JPWO2017078039A1 - Thermosetting resin film, first protective film forming sheet, and first protective film forming method - Google Patents

Abstract

This thermosetting resin film is used to form a first protective film on the surface of the semiconductor wafer by sticking it to the surface of the semiconductor wafer having bumps and thermosetting, and this thermosetting resin film before curing When the film is heated at a heating rate of 10 ° C./min, the time during which the viscosity at the shear rate of 1 s-1 of this film is 100,000 Pa · s or less is 500 seconds or more. The first protective film forming sheet includes a first support sheet, and the thermosetting resin film is provided on one surface of the first support sheet. This thermosetting resin film forms a first protective film by being thermoset while being pressurized at a pressure of 0.1 Pa or more.

Description

The present invention relates to a thermosetting resin film, a first protective film forming sheet using the thermosetting resin film, and a method for forming the first protective film.
This application claims priority based on Japanese Patent Application No. 2015-217117 for which it applied to Japan on November 4, 2015, and uses the content here.

  Conventionally, when a multi-pin LSI package used for an MPU, a gate array or the like is mounted on a printed wiring board, a projecting electrode (bump) made of eutectic solder, high-temperature solder, gold or the like is formed as a semiconductor chip on its connection pad portion. The flip chip mounting method has been employed in which the bumps are brought into contact with the corresponding terminal portions on the chip mounting substrate in a so-called face-down manner, and are melted / diffusion bonded. .

  The semiconductor chip used in this mounting method can be obtained, for example, by grinding a surface of a semiconductor wafer having bumps formed on the circuit surface opposite to the circuit surface, or by dicing into individual pieces. In the process of obtaining such a semiconductor chip, a curable resin film is usually applied to the bump forming surface for the purpose of protecting the circuit surface and bumps of the semiconductor wafer, and this film is cured to protect the bump forming surface. A film is formed. As such a curable resin film, those containing a thermosetting component that is cured by heating are widely used, and as the protective film-forming sheet provided with such a thermosetting resin film, the film In which a thermoplastic resin layer having a specific thermoelastic modulus is laminated, and a thermoplastic resin layer non-plasticized at 25 ° C. is laminated on the uppermost layer of the thermoplastic resin layer ( Patent Document 1). According to Patent Document 1, this protective film forming sheet is said to be excellent in bump filling property of the protective film, wafer processability, electrical connection reliability after resin sealing, and the like.

  However, the protective film formed from the thermosetting resin film has a problem that it may contain bubbles in some cases. If air bubbles are present in the protective film, the protective film will function sufficiently, such as reducing the adhesion between the bump forming surface and the protective film, and reducing the protective performance of the protective film against the circuit surface and bump. May not be possible. Also, if air bubbles are present in the protective film, when the protective film is heated by solder reflow or the like, the air bubbles expand and the adhesion between the bump forming surface and the protective film decreases, or the air bubbles rapidly In the case of expansion, the protective film ruptures and the protective film and the semiconductor chip are separated, or the semiconductor chip including the circuit surface and bumps is damaged. And it is not certain whether the protective film disclosed in Patent Document 1 can suppress the inclusion of bubbles.

JP 2005-028734 A

  The present invention provides a thermosetting resin film capable of forming a protective film on which a bubble is suppressed on a bump forming surface, a protective film forming sheet using the thermosetting resin film, and a method for forming the protective film. The purpose is to do.

The present invention is a thermosetting resin film for forming a first protective film on the surface by sticking to a surface of a semiconductor wafer having bumps and thermosetting, and the thermosetting resin before curing Provided is a thermosetting resin film in which, when the film is heated at a heating rate of 10 ° C./min, the time at which the viscosity at a shear rate of 1 s ⁻¹ is 100000 Pa · s or less is 500 seconds or more. To do.
Moreover, this invention provides the sheet | seat for 1st protective film formation provided with the said thermosetting resin film on one surface of a 1st support sheet.
Moreover, this invention provides the formation method of a 1st protective film which forms a 1st protective film by thermosetting the said thermosetting resin film, pressurizing with the pressure of 0.1 Pa or more.

  By using the thermosetting resin film and the first protective film forming sheet of the present invention, and by adopting the protective film forming method of the present invention, the protective film in which the inclusion of bubbles is suppressed is formed on the bump forming surface. Can be formed.

It is sectional drawing which shows typically an example of the state which formed the 1st protective film in the bump formation surface using the thermosetting resin film of this invention. It is sectional drawing which shows typically an example of the state which formed the protective film in the bump formation surface using the conventional thermosetting resin film. It is sectional drawing which shows typically one Embodiment of the sheet | seat for 1st protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the sheet | seat for 1st protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the sheet | seat for 1st protective film formation of this invention. It is a graph which shows the relationship of the heating time of a sample, temperature, and shear viscosity (V1) in Examples 1-2 and the comparative example 1. FIG.

The thermosetting resin film of the present invention is a thermosetting resin film for forming a first protective film on the surface of the semiconductor wafer by sticking it on the surface of the semiconductor wafer having bumps and thermosetting the film. When the thermosetting resin film is heated at a heating rate of 10 ° C./min, the time at which the viscosity at a shear rate of 1 s ⁻¹ is 100,000 Pa · s or less is 500 seconds or longer. is there.
Moreover, the 1st sheet | seat for protective film formation of this invention equips the one surface of a 1st support sheet with the thermosetting resin film of said this invention. In the first protective film forming sheet, the “thermosetting resin film” may be referred to as a “thermosetting resin layer”.

The first protective film-forming sheet of the present invention is used by being attached to a surface (that is, a circuit surface) having bumps of a semiconductor wafer via the thermosetting resin layer (thermosetting resin film). Then, the thermosetting resin layer after application increases in fluidity by heating, spreads between the bumps so as to cover the bumps, adheres to the circuit surface, and also on the surface of the bump, particularly in the vicinity of the circuit surface. Cover the surface and embed bumps. The thermosetting resin layer in this state is further thermoset by heating to finally form a first protective film, and protects the bumps in close contact with the surface on the circuit surface. For example, after the surface opposite to the circuit surface is ground on the semiconductor wafer after the first protective film forming sheet is pasted, the first support sheet is removed, and then the thermosetting resin layer is heated. Bump embedding and formation of the first protective film are performed, and finally, the semiconductor device is incorporated with the first protective film.
In this specification, the bump surface and the circuit surface of the semiconductor wafer may be collectively referred to as a “bump formation surface”.

As described above, the thermosetting resin film (thermosetting resin layer) of the present invention has a shear rate of 1 s ⁻¹ when the temperature is increased from the state before curing at a temperature increase rate of 10 ° C./min. The time during which the viscosity (hereinafter sometimes abbreviated as “shear viscosity (V1)”) is 100000 Pa · s or less (hereinafter sometimes abbreviated as “Δt1”) is 500 seconds or longer. . That is, when the thermosetting resin film of the present invention is heated so as to satisfy the above temperature increase rate before being cured, it is once softened to decrease the shear viscosity (V1), and then the shear viscosity ( V1) starts to increase, and finally the first protective film is formed as a cured product. And in such a time zone in which the shear viscosity (V1) decreases and starts to increase, a low shear viscosity (V1) of 100,000 Pa · s or less is exhibited, and the low shear viscosity (V1) is compared to 500 seconds or more. It can be maintained for a long time. While the thermosetting resin film of the present invention maintains such a low shear viscosity (V1) for a long time, the bubbles (voids) contained in the stage before curing are contained in the thermosetting resin film itself. It is sufficiently possible to permeate the inside and release it to the outside, and when curing is completed, there is almost or no bubbles. In addition, in this specification, the bubble which the thermosetting resin film before hardening contains includes the bubble which exists between a thermosetting resin film and a bump formation surface.
Therefore, when the thermosetting resin film of the present invention is used, the first protective film finally contains almost or no bubbles, so that the adhesiveness between the bump forming surface and the first protective film is high. The first protective film can sufficiently perform its function, for example, the ability of the protective film to protect the circuit surface and bumps is high. Further, even if the first protective film is heated by solder reflow or the like, the expansion of bubbles does not occur or is suppressed at all, so that the adhesion between the bump forming surface and the first protective film is reduced, or the first protection film is protected. Rupture of the film is suppressed, the protective ability of the first protective film is maintained, and damage to the semiconductor chip is suppressed. Thus, by using the thermosetting resin film of the present invention, the circuit surface and the portion in the vicinity of the circuit surface of the bump, that is, the base portion are sufficiently protected by the first protective film.

