl ethyl ketone was stirred at 23 ° C to obtain a resin layer-forming composition (III-1) having a solid content concentration of 55% by mass as a thermosetting resin layer-forming composition.

(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 crosslinking agent, stirred at 23 ° C, thereby obtaining a solid component The first adhesive composition (I-2) having a concentration of 30% by mass was used as the 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 protective film)

The peeling 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 fluorenone treatment was applied to the above-mentioned peeling treatment surface. The obtained first adhesive composition was dried by heating at 110 ° C for 1 minute to form a first adhesive layer having a thickness of 30 μm on the release film.

Then, on the exposed surface of the first adhesive layer, the polyolefin film (thickness 25 μm), the adhesive layer (thickness 2.5 μm), and the polyethylene terephthalate film (thickness) adhered to the first substrate. 50 μm), an adhesive layer (thickness: 2.5 μm), and a laminate film of a thickness of 105 μm in which a polyolefin film (thickness: 25 μm) was sequentially laminated, thereby obtaining a first support sheet.

The peeling 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 fluorenone treatment was applied to the above-mentioned peeling treatment surface. The obtained thermosetting resin layer-forming composition was dried at 100 ° C for 2 minutes to prepare a thermosetting resin layer having a thickness of 40 μm.

Then, the first adhesive layer of the first support sheet obtained above is removed from the release film, and the heat obtained is adhered to the exposed surface of the first adhesive layer. In the exposed surface of the curable resin layer, a sheet for forming a protective film in which the first base material, the first adhesive layer, the thermosetting resin layer, and the release film are sequentially laminated in the thickness direction is obtained.

[Comparative Example 1]

(Manufacture of the first adhesive composition)

Toluene diisocyanate trimer adduct of trimethylolpropane (manufactured by Tosoh Corporation), "Coronate L", was added to the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 2. (1) parts by mass of the first adhesive composition (I-2') having a solid content concentration of 30% by mass as an isocyanate-based crosslinking agent, and stirring at 23 ° C 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 protective film)

The first support sheet was obtained in the same manner as in Example 1 except that the first adhesive composition described in Example 1 was changed to the first adhesive composition of Comparative Example 1 obtained above.

The peeling 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 fluorenone treatment was applied to the above-mentioned peeling treatment surface. The obtained thermosetting resin layer-forming composition was dried at 100 ° C for 2 minutes to prepare a thermosetting resin layer having a thickness of 40 μm.

Then, the release film was removed from the first adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin layer similar to that of Example 1 obtained above was bonded to the exposed surface of the first adhesive layer. A sheet for forming a protective film of Comparative Example 1 in which the first base material, the first adhesive layer, the thermosetting resin layer, and the release film were sequentially laminated in the thickness direction.

[Embodiment 2]

(Manufacture of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 3, a toluene diisocyanate trimer adduct of trimethylolpropane (manufactured by Tosoh Corporation, "Coronate L" was added. (1.0 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 protective film)

A sheet for forming a protective film of Example 2 was obtained in the same manner as in Example 1 except that the first adhesive composition described in Example 1 was changed to the first adhesive composition of Example 2 obtained above.

[Example 3]

(Manufacture of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 4, a toluene diisocyanate trimer adduct of trimethylolpropane (manufactured by Tosoh Corporation, "Coronate L" was added. (1.0 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 protective film)

A sheet for forming a protective film of Example 3 was obtained in the same manner as in Example 1 except that the first adhesive composition described in Example 1 was changed to the first adhesive composition of Example 3 obtained above.

[Example 4]

(Manufacture of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 5, a toluene diisocyanate trimer adduct of trimethylolpropane (manufactured by Tosoh Corporation, "Coronate L" was added. (1.0 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 protective film)

A sheet for forming a protective film of Example 4 was obtained in the same manner as in Example 1 except that the first adhesive composition described in Example 1 was changed to the first adhesive composition of Example 4 obtained above.

<Evaluation of Sheet for Forming Protective Film>

With respect to the thermosetting resin layer and the first adhesive layer obtained in Example 1 and Comparative Example 1, the contact angles of pure water, diiodomethane, and 1-bromonaphthalene were determined in an environment of a temperature of 23 ° C and a humidity of 50%. The surface free energy of each of the dispersive force component γ _s ^d , the polar component γ _s ^p , and the hydrogen bond component γ _s ^h is obtained based on the above, and the surface free energy γ _s ^{total of} each layer surface is obtained from each of the layers. .

The results are shown in Table 1.

Table 1 shows the difference between γ _s ^total of the thermosetting resin layer and the γ _s ^total of the first adhesive layer in each of the protective film forming sheets of Example 1 and Comparative Example 1.

The difference between the contact angle of water of the thermosetting resin layer and the water contact angle of the first adhesive layer in each of the protective film-forming sheets of Example 1 and Comparative Example 1 is also shown in Table 1.