  FIG. 1 is a cross-sectional view schematically showing an example of a state in which a first protective film is formed on a bump forming surface using the thermosetting resin film of the present invention. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

A plurality of bumps 91 are provided on the circuit surface 90 a of the semiconductor wafer 90 shown here. The bump 91 has a shape in which a part of a sphere is cut out by a flat surface, and a flat surface corresponding to the cut and exposed portion is in contact with the circuit surface 90 a of the semiconductor wafer 90.
The first protective film 12 ′ is formed using the thermosetting resin film of the present invention, covers the circuit surface 90 a of the semiconductor wafer 90, and further, the top of the bump 91 among the surface 91 a of the bump 91. And the area other than the vicinity thereof. As described above, the first protective film 12 ′ is in close contact with the surface 91 a other than the top of the bump 91 and the vicinity thereof, and is also in close contact with the circuit surface 90 a of the semiconductor wafer 90 to embed the bump 91.
There is no bubble between the surface 91a of the bump 91 and the circuit surface 90a of the semiconductor wafer 90, that is, the bump forming surface, and the first protective film 12 ', and there is no bubble inside the first protective film 12'. There are no bubbles. Such a substantially spherical shape of the bump 91 is particularly advantageous for forming the first protective film in which the inclusion of bubbles is suppressed.

The diameter of the bump 91 in the direction parallel to the circuit surface 90a increases as the height from the lowermost portion of the bump 91 (in other words, the contact portion with the circuit surface 90a) increases. After that, it starts to decrease. That is, the space sandwiched between the surface 91a and the circuit surface 90a at the base of the bump 91 (the vicinity of the circuit surface 90a) and the circuit surface 90a is particularly narrow in the space on the bump formation surface. It gets narrower as you get closer to the bottom. In such a space, it is difficult to fill the protective film, and it is difficult for bubbles in the protective film to escape.
However, by using the thermosetting resin film of the present invention, it is possible to form the first protective film 12 ′ in which the bubble content is sufficiently suppressed even in such a narrow space. Therefore, the substantially spherical shape of the bump 91 as described above is particularly advantageous in that the protective action of the first protective film 12 ′ can be sufficiently obtained at the base of the bump 91.

In addition, the semiconductor wafer which is a use object of the thermosetting resin film of this invention is not limited to what is shown in FIG. 1, In the range which does not impair the effect of this invention, a part of structure is changed, deleted, or added. It may be what was done. For example, FIG. 1 shows a substantially spherical shape as described above (a shape in which a part of the sphere is cut off by a flat surface) as a bump. In FIG. 1, the shape stretched in the direction orthogonal to the circuit surface 90 a of the semiconductor wafer 90, that is, the shape of a spheroid that is almost an oval (the major axis of the spheroid that is an oval). Bumps in a shape where a part including one end is cut off by a flat surface, or a shape obtained by crushing a substantially spherical shape as described above in the height direction, that is, a shape of a spheroid that is substantially oblate (in oblate shape) A bump having a shape in which a portion including one end in the minor axis direction of a certain spheroid is cut off by a flat surface is also exemplified as a bump having a preferable shape. Such a substantially spheroid shaped bump is also particularly advantageous for forming the first protective film in which the inclusion of bubbles is suppressed, like the substantially spherical bump.
In addition, the shape of the bump demonstrated so far is only an example of a preferable thing in the application of the thermosetting resin film of the present invention, and the shape of the bump is not limited to these in the present invention.

On the other hand, FIG. 2 is a cross-sectional view schematically showing an example of a state in which a protective film is formed on a bump forming surface using a conventional thermosetting resin film. 2, the same components as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted.
The protective film 92 ′ shown here is formed using a conventional thermosetting resin film. Bubbles 8 exist inside the protective film 92 ′, and the bubbles 8 are also formed between the surface 91 a of the bump 91 or the circuit surface 90 a of the semiconductor wafer 90, that is, the bump forming surface, and the protective film 92 ′. Exists. In particular, the bubbles 8 are likely to remain between the surface 91a at the base of the bump 91 and the protective film 92 ′. Further, the bubbles 8 are likely to remain in the protective film 92 ′ at the portion sandwiched between the surface 91 a at the base of the bump 91 and the circuit surface 90 a.

As described above, when the thermosetting resin film of the present invention is heated at a rate of temperature increase of 10 ° C./min from before curing, Δt1 is 500 seconds or more, and Δt1 is, for example, It can adjust with the kind and quantity of the component which a thermosetting resin film mentions later.
Δt1 of the thermosetting resin film of the present invention is preferably 520 seconds or longer, for example, any of 540 seconds or longer, 560 seconds or longer, 580 seconds or longer, 600 seconds or longer, 620 seconds or longer, 640 seconds or longer, etc. It may be.
On the other hand, the upper limit value of Δt1 of the thermosetting resin film of the present invention is not particularly limited. In that the thermosetting resin film has good thermosetting property, Δt1 is preferably 10,000 seconds or less, more preferably 5000 seconds or less, and further preferably 3000 seconds or less, It is particularly preferably 2000 seconds or less, and for example, it may be 1000 seconds or less.

  As described above, the thermosetting resin film of the present invention is softened once when the temperature is increased at a temperature increase rate of 10 ° C./min from before the curing, and the shear viscosity (V1) is decreased, and is 500 seconds or more. During this period, the shear viscosity (V1) is 100,000 Pa · s or less. The lower limit value of the shear viscosity (V1) exhibited by the thermosetting resin film of the present invention in the process of raising the temperature is not particularly limited, but is preferably 3000 Pa · s, more preferably 6000 Pa · s. Preferably, it is 9000 Pa · s.

When the thermosetting resin film before curing of the present invention is heated at a heating rate of 10 ° C./min, the lower limit of the temperature of the thermosetting resin film at which the shear viscosity is 100000 Pa · s or less is particularly Although not limited, it is preferably 60 ° C, more preferably 65 ° C, and particularly preferably 70 ° C.
Although the thermosetting resin film of the present invention is heated at a heating rate of 10 ° C./min, the upper limit of the temperature of the thermosetting resin film at which the shear viscosity is 100000 Pa · s or less is not particularly limited. 160 ° C., more preferably 150 ° C., and particularly preferably 140 ° C.
By the said temperature of a thermosetting resin film being such a range, the effect which suppresses inclusion of the bubble of a 1st protective film becomes higher.

  In the present invention, the rate of temperature increase of the thermosetting resin film when determining Δt1 is 10 ° C./min. For example, 10 ° C./min, such as about 9.8 to 10.2 ° C./min. Even when the time at which the shear viscosity is 100000 Pa · s or less is measured at a temperature elevation rate other than that, the time is usually not significantly different from Δt1.

  The thermosetting resin film before curing according to the present invention is preferably affixed to a bump forming surface of a semiconductor wafer and then thermally cured under pressure, and the fluidity is increased (ie, softened) by heating to embed the bump. Further, when the first protective film is formed by heat curing by heating, it is more preferable to apply pressure together. Thus, the effect which suppresses the bubble inclusion of a 1st protective film becomes higher by pressing at the time of hardening by heating.

  The pressure applied at the time of softening and curing by heating of the thermosetting resin film of the present invention may be appropriately adjusted, but is preferably 0.1 Pa or more, more preferably 0.1 MPa to 1 MPa, and 2 MPa to 0.8 MPa is more preferable, and 0.4 MPa to 0.6 MPa is particularly preferable. When the pressure is equal to or higher than the lower limit value, the effect of suppressing the inclusion of bubbles in the first protective film is further increased. When the pressure is equal to or lower than the upper limit value, the circuit surface of the semiconductor wafer is damaged. The suppression effect becomes high.

  The thermosetting resin film before curing of the present invention is preferably pressurized by placing it in a pressurized atmosphere during softening and curing by heating. By doing in this way, a thermosetting resin film can be pressurized easily.

What is necessary is just to adjust suitably the heating temperature when making the thermosetting resin film of this invention soften and harden | cure by heating according to the kind etc. of a thermosetting resin film, It is preferable that it is 60-200 degreeC.
Hereinafter, the configuration of the present invention will be described in detail.

◎ First support sheet The first support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of 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 as long as the effects of the present invention are not impaired.
In the present specification, not only the case of the first support sheet, but “a 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, and only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent material and thickness of each layer is different from each other ” "Means.

  As a preferable first support sheet, for example, a sheet in which a first pressure-sensitive adhesive layer is laminated on a first substrate, a first intermediate layer is laminated on a first substrate, and a first intermediate layer is formed on the first intermediate layer. Examples include one in which one pressure-sensitive adhesive layer is laminated, one made only of a first base material, and the like.

Examples of the first protective film-forming sheet of the present invention will be described below for each kind of the first support sheet with reference to the drawings.
FIG. 3 is a cross-sectional view schematically showing an embodiment of the first protective film-forming sheet of the present invention. The 1st sheet | seat 1 for protective film formation shown here uses as a 1st support sheet what laminated | stacked the 1st adhesive layer on the 1st base material. That is, the first protective film forming sheet 1 includes a first pressure-sensitive adhesive layer 13 on a first base material 11, and a thermosetting resin layer (thermosetting resin film) 12 on the first pressure-sensitive adhesive layer 13. It is prepared and configured. The first support sheet 101 is a laminate of the first base material 11 and the first pressure-sensitive adhesive layer 13, and is on one surface 101 a of the first support sheet 101, that is, on one surface 13 a of the first pressure-sensitive adhesive layer 13. Further, a thermosetting resin layer 12 is provided.
In the first protective film forming sheet 1, as described above, when the thermosetting resin layer 12 is heated at a rate of temperature increase of 10 ° C./min from before curing, Δt 1 becomes 500 seconds or more.

FIG. 4 is a cross-sectional view schematically showing another embodiment of the first protective film-forming sheet of the present invention. 4, the same components as those shown in FIG. 3 are denoted by the same reference numerals as those in FIG. 3, and detailed description thereof is omitted. The same applies to the drawings after FIG.
The first protective film forming sheet 2 shown here is a first support sheet in which a first intermediate layer is laminated on a first base material, and a first adhesive layer is laminated on the first intermediate layer. Something is used. That is, the first protective film forming sheet 2 includes 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 Are provided with a thermosetting resin layer (thermosetting resin film) 12. The first support sheet 102 is a laminate in which the first base material 11, the first intermediate layer 14, and the first pressure-sensitive adhesive layer 13 are laminated in this order, and on the one surface 102a of the first support sheet 102, that is, A thermosetting resin layer 12 is provided on one surface 13 a of the first pressure-sensitive adhesive layer 13.
In other words, in the first protective film forming sheet 1 shown in FIG. 3, the first protective film forming sheet 2 further includes a first intermediate layer 14 between the first base material 11 and the first pressure-sensitive adhesive layer 13. It is equipped with.
In the first protective film forming sheet 2, as described above, when the thermosetting resin layer 12 is heated at a temperature rising rate of 10 ° C./min from before the curing, Δt 1 becomes 500 seconds or more.

FIG. 5 is a cross-sectional view schematically showing still another embodiment of the first protective film-forming sheet of the present invention.
In the first protective film forming sheet 3 shown here, a first support sheet made of only the first base material is used. That is, the first protective film forming sheet 3 includes a thermosetting resin layer (thermosetting resin film) 12 on the first base material 11 and is configured. The first support sheet 103 includes only the first base material 11, and the thermosetting resin layer 12 is formed on one surface 103 a of the first support sheet 103, that is, on one surface 11 a of the first base material 11. Provided in direct contact.
In other words, the first protective film forming sheet 3 is obtained by removing the first pressure-sensitive adhesive layer 13 from the first protective film forming sheet 1 shown in FIG.
In the first protective film forming sheet 3, as described above, when the thermosetting resin layer 12 is heated at a rate of temperature increase of 10 ° C./min from before curing, Δt 1 becomes 500 seconds or more.
Next, the configuration of the first support sheet will be described in detail.

-1st base material The said 1st base material is a sheet form or a film form, As a constituent material, various resin is mentioned, for example.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyolefin; Ethylene-based copolymer such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer) A copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have aromatic cyclic groups; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

  In this specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid. For example, “(meth) acrylate” is a concept including both “acrylate” and “methacrylate”, and “(meth) acryloyl group” Is a concept including both an “acryloyl group” and a “methacryloyl group”.

  Only 1 type may be sufficient as resin which comprises a 1st base material, and when it is 2 or more types and they are 2 or more types, those combinations and ratios can be selected arbitrarily.

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

The thickness of the first substrate is preferably 5 to 1000 μm, more preferably 10 to 500 μm, still more preferably 15 to 300 μm, and particularly preferably 20 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 all of the first base material. Means the total thickness of the layers.

  The first base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to construct the first base material having such a high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. Examples include coalescence.

  The first base material contains various known 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. You may do it.

The first substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
When the 1st adhesive layer or curable resin layer mentioned later has energy-beam sclerosis | hardenability, what transmits an energy beam is preferable for a 1st base material.

  The first substrate can be manufactured by a known method. For example, the 1st base material containing resin can be manufactured by shape | molding the resin composition containing the said resin.

-1st adhesive layer The said 1st adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the pressure-sensitive adhesive include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber resin (a resin having a rubber structure). ), Silicone resins (adhesives composed of resins having a siloxane bond), epoxy resins (adhesives composed of resins having an epoxy group), polyvinyl ether, polycarbonate, and other adhesive resins. Based resins are preferred.

  In the present invention, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself has an adhesive property, Also included are resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water.

  The first pressure-sensitive adhesive layer may be only one layer (single layer), or may be 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. The combination is not particularly limited.

The thickness of the first pressure-sensitive adhesive layer is preferably 1-1000 μm, more preferably 5-500 μm, and particularly preferably 10-100 μm.
Here, the “thickness of the first pressure-sensitive adhesive layer” means the thickness of the entire first pressure-sensitive adhesive layer. For example, the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers means the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.

The first pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive. The first pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
In the present invention, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present invention, “energy ray curable” means the property of being cured by irradiation with energy rays, and “non-energy ray curable” means the property of not being cured even when irradiated with energy rays. .

<< 1st adhesive composition >>
A 1st adhesive layer can be formed using the 1st adhesive composition containing an adhesive. For example, a 1st adhesive layer can be formed in the target site | part by applying a 1st adhesive composition to the formation object surface of a 1st adhesive layer, and making it dry as needed. A more specific method for forming the first pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers. In the first pressure-sensitive adhesive composition, the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the first pressure-sensitive adhesive layer. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example.

  The first pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.

  Although the drying conditions of a 1st adhesive composition are not specifically limited, When the 1st adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. The first pressure-sensitive adhesive composition containing the solvent is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes, for example.

  When the first pressure-sensitive adhesive layer is energy ray-curable, the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable first pressure-sensitive adhesive composition is, for example, non-energy A first pressure-sensitive adhesive composition containing a linear curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound. (I-1); energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter referred to as “adhesiveness”) A first pressure-sensitive adhesive composition (I-2) containing the resin (I-2a) ”; the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound; The 1st adhesive composition (I-3) etc. to contain are mentioned.

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

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
The acrylic resin may have only one type of structural unit, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred.
More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meta ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, icosyl (meth) acrylate, and the like.

  From the viewpoint of improving the adhesive strength of the first pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms. And from the point which the adhesive force of a 1st adhesive layer improves more, it is preferable that carbon number of the said alkyl group is 4-12, and it is more preferable that it is 4-8. In addition, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group reacts with a crosslinking agent to be described later to become a starting point of crosslinking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound, The thing which enables introduction | transduction of an unsaturated group to the side chain of an acrylic polymer is mentioned.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino 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, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic polymers such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.

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

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

  As for the functional group-containing monomer constituting the acrylic polymer, only one type may be used, or two or more types may be used, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

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

  The other monomer constituting the acrylic polymer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
On the other hand, the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).
In the present invention, “energy beam polymerizability” means a property of polymerizing by irradiation with energy rays.

  Only 1 type may be sufficient as adhesive resin (I-1a) which a 1st adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios are Can be arbitrarily selected.

  In 1st adhesive composition (I-1), it is preferable that content of adhesive resin (I-1a) is 5-99 mass%, It is more preferable that it is 10-95 mass%, 15 It is especially preferable that it is -90 mass%.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4. Polyhydric (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the first pressure-sensitive adhesive layer is difficult to be lowered.

  The energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and when two or more types, the combination and ratio thereof are arbitrary. You can choose.

  In the first pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, It is especially preferable that it is 85 mass%.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used in addition to the structural unit derived from an alkyl (meth) acrylate as the adhesive resin (I-1a), the first pressure-sensitive adhesive composition It is preferable that a thing (I-1) contains a crosslinking agent further.

The said crosslinking agent reacts with the said functional group, for example, and bridge | crosslinks adhesive resin (I-1a).
As a crosslinking agent, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based crosslinking agents such as adducts of these diisocyanates (crosslinking agent having an isocyanate group); epoxy-based crosslinking agents such as ethylene glycol glycidyl ether ( A cross-linking agent having a glycidyl group); an aziridine-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (a cross-linking agent having an aziridinyl group); a metal chelate cross-linking agent such as an aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanuric acid skeleton) and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and improving the adhesive strength of the first pressure-sensitive adhesive layer, and being easily available.

  Only 1 type may be sufficient as the crosslinking agent which 1st adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In said 1st adhesive composition (I-1), content of a crosslinking agent is 0.01-50 mass parts with respect to 100 mass parts of adhesive resin (I-1a) content. Preferably, it is 0.1-20 mass parts, More preferably, it is 1-10 mass parts.

[Photopolymerization initiator]
The first pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. Even if the 1st adhesive composition (I-1) containing a photoinitiator irradiates energy rays of comparatively low energy, such as an ultraviolet-ray, hardening reaction fully advances.

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, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as 2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc. Α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

  Only 1 type may be sufficient as the photoinitiator which 1st adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

  In 1st adhesive composition (I-1), it is preferable that content of a photoinitiator is 0.01-20 mass parts with respect to 100 mass parts of contents of the said energy-beam curable compound. 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.

[Other additives]
The 1st adhesive composition (I-1) may contain the other additive which does not correspond to any of the above-mentioned components in the range which does not impair the effect of this invention.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
The reaction retarder is, for example, in the first pressure-sensitive adhesive composition (I-1) being stored by the action of the catalyst mixed in the first pressure-sensitive adhesive composition (I-1). It suppresses that the crosslinking reaction which does not progress. Examples of the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C (═O) —) in one molecule. Can be mentioned.

  As for the other additive which 1st adhesive composition (I-1) contains, only 1 type may be sufficient, and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

  In 1st adhesive composition (I-1), content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[solvent]
The first pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the first pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for application to the surface to be coated is improved.

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

  As the solvent, for example, the solvent used in the production of the adhesive resin (I-1a) is used as it is in the first adhesive composition (I-1) without being removed from the adhesive resin (I-1a). Alternatively, the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the first pressure-sensitive adhesive composition (I-1).

  Only 1 type may be sufficient as the solvent which 1st adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In 1st adhesive composition (I-1), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<First pressure-sensitive adhesive composition (I-2)>
As described above, the first pressure-sensitive adhesive composition (I-2) is an energy-ray-curable adhesive in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable adhesive resin (I-1a). Containing a functional resin (I-2a).

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

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group. A compound having a group.
Examples of the energy ray polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethenyl group), an allyl group (2-propenyl group), and the like, and a (meth) acryloyl group is preferable.
Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of binding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of binding to a carboxy group or an epoxy group. Etc.

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

  Only 1 type may be sufficient as the adhesive resin (I-2a) which 1st adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios are Can be arbitrarily selected.

  In the first pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass. It is especially preferable that it is -90 mass%.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, the first adhesive composition The product (I-2) may further contain a crosslinking agent.

As said crosslinking agent in 1st adhesive composition (I-2), the same thing as the crosslinking agent in 1st adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the crosslinking agent which 1st adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the first pressure-sensitive adhesive composition (I-2), the content of the crosslinking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). Preferably, it is 0.1-20 mass parts, More preferably, it is 1-10 mass parts.

[Photopolymerization initiator]
The first pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the 1st adhesive composition (I-2) containing a photoinitiator irradiates energy rays of comparatively low energy, such as an ultraviolet-ray, hardening reaction fully advances.

Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the first pressure-sensitive adhesive composition (I-1).
1 type may be sufficient as the photoinitiator which 1st adhesive composition (I-2) contains, and when it is 2 or more types and they are 2 or more types, those combinations and ratios can be selected arbitrarily. .

  In 1st adhesive composition (I-2), content of a photoinitiator is 0.01-20 mass parts with respect to 100 mass parts of adhesive resin (I-2a) content. Is preferable, 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.

[Other additives]
The 1st adhesive composition (I-2) may contain the other additive which does not correspond to any of the above-mentioned components in the range which does not impair the effect of this invention.
As said other additive in 1st adhesive composition (I-2), the same thing as the other additive in 1st adhesive composition (I-1) is mentioned.
As for the other additive which 1st adhesive composition (I-2) contains, 1 type may be sufficient and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

  In 1st adhesive composition (I-2), content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[solvent]
The first pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
As said solvent in 1st adhesive composition (I-2), the same thing as the solvent in 1st adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the solvent which 1st adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In 1st adhesive composition (I-2), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

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

  In 1st adhesive composition (I-3), it is preferable that content of adhesive resin (I-2a) is 5-99 mass%, It is more preferable that it is 10-95 mass%, 15 It is especially preferable that it is -90 mass%.

[Energy ray curable low molecular weight compound]
Examples of the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) include monomers and oligomers that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays. The same thing as the energy-beam curable compound which 1st adhesive composition (I-1) contains is mentioned.
1 type may be sufficient as the said energy-beam curable low molecular weight compound which 1st adhesive composition (I-3) contains, and when it is 2 or more types, those combinations and ratios are Can be arbitrarily selected.

  In the first pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable low molecular weight compound is 0.01 to 300 with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). It is preferable that it is a mass part, It is more preferable that it is 0.03-200 mass part, It is especially preferable that it is 0.05-100 mass part.

[Photopolymerization initiator]
The first pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. Even if the 1st adhesive composition (I-3) containing a photoinitiator irradiates energy rays of comparatively low energy, such as an ultraviolet-ray, hardening reaction fully advances.

Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiator as in the first pressure-sensitive adhesive composition (I-1).
Only 1 type may be sufficient as the photoinitiator which 1st adhesive composition (I-3) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

  In 1st adhesive composition (I-3), content of a photoinitiator is with respect to 100 mass parts of total content of adhesive resin (I-2a) and the said energy-beam curable low molecular compound. The amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The 1st adhesive composition (I-3) may contain the other additive which does not correspond to any of the above-mentioned components in the range which does not impair the effect of this invention.
As said other additive, the same thing as the other additive in 1st adhesive composition (I-1) is mentioned.
1 type of other additives which a 1st adhesive composition (I-3) contains may be only 1 type, and may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

  In 1st adhesive composition (I-3), content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[solvent]
The first pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
As said solvent in 1st adhesive composition (I-3), the same thing as the solvent in 1st adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the solvent which 1st adhesive composition (I-3) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In 1st adhesive composition (I-3), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<First pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3)>
Up to this point, the first pressure-sensitive adhesive composition (I-1), the first pressure-sensitive adhesive composition (I-2) and the first pressure-sensitive adhesive composition (I-3) have been mainly described. Are described as general first pressure-sensitive adhesive compositions other than these three types of first pressure-sensitive adhesive compositions (in this specification, “first pressure-sensitive adhesive compositions (I-1) to (I- It is also possible to use the same in the first pressure-sensitive adhesive composition other than 3).

As the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable pressure-sensitive adhesive composition, a non-energy ray-curable pressure-sensitive adhesive composition. Also mentioned.
Non-energy ray curable adhesive compositions include, for example, acrylic resins (resins having (meth) acryloyl groups), urethane resins (resins having urethane bonds), rubber resins (resins having a rubber structure). , Silicone resins (resins having a siloxane bond), epoxy resins (resins having an epoxy group), polyvinyl ethers, or resins containing an adhesive resin such as polycarbonate, and those containing acrylic resins are preferred. .

  It is preferable that 1st adhesive compositions other than 1st adhesive composition (I-1)-(I-3) contain 1 type, or 2 or more types of crosslinking agents, The content is the above-mentioned. It can be the same as in the case of the first pressure-sensitive adhesive composition (I-1) and the like.

<< Method for Producing First Adhesive Composition >>
The first pressure-sensitive adhesive composition, such as the first pressure-sensitive adhesive compositions (I-1) to (I-3), includes the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive. It is obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

-1st intermediate | middle layer The said 1st intermediate | middle layer is a sheet form or a film form, The constituent material should just be suitably selected according to the objective, and is not specifically limited.
For example, when the protective film covering the semiconductor surface is intended to suppress the deformation of the protective film by reflecting the shape of the bump existing on the semiconductor surface, the preferred constituent material of the first intermediate layer Examples thereof include urethane (meth) acrylate and the like from the viewpoint that the adhesiveness of the first intermediate layer is further improved.

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

The thickness of the first intermediate layer can be adjusted as appropriate according to the height of the bumps on the semiconductor surface to be protected, but is 50 to 600 μm because the influence of the relatively high bumps can be easily absorbed. It is preferable that it is 70-500 micrometers, and it is especially preferable that it is 80-400 micrometers.
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 means all of the first intermediate layer. Means the total thickness of the layers.

<< first intermediate layer forming composition >>
A 1st intermediate | middle layer can be formed using the composition for 1st intermediate | middle layer formation containing the constituent material. For example, the first intermediate layer-forming composition is applied to the surface of the first intermediate layer and dried as necessary, or cured by irradiation with energy rays, so that the first intermediate layer is formed on the target site. Layers can be formed. A more specific method for forming the first intermediate layer will be described in detail later along with methods for forming other layers. The ratio of the content of components that do not vaporize at room temperature in the first intermediate layer forming composition is usually the same as the content ratio of the components of the first intermediate layer. Here, “normal temperature” is as described above.

  The first intermediate layer forming composition may be applied by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife. Examples include a method using various coaters such as a coater, a screen coater, a Meyer bar coater, and a kiss coater.

The drying conditions for the first intermediate layer forming composition are not particularly limited. For example, the composition for forming a first intermediate layer containing a solvent described later is preferably heat-dried. In this case, for example, it is preferably dried at 70 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 energy rays after drying.

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

<First Intermediate Layer Forming Composition (II-1)>
As described above, the first intermediate layer forming composition (II-1) contains urethane (meth) acrylate.

[Urethane (meth) acrylate]
Urethane (meth) acrylate is a compound having at least a (meth) acryloyl group and a urethane bond in one molecule, and has energy ray polymerizability.
The urethane (meth) acrylate may be monofunctional (having only one (meth) acryloyl group in one molecule) or bifunctional or more ((meth) acryloyl group in one molecule). Having two or more), that is, a polyfunctional one. However, in the present invention, it is preferable to use at least a monofunctional urethane (meth) acrylate.

  Examples of the urethane (meth) acrylate contained in the first intermediate layer forming composition include, for example, a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound and a polyvalent isocyanate compound, a hydroxyl group and What was obtained by making the (meth) acrylic-type compound which has a (meth) acryloyl group react is mentioned. Here, the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

  1 type of urethane (meth) acrylate which the composition (II-1) for 1st intermediate | middle layer formation contains may be one, 2 or more types, and when they are 2 or more types, those combinations and ratios are arbitrary. Can be 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 said polyol compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

Examples of the polyol compound include alkylene diol, polyether type polyol, polyester type polyol, and polycarbonate type polyol.
The polyol compound may be any of a bifunctional diol, a trifunctional triol, a tetrafunctional or higher polyol, etc., but a diol is preferable in terms of easy availability and excellent versatility and reactivity. .

-Polyether type polyol The polyether type polyol is not particularly limited, but is preferably a polyether type diol, and examples of the polyether type diol include compounds represented by the following general formula (1). It is done.

(In the formula, 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 general formula “—R—O—” and is not particularly limited as long as it is an integer of 2 or more. Especially, it is preferable that n is 10-250, It is more preferable that it is 25-205, It is especially preferable that it is 40-185.

  In the formula, R is not particularly limited as long as it is a divalent hydrocarbon group, but is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, an ethylene group, a propylene group, or a tetra group. A methylene group is more preferable, and a propylene group or a tetramethylene group is particularly preferable.

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

  By reacting the polyether type diol and the polyvalent isocyanate compound, the terminal isocyanate urethane prepolymer having an ether bond portion represented by the following general formula (1a) is obtained. And by using such a terminal isocyanate urethane prepolymer, the urethane (meth) acrylate has the ether bond part, that is, the structural unit derived from the polyether type diol. .

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

-Polyester type polyol Although the said polyester type polyol is not specifically limited, For example, what was obtained by performing esterification reaction using a polybasic acid or its derivative (s), etc. are mentioned. In the present specification, “derivative” means a compound in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified. Here, the “group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.

As said polybasic acid and its derivative (s), the polybasic acid normally used as a manufacturing raw material of polyester and its derivative (s) are mentioned.
Examples of the polybasic acid include saturated aliphatic polybasic acids, unsaturated aliphatic polybasic acids, aromatic polybasic acids, and the like, and dimer acids corresponding to any of these may be used.

Examples of the saturated aliphatic polybasic acid include saturated aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. .
Examples of the unsaturated aliphatic polybasic acid include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.
Examples of the aromatic polybasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid; aromatic tribasic acids such as trimellitic acid; pyromellitic acid and the like And aromatic tetrabasic acids.

  Examples of the derivative of the polybasic acid include the above-described saturated aliphatic polybasic acids, acid anhydrides of unsaturated aliphatic polybasic acids and aromatic polybasic acids, and hydrogenated dimer acids.

  Any of the polybasic acids or derivatives thereof may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected. .

  The polybasic acid is preferably an aromatic polybasic acid in that it is suitable for forming a coating film having an appropriate hardness.

In the esterification reaction for obtaining the polyester type polyol, a known catalyst may be used as necessary.
Examples of the catalyst include tin compounds such as dibutyltin oxide and stannous octylate; alkoxy titanium such as tetrabutyl titanate and tetrapropyl titanate.

-Polycarbonate type polyol The polycarbonate type polyol is not particularly limited, and examples thereof include those obtained by reacting the same glycol as the compound represented by the formula (1) with an alkylene carbonate.
Here, each of glycol and alkylene carbonate may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected. .

The number average molecular weight calculated from the hydroxyl value of the polyol compound is preferably 1000 to 10,000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000. When the number average molecular weight is 1000 or more, excessive generation of urethane bonds is suppressed, and control of the viscoelastic characteristics of the first intermediate layer becomes easier. Moreover, the excessive softening of a 1st intermediate | middle layer is suppressed because the said number average molecular weight is 10,000 or less.
The number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.
[Number average molecular weight of polyol compound] = [Number of functional groups of polyol compound] × 56.11 × 1000 / [Hydroxyl value of polyol compound (unit: mgKOH / g)]

  The polyol compound is preferably a polyether type polyol, and more preferably a polyether type 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.
A polyvalent isocyanate compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

Examples of the polyvalent isocyanate compound include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and dicyclohexylmethane-2. , 4′-diisocyanate, ω, ω′-diisocyanate dimethylcyclohexane, and the like; 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1, And aromatic diisocyanates such as 5-diisocyanate.
Among these, the polyvalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylylene diisocyanate from the viewpoint of handleability.

((Meth) acrylic compound)
The (meth) acrylic compound to be reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in one molecule.
The said (meth) acrylic-type compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

Examples of the (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyl-3-phenyloxypropyl, pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, hydroxyl group-containing (meth) acrylate such as polypropylene glycol mono (meth) acrylate; N-methylol (meth) acrylamid Hydroxyl group-containing (meth) acrylamide and the like; vinyl alcohol, vinyl phenol or bisphenol A diglycidyl ether (meth) reaction products obtained by reacting acrylic acid.
Among these, the (meth) acrylic compound is preferably a hydroxyl group-containing (meth) acrylic acid ester, more preferably a hydroxyl group-containing (meth) acrylic acid alkyl ester, and (meth) acrylic acid 2- Particularly preferred is hydroxyethyl.

  You may perform reaction with the said terminal isocyanate urethane prepolymer and the said (meth) acrylic-type compound using a solvent, a catalyst, etc. as needed.

  Conditions for reacting the terminal isocyanate urethane prepolymer with the (meth) acrylic compound may be appropriately adjusted. For example, the reaction temperature is preferably 60 to 100 ° C., and the reaction time is 1 to 1. It is preferably 4 hours.

The urethane (meth) acrylate may be an oligomer, a polymer, or a mixture of an oligomer and a polymer, but is preferably an oligomer.
For example, the weight average molecular weight of the urethane (meth) acrylate is preferably 1000 to 100,000, more preferably 3000 to 80000, and particularly preferably 5000 to 65000. Due to the intermolecular force between the structures derived from urethane (meth) acrylate in the polymer of urethane (meth) acrylate and a polymerizable monomer described later, the weight average molecular weight is 1000 or more. Optimization of layer hardness is facilitated.
In the present specification, the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

[Polymerizable monomer]
The first intermediate layer forming composition (II-1) may contain a polymerizable monomer in addition to the urethane (meth) acrylate, from the viewpoint of further improving the film-forming property.
The polymerizable monomer is a compound having energy ray polymerizability and excluding oligomers and polymers having a weight average molecular weight of 1000 or more and having at least one (meth) acryloyl group in one molecule. It is preferable.

  Examples of the polymerizable monomer include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester is a chain having 1 to 30 carbon atoms; a hydroxyl group, an amide group, an amino group, an epoxy group, or the like (Meth) acrylic compound having a functional group of (meth) acrylic ester having an aliphatic cyclic group; (meth) acrylic ester having an aromatic hydrocarbon group; having a heterocyclic group ( (Meth) acrylic acid ester; compound having vinyl group; compound having allyl group.

  Examples of the alkyl (meth) acrylate having a chain alkyl group having 1 to 30 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( (Meth) acrylic acid isopropyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid pentyl, (meth) Hexyl acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic acid Isononyl, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (Lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((meth) Palmiticyl acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), isooctadecyl (meth) acrylate (isostearyl (meth) acrylate), nonadecyl (meth) acrylate , Icosyl (meth) acrylate, and the like.

  Examples of the functional group-containing (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (Meth) acrylamides such as N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide and the like Derivative; having amino group (medium ) Acrylic acid ester (hereinafter sometimes referred to as “amino group-containing (meth) acrylic acid ester”); having a monosubstituted amino group in which one hydrogen atom of the amino group is substituted with a group other than a hydrogen atom (Meth) acrylic acid ester (hereinafter sometimes referred to as “monosubstituted amino group-containing (meth) acrylic acid ester”); two-substitution in which two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms (Meth) acrylic acid ester having an amino group (hereinafter sometimes referred to as “disubstituted amino group-containing (meth) acrylic acid ester”); epoxy such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate (Meth) acrylic acid ester having a group (hereinafter sometimes referred to as “epoxy group-containing (meth) acrylic acid ester”) and the like.

Here, “amino group-containing (meth) acrylic acid ester” means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with an amino group (—NH ₂ ). . Similarly, “monosubstituted amino group-containing (meth) acrylic acid ester” means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a monosubstituted amino group, “Disubstituted amino group-containing (meth) acrylic acid ester” means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a disubstituted amino group.
Examples of the group other than the hydrogen atom in which the hydrogen atom is substituted in the “monosubstituted amino group” and the “disubstituted amino group” (that is, a substituent) include an alkyl group.

  Examples of the (meth) acrylic acid ester having an aliphatic cyclic group include, for example, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and (meth) acrylic acid. Examples include dicyclopentenyloxyethyl, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, and the like.

  Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenylhydroxypropyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Can be mentioned.

The heterocyclic group in the (meth) acrylic acid ester having a heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group.
Examples of the (meth) acrylic acid ester having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryloylmorpholine.

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

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

  The polymerizable monomer preferably has a relatively bulky group from the viewpoint of good compatibility with the urethane (meth) acrylate. Examples of such a polymerizable monomer include (meth) acrylic acid ester having an aliphatic cyclic group, (meth) acrylic acid ester having an aromatic hydrocarbon group, and (meth) acrylic acid having a heterocyclic group. (Meth) acrylic acid ester having an aliphatic cyclic group is more preferable.

  The polymerizable monomer contained in the first intermediate layer forming composition (II-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrarily selected. it can.

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

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

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

  Only 1 type may be sufficient as the photoinitiator which the composition (II-1) for 1st intermediate | middle layer formation contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios are arbitrary. You can choose.

  In the first intermediate layer forming composition (II-1), the content of the photopolymerization initiator is 0.01 to 20 with respect to 100 parts by mass of the total content of the urethane (meth) acrylate and the polymerizable monomer. The amount is preferably part by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Resin components other than urethane (meth) acrylate]
The first intermediate layer forming composition (II-1) may contain a resin component other than the urethane (meth) acrylate within a range not impairing the effects of the present invention.
The kind of the resin component and the content in the first intermediate layer forming composition (II-1) may be appropriately selected according to the purpose, and are not particularly limited.

[Other additives]
The composition for forming the first intermediate layer (II-1) may contain other additives that do not fall under any of the above-described components within a range not impairing the effects of the present invention.
Examples of the other additives include known crosslinking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), and the like. An additive is mentioned.
For example, the chain transfer agent includes a thiol compound having at least one thiol group (mercapto group) in one molecule.

  Examples of the thiol compound include nonyl mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, triazinetrithiol, 1,2,3-propanetrithiol, Tetraethylene glycol-bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakisthioglucorate, dipentaerythritol hexa Kiss (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,4-bis (3-mercaptobutyryloxy) butane, penta Lithritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione Etc.

  The other additive contained in the first intermediate layer forming composition (II-1) may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary. You can choose.

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

[solvent]
The first intermediate layer forming composition (II-1) may contain a solvent. The first intermediate layer forming composition (II-1) contains a solvent, so that the coating suitability to the surface to be coated is improved.

<< Method for Producing First Intermediate Layer Forming Composition >>
The first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) can be obtained by blending each component for constituting the first intermediate layer forming composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

◎ Thermosetting resin layer The thermosetting resin layer (thermosetting resin film) is a layer for protecting the circuit surface of the semiconductor wafer and the bumps provided on the circuit surface. A protective film is formed.

As described above, when the temperature of the thermosetting resin layer is raised at a rate of temperature increase of 10 ° C./min from the state before curing, Δt1 becomes 500 seconds or more.
Moreover, the said thermosetting resin layer can be formed using the composition for thermosetting resin layer formation containing the constituent material.
Therefore, Δt1 of the thermosetting resin layer can be adjusted by adjusting either or both of the types and amounts of the components contained in the thermosetting resin layer forming composition.
The composition for forming a thermosetting resin layer and the production method thereof will be described in detail later.

For example, among the components contained in the composition for forming a thermosetting resin layer, Δt1 can be more easily adjusted to a preferred range by reducing the content of the component that increases the viscosity in the composition. Examples of the component that increases the viscosity include a filler (D) described later, but are not limited thereto.
In addition, for example, among the components contained in the composition for forming a thermosetting resin layer, Δt1 can be more easily adjusted to a preferred range by increasing the content of the component that particularly reduces the viscosity in the composition. . Examples of the component for reducing the viscosity include, but are not limited to, a thermoplastic resin described later.
In addition, for example, among the components of the composition for forming a thermosetting resin layer, in particular, the content of the thermosetting component in the composition is reduced, or the effect of the thermosetting component is mild. By using this, Δt1 can be more easily adjusted to the preferred range. Although the said thermosetting component can be suitably selected from the thermosetting component (B) mentioned later (for example, an epoxy resin (B1) and a thermosetting agent (B2)) etc., for example, it is not limited to this.

  As a preferable thermosetting resin layer, what contains a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is a component that can be regarded as formed by polymerization reaction of the polymerizable compound. The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger. In the present invention, the polymerization reaction includes a polycondensation reaction.

The thermosetting resin layer may be only one layer (single layer), or may be two or more layers. When there are a plurality of layers, these layers may be the same or different from each other. The combination of is not particularly limited.
When the thermosetting resin layer is a plurality of layers, the entire thermosetting resin layer only needs to satisfy the above-described condition of Δt1.

The thickness of the thermosetting resin layer is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the thermosetting resin layer is equal to or more than the lower limit value, it is possible to form a first protective film with higher protection ability. Moreover, the effect which suppresses the bubble content of a 1st protective film becomes higher because the thickness of a thermosetting resin layer is below the said upper limit.
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 the thermosetting resin layer. Means the total thickness of all the layers that make up.

<< Composition for forming thermosetting resin layer >>
A thermosetting resin layer can be formed using the composition for thermosetting resin layer formation containing the constituent material. For example, a thermosetting resin layer can be formed at a target site by applying a thermosetting resin layer forming composition to the surface on which the thermosetting resin layer is to be formed and drying it as necessary. In the composition for forming a thermosetting resin layer, the ratio of the contents of components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the thermosetting resin layer. Here, “normal temperature” is as described above.

  The thermosetting resin layer forming composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, Examples include a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

  Although the drying conditions of the composition for thermosetting resin layer formation are not specifically limited, When the composition for thermosetting resin layer formation contains the solvent mentioned later, it is preferable to heat-dry. The composition for forming a thermosetting resin layer containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.

<Resin layer forming composition (III-1)>
As the composition for forming a thermosetting resin layer, for example, a composition for forming a thermosetting resin layer (III-1) containing a polymer component (A) and a thermosetting component (B) (in this specification) May be simply abbreviated as “resin layer forming composition (III-1)”).

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility and the like 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 only one type, two or more types, or two or more types. Combinations and ratios can be arbitrarily selected.

  Examples of the polymer component (A) include an acrylic resin (a resin having a (meth) acryloyl group), a polyester, a urethane resin (a resin having a urethane bond), an acrylic urethane resin, and a silicone resin (having a siloxane bond). Resin), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide and the like, and acrylic resin is preferable.

As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is not less than the lower limit, the shape stability of the thermosetting resin layer (time stability during storage) is improved. Moreover, it becomes easy for a thermosetting resin layer to follow the uneven surface of a to-be-adhered body because the weight average molecular weight of acrylic resin is below the said upper limit.

  The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. When Tg of the acrylic resin is equal to or more than the lower limit value, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved. Moreover, adhesive force with the to-be-adhered body of a thermosetting resin layer and a 1st protective film improves because Tg of acrylic resin is below the said upper limit.

  The acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. Examples include copolymers of two or more monomers.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) acrylic acid (Uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as heptadecyl acrylate and octadecyl (meth) acrylate (stearyl (meth) acrylate), has a chain structure having 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic esters such as (meth) acrylic acid N-methylaminoethyl. Here, the “substituted amino group” means a group formed by replacing one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

  The acrylic resin is, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like in addition to the (meth) acrylic acid ester. May be obtained by copolymerization.

  The monomer constituting the acrylic resin may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

  The acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). . When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the first protective film forming sheet tends to be improved.

  In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used alone without using an acrylic resin. Alternatively, it may be used in combination with an acrylic resin. By using the thermoplastic resin, the peelability of the first protective film from the first support sheet is improved, and the thermosetting resin layer easily follows the uneven surface of the adherend.

  The thermoplastic resin preferably has a weight average molecular weight of 1000 to 100,000, more preferably 3000 to 80,000.

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

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

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

  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 polymer component (A) of the thermosetting resin layer) Content) is preferably 5 to 85% by mass, more preferably 5 to 80% by mass, for example, 5 to 70% by mass, regardless of the type of the polymer component (A). -60 mass%, 5-50 mass%, 5-40 mass%, and 5-30 mass% may be sufficient. However, these content in the composition (III-1) for resin layer formation is an example.

  The polymer component (A) may also correspond to the thermosetting component (B). In this invention, when the composition (III-1) for resin layer formation contains the component applicable to both such a polymer component (A) and a thermosetting component (B), for resin layer formation The composition (III-1) is considered to contain a polymer component (A) and a thermosetting component (B).

[Thermosetting component (B)]
The thermosetting component (B) is a component for 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 only one type, two or more types, and when two or more types, These combinations and ratios can be arbitrarily selected.

  Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like, and epoxy thermosetting resins are preferable.

(Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy-type thermosetting resin contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one type, two or more types, or two or more types. Combinations and ratios can be arbitrarily selected.

・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.

  As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the 1st sheet | seat for protective film formation improves by using the epoxy resin which has an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth). An acrylamide group etc. are mentioned, An acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000 from the viewpoints of curability of the thermosetting resin layer and strength and heat resistance of the first protective film after curing. 400 to 10,000 is more preferable, and 500 to 3000 is particularly preferable.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.

  As the epoxy resin (B1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
As a thermosetting agent (B2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins.
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.

  In the case of using a phenolic curing agent as the thermosetting agent (B2), the thermosetting agent (B2) has a softening point or a glass transition temperature from the viewpoint of improving the peelability of the first protective film from the first support sheet. A high one is preferred.

Among the thermosetting agents (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-based phenol resin, an aralkyl phenol resin is preferably 300 to 30000, More preferably, it is 400-10000, and it is especially preferable that it is 500-3000.
Among the thermosetting agents (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

  A thermosetting agent (B2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  In the resin layer forming composition (III-1) and the thermosetting resin layer, the content of the thermosetting agent (B2) is 0.1 to 500 parts per 100 parts by mass of the epoxy resin (B1). It is preferable that it is a mass part, and it is more preferable that it is 1-200 mass parts, for example, 5-100 mass parts, 10-80 mass parts, and 15-60 mass parts may be sufficient. When the content of the thermosetting agent (B2) is equal to or more than the lower limit, curing of the thermosetting resin layer is more likely to proceed. Moreover, the moisture absorption rate of a thermosetting resin layer is reduced because the said content of a thermosetting agent (B2) is below the said upper limit, The package obtained using the sheet | seat for 1st protective film formation Reliability is further improved.

  In the resin layer forming composition (III-1) and the thermosetting resin layer, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is The content of the polymer component (A) is preferably 50 to 1000 parts by mass, more preferably 100 to 900 parts by mass, and particularly preferably 150 to 800 parts by mass with respect to 100 parts by mass of the polymer component (A). Preferably, for example, any of 200 to 700 parts by mass and 250 to 650 parts by mass may be used. When the content of the thermosetting component (B) is within such a range, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[Curing accelerator (C)]
The resin layer forming composition (III-1) and the thermosetting resin layer may 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 curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms) An imidazole substituted with a group of; an organic phosphine such as tributylphosphine, diphenylphosphine, triphenylphosphine (a phosphine having one or more hydrogen atoms substituted with an organic group); tetraphenylphosphonium tetraphenylborate Tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.

  As for the hardening accelerator (C) which the composition (III-1) for resin layer formation and a thermosetting resin layer contain, 1 type may be sufficient, 2 or more types may be sufficient, Combinations and ratios can be arbitrarily selected.

  When the curing accelerator (C) is used, in the resin layer forming composition (III-1) and the thermosetting resin layer, the content of the curing accelerator (C) is the content of the thermosetting component (B). It is preferable that it is 0.01-10 mass parts with respect to 100 mass parts, It is more preferable that it is 0.05-5 mass parts, For example, 0.1-5 mass parts may be sufficient. The effect by using a hardening accelerator (C) is acquired more notably because the said content of a hardening accelerator (C) is more than the said lower limit. Further, since the content of the curing accelerator (C) is not more than the above upper limit value, for example, the highly polar curing accelerator (C) is deposited in the thermosetting resin layer under high temperature and high humidity conditions. The effect of suppressing segregation by moving toward the adhesion interface with the body is enhanced, and the reliability of the package obtained using the first protective film forming sheet is further improved.

[Filler (D)]
The resin layer forming composition (III-1) and the thermosetting resin layer may contain a filler (D). When the thermosetting resin layer contains the filler (D), the first protective film obtained by curing the thermosetting resin layer can easily adjust the thermal expansion coefficient. And the reliability of the package obtained using the sheet | seat for 1st protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation object of a 1st protective film. Moreover, when the thermosetting resin layer contains the filler (D), the moisture absorption rate of the first protective film can be reduced or the heat dissipation can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

  The resin layer forming composition (III-1) and the filler (D) contained in the thermosetting resin layer may be only one type, two or more types, or combinations of two or more types. The ratio can be arbitrarily selected.

  When the filler (D) is used, 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 resin) The content of the filler (D) in the layer is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, for example, 7 to 25% by mass. When the content of the filler (D) is equal to or higher than the lower limit, the adjustment of the thermal expansion coefficient becomes easier, and when the content of the filler (D) is equal to or lower than the upper limit, Δt1 Adjustment is easier.

  In the present invention, the ratio of the content of the filler (D) to the total content of all components other than the solvent in the resin layer forming composition (III-1) is that the adjustment of Δt1 is easier. (That is, the content of the filler (D) of the thermosetting resin layer) is preferably 35% by mass or less, more preferably 30% by mass or less, for example, 25% by mass or less. Or 0% by mass.

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

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. It is done.

  As for the coupling agent (E) which the composition for resin layer formation (III-1) and a thermosetting resin layer contain, 1 type may be sufficient, 2 or more types may be sufficient, Combinations and ratios can be arbitrarily selected.

  When the coupling agent (E) is used, in the resin layer forming composition (III-1) and the thermosetting resin layer, the content of the coupling agent (E) is the polymer component (A) and the thermosetting. It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of a component (B), It is more preferable that it is 0.05-10 mass parts, 0.1-5 mass parts It is particularly preferred. When the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) in the resin and the adhesion of the thermosetting resin layer to the adherend are improved. The effect by using a coupling agent (E) etc. is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]
As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin. When used, the resin layer forming composition (III-1) and the thermosetting resin layer may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the functional group in the polymer component (A) with another compound to cross-link, and by this cross-linking, initial adhesion of the thermosetting resin layer Force and cohesion can be adjusted.

  Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.

  Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” is as described above.

  More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Like lysine diisocyanate and the like; the compound or two or more are added.

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

  When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a cross-linked structure is formed on the thermosetting resin layer by a reaction between the crosslinking agent (F) and the polymer component (A). Easy to introduce.

  The composition for forming a resin layer (III-1) and the crosslinking agent (F) contained in the thermosetting resin layer may be only one kind, two or more kinds, and combinations thereof when they are two or more kinds. The ratio can be arbitrarily selected.

  In the case of using the crosslinking agent (F), in the resin layer forming composition (III-1), the content of the crosslinking agent (F) is 0. 0 parts by mass relative to 100 parts by mass of the polymer component (A). It is preferably 01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. The effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit. Moreover, the excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.

[Energy ray curable resin (G)]
The resin layer forming composition (III-1) may contain an energy ray curable resin (G). Since the thermosetting resin layer contains the energy ray curable resin (G), the characteristics can be changed by irradiation with energy rays.

The energy beam curable resin (G) is obtained by polymerizing (curing) an energy beam curable compound.
Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.

  Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; Rigoesuteru (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.

  The energy ray curable compound preferably has a weight average molecular weight of 100 to 30,000, and more preferably 300 to 10,000.

  The energy ray-curable compound used for the polymerization may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

  The energy ray curable resin (G) contained in the resin layer forming composition (III-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are as follows: Can be arbitrarily selected.

  When using energy-beam curable resin (G), it is preferable that content of energy-beam curable resin (G) of the composition (III-1) for resin layer formation is 1-95 mass%, More preferably, it is 90 mass%, and it is especially preferable that it is 10-85 mass%.

[Photopolymerization initiator (H)]
When the resin layer forming composition (III-1) contains the energy beam curable resin (G), in order to efficiently advance the polymerization reaction of the energy beam curable resin (G), a photopolymerization initiator (H ) May be contained.

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

  1 type may be sufficient as the photoinitiator (H) which the composition for resin layer formation (III-1) contains, and when it is 2 or more types, those combinations and ratios are arbitrary. Can be selected.

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

[General-purpose additive (I)]
The resin layer forming composition (III-1) and the thermosetting resin layer may contain a general-purpose additive (I) within a range not impairing the effects of the present invention.
The general-purpose additive (I) may be a known one, and can be arbitrarily selected according to the purpose. The general-purpose additive (I) is not particularly limited, but preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye Pigments), gettering agents and the like.

The resin layer forming composition (III-1) and the general-purpose additive (I) contained in the thermosetting resin layer may be only one type, two or more types, and when two or more types, Combinations and ratios can be arbitrarily selected.
The contents of the resin layer forming composition (III-1) and the general-purpose additive (I) in the thermosetting resin layer are 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 resin layer forming composition (III-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. An ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; an amide (a compound having an amide bond) such as dimethylformamide or N-methylpyrrolidone;
The solvent contained in the resin layer forming composition (III-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

<< Method for producing composition for forming thermosetting resin layer >>
The thermosetting resin layer forming composition such as the resin layer forming composition (III-1) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

◇ Method for Producing First Protective Film Forming Sheet The first protective film forming sheet can be produced by sequentially laminating the above-described layers so as to have a corresponding positional relationship. The method for forming each layer is as described above.
For example, when the first support sheet is produced, when the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material, the above-mentioned first pressure-sensitive adhesive composition or A 1st adhesive layer or a 1st intermediate | middle layer can be laminated | stacked by applying the composition for 1st intermediate | middle layer forming, making it dry as needed, or irradiating an energy ray.

  On the other hand, for example, when a thermosetting resin layer is further laminated on the first pressure-sensitive adhesive layer that has been laminated on the first base material, a composition for forming a thermosetting resin layer on the first pressure-sensitive adhesive layer. It is possible to directly form a thermosetting resin layer by coating an object. Similarly, when further laminating the first pressure-sensitive adhesive layer on the first intermediate layer already laminated on the first base material, the first pressure-sensitive adhesive composition is applied on the first intermediate layer. The first pressure-sensitive adhesive layer can be directly formed. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed. However, the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers that have already been formed. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after forming the laminated structure.

For example, a first protective film forming sheet (a first support sheet is a first support sheet) is formed by laminating a first pressure-sensitive adhesive layer on a first base material and laminating a thermosetting resin layer on the first pressure-sensitive adhesive layer. In the case of producing a first protective film-forming sheet that is a laminate of a base material and a first pressure-sensitive adhesive layer), the first pressure-sensitive adhesive composition is applied onto the first base material, and dried as necessary. By laminating the first pressure-sensitive adhesive layer on the first substrate, separately applying a thermosetting resin layer forming composition on the release film, and drying as necessary, A thermosetting resin layer is formed on the release film, and the exposed surface of the thermosetting resin layer is bonded to the exposed surface of the first pressure-sensitive adhesive layer laminated on the first substrate, and thermosetting is performed. A first protective film-forming sheet is obtained by laminating the adhesive resin layer on the first pressure-sensitive adhesive layer.
For example, in the case of producing a first support sheet in which a first intermediate layer is laminated on a first substrate and a first pressure-sensitive adhesive layer is laminated on the first intermediate layer, the first substrate The first intermediate layer-forming composition is applied on the top and dried as necessary, or by irradiating energy rays, so that the first intermediate layer is laminated on the first base material, By applying the first pressure-sensitive adhesive composition on the release film and drying it as necessary, a first pressure-sensitive adhesive layer is formed on the release film, and the exposed surface of the first pressure-sensitive adhesive layer is A first support sheet is obtained by laminating the first pressure-sensitive adhesive layer on the first intermediate layer by laminating the exposed surface of the first intermediate layer already laminated on the first base material. In this case, for example, separately, a thermosetting resin layer forming composition is applied onto the release film, and if necessary, dried to form a thermosetting resin layer on the release film. By laminating the exposed surface of this thermosetting resin layer with the exposed surface of the first pressure-sensitive adhesive layer laminated on the first intermediate layer, the thermosetting resin layer is laminated on the first pressure-sensitive adhesive layer. Thus, a first protective film forming sheet is obtained.

In addition, when laminating | stacking a 1st adhesive layer or a 1st intermediate | middle layer on a 1st base material, as above-mentioned, a 1st adhesive composition or a composition for 1st intermediate | middle layer formation on a 1st base material Instead of the method of applying the product, the first pressure-sensitive adhesive composition or the first intermediate layer-forming composition is applied on the release film, and is dried or irradiated with energy rays as necessary. The first pressure-sensitive adhesive layer or the first intermediate layer is formed on the release film, and the exposed surface of these layers is bonded to one surface of the first base material, whereby the first pressure-sensitive adhesive layer or the first intermediate layer is bonded. An intermediate layer may be laminated on the first substrate.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.

  Thus, since layers other than the first base material constituting the first protective film forming sheet can be formed in advance on the release film and laminated by the method of bonding to the surface of the target layer, What is necessary is just to manufacture the 1st sheet | seat for 1st protective film formation by selecting suitably the layer which employ | adopts such a process as needed.

  In addition, the sheet | seat for 1st protective film formation is normally stored in the state by which the peeling film was bonded together on the surface of the outermost layer (for example, thermosetting resin layer) on the opposite side to the 1st support sheet. Accordingly, a composition for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting resin layer, is applied on the release film (preferably the release-treated surface), and if necessary, By drying, a layer constituting the outermost layer is formed on the release film, and each of the remaining layers is placed on the exposed surface of the layer opposite to the side in contact with the release film. The first protective film-forming sheet can also be obtained by laminating by the method and leaving the laminated film without removing the release film.

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

The component used for manufacture of the composition for thermosetting resin layer formation is shown below.
Polymer component Polymer component (A) -1: butyl acrylate (hereinafter abbreviated as “BA”) (55 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) (10 parts by mass) Acrylic copolymer obtained by copolymerizing glycidyl methacrylate (hereinafter abbreviated as “GMA”) (20 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass). Resin (weight average molecular weight 800,000, glass transition temperature -28 ° C).
Epoxy resin Epoxy resin (B1) -1: Liquid bisphenol F-type epoxy resin (“YL983U” manufactured by Mitsubishi Chemical Corporation)
Epoxy resin (B1) -2: polyfunctional aromatic epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin (B1) -3: dicyclopentadiene type epoxy resin (“EPICLON HP-7200” manufactured by DIC)
Thermosetting agent Thermosetting agent (B2) -1: Novolac type phenolic resin ("BRG-556" manufactured by Showa Denko KK)
Curing accelerator Curing accelerator (C) -1: 2-phenyl-4,5-dihydroxymethylimidazole (“Curesol 2PHZ-PW” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Filler Filler (D) -1: Spherical silica modified with an epoxy group (“Admanano YA050C-MKK” manufactured by Admatechs)

[Production Example 1]
(Production of adhesive resin (I-2a))
Acrylic polymer was obtained by carrying out a polymerization reaction using 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (80 parts by mass) and HEA (20 parts by mass) as raw materials for the copolymer. .
To this acrylic polymer, 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as “MOI”) (22 parts by mass, about 80 mol% with respect to HEA) was added and added at 50 ° C. for 48 hours in an air stream. By carrying out the reaction, the intended adhesive resin (I-2a) was obtained.

[Example 1]
<Manufacture of sheet for forming first protective film>
(Production of thermosetting resin layer forming composition)
Polymer component (A) -1, epoxy resin (B1) -1, epoxy resin (B1) -2, epoxy resin (B1) -3, thermosetting agent (B2) -1, curing accelerator (C) -1 , And filler (D) -1 are dissolved or dispersed in methyl ethyl ketone so that the ratio of these contents is the value shown in Table 1, and stirred at 23 ° C. to form a thermosetting resin layer. As the composition, a resin layer forming composition (III-1) having a solid content concentration of 55% by mass was obtained. In addition, description of "-" of the column of the containing component in Table 1 means that the composition for thermosetting resin layer formation does not contain the component.

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

(Manufacture of sheet for forming first protective film)
The first pressure-sensitive adhesive composition obtained above is applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. The first pressure-sensitive adhesive layer having a thickness of 60 μm was formed by heating and drying at 120 ° C. for 2 minutes.
Next, on the exposed surface of the first pressure-sensitive adhesive layer, as a first substrate, a polyolefin film (thickness 25 μm), an adhesive layer (thickness 2.5 μm), a polyethylene terephthalate film (thickness 50 μm), an adhesive layer A first support sheet was obtained by laminating a laminated film having a thickness of 105 μm in which a (thickness of 2.5 μm) and a polyolefin film (thickness of 25 μm) were laminated in this order.

  The composition for forming a thermosetting resin layer obtained above on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment The product was applied and dried at 100 ° C. for 2 minutes to prepare a thermosetting resin film (thermosetting resin layer) having a thickness of 40 μm.

  Next, the release film is removed from the first pressure-sensitive adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin film obtained above is bonded to the exposed surface of the first pressure-sensitive adhesive layer. And the 1st base material, the 1st adhesive layer, the thermosetting resin layer, and the peeling film obtained the 1st sheet | seat for protective film formation formed by laminating | stacking in this order in these thickness directions.

<Evaluation of thermosetting resin film>
(Measurement of shear viscosity (V1) and Δt1 of thermosetting resin film)
Using the composition for forming a thermosetting resin layer obtained above, the thickness of 500 μm is the same as in the production of the first protective film-forming sheet, except that the coating amount is different. A thermosetting resin film was produced.
Next, a sample for evaluation having a diameter of 25 mm and a thickness of 500 μm was prepared from this thermosetting resin film, and this sample was placed in a shear viscosity measuring apparatus. At this time, in the shear viscosity measuring apparatus, the sample installation location is kept warm at 70 ° C., the sample is placed on the installation location in this state, and the measurement jig is pressed from the upper surface of the sample. The sample was fixed and installed at the installation location.
After maintaining this state for 5 minutes, the sample was heated at a set temperature of 130 ° C. using a temperature control system. Thus, the uncured sample was softened and then cured to form a cured product. The temperature rising rate of the sample at this time was 10 ° C./min. Then