For the first adhesive layers obtained in Examples 1 to 4 and Comparative Example 1, an ultraviolet (ultraviolet) irradiation apparatus (RAD-2000m/8, manufactured by Lintec Co., Ltd.) was used at an illuminance of 230 mW/cm ² and a light amount of 760 mJ/cm. After UV irradiation under conditions of ² , the contact angles of pure water, diiodomethane, and 1-bromonaphthalene were determined at 23 ° C and a humidity of 50%, and the dispersing force component γ _s ^d and polarity were determined based on the above. The surface free energy of each of the component γ _s ^p and the hydrogen bond component γ _s ^h is obtained from the sum of the surfaces, and the surface free energy γ _s ^total of the surface of each layer is obtained.

The results are shown in Table 2 together with the results of the uncured thermosetting resin layer.

Table 2 shows the difference between γ _s ^total of the thermosetting resin layer in each of the protective film forming sheets of Example 1 and Comparative Example 1 and γ _s ^total of the first adhesive layer after UV curing.

The difference in contact angle between the water contact point of the thermosetting resin layer in each of the protective film forming sheets of Example 1 and Comparative Example 1 and the water contact angle of the first adhesive layer after UV curing is also shown in Table 2. Show.

(Table 2)

<Evaluation of peelability after UV curing>

After the sheets for forming a protective film of Examples 1 to 4 and Comparative Example 1 were produced, the peeling property after UV curing was evaluated in the following order one week later.

A sheet for forming a protective film was attached to a circuit surface of a 6-inch bump semiconductor wafer by thermal lamination at 70 °C.

After return to room temperature (after about 5 minutes) after attachment by UV irradiation apparatus (manufactured by Lintec Corporation, RAD-2000m / 8) at an illuminance 230mW / cm ^2, subjected to UV irradiation / cm condition of 760mJ ² of the light amount, so that The first adhesive layer is cured. Thereafter, the first support sheet is peeled off from the thermosetting resin layer, and as a result, the protective film forming sheets of Examples 1 to 4 can be composed of the first substrate and the first adhesive layer. The support sheet was easily peeled off from the interface with the thermosetting resin layer (the peeling property was "good"), and in the sheet for forming a protective film of Comparative Example 1, the first adhesive layer was held next to the thermosetting resin layer. In the state where the first base material is peeled off, the first adhesive layer locally collapses and remains on the surface of the thermosetting resin layer (peelability "defect").

Although γ _s ^total difference of the first adhesive layer of the heat-curable resin gamma] _s ^total layer with UV-curable or thermosetting resin layer on the first adhesive agent layer after the water contact angle of water with UV curing The difference in contact angle was not as large as shown in Table 2, but the peeling property of the first support sheet and the thermosetting resin layer showed a large difference. That is, the difference between the γ _s ^total of the thermosetting resin layer before UV curing rather than the UV curing and the γ _s ^total of the first adhesive layer, or the contact angle of the thermosetting resin layer with water before UV curing The difference in contact angle of the first adhesive layer with water has a large influence on the peelability of the first support sheet and the thermosetting resin layer.

In the sheets for forming a protective film of Examples 1 to 4 and Comparative Example 1, a polymer component (A)-1 having butyl acrylate (BA) as a main component was used for the thermosetting resin layer. In the first adhesive layer of Examples 1 to 4, an adhesive resin (I-2a) containing 2-ethylhexyl acrylate (2EHA) or lauryl acrylate (LA) as a main component is used. In the first adhesive layer of Comparative Example 1, butyl acrylate (BA) was used as a main component in the same manner as the thermosetting resin layer, in which the difference in the surface free energy was 10 mJ/m ² or more. Since the adhesive resin (I-2a) is used, the difference in surface free energy is small.

It is considered that it takes about one week to form a sheet for forming a protective film until the quality such as adhesion is stable. Therefore, in the sheet for forming a protective film of Comparative Example 1 in which the difference in surface free energy of the thermosetting resin layer and the surface free energy of the first support sheet is small, it is considered that the movement of the component occurs at the interface between the two. Then the force rises abnormally, resulting in poor peeling.

In the sheet for forming a protective film of Example 1 in which the difference between the surface free energy of the thermosetting resin layer and the surface free energy of the first support sheet is large, it is considered that there is no component movement at the interface between the two, and then the force is stabilized. The easy peeling property of the interface between the first support sheet and the thermosetting resin layer is excellent.

(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‧‧‧Protective film forming sheet

11‧‧‧First substrate

12‧‧‧ Curable resin layer

13‧‧‧First adhesive layer

13a‧‧‧ Surface of the first adhesive layer

101‧‧‧First Support

101a‧‧‧ Surface of the first support sheet

Claims (2)

A sheet for forming a protective film obtained by laminating a thermosetting resin layer on a first support sheet; and the thermosetting resin layer is used for attaching to a surface of a semiconductor wafer having bumps and performing heat a layer formed on the surface to form a protective film; a surface free energy before heat curing of the first support sheet side surface of the thermosetting resin layer, and a surface of the thermosetting resin layer side surface of the first support sheet The difference in free energy is 10 mJ/m ² or more. The sheet for forming a protective film according to claim 1, wherein a contact angle with water of the first support sheet side surface of the thermosetting resin layer before heat curing and the thermosetting resin of the first support sheet are the same. The difference in contact angle with respect to water on the layer side surface is 30 or more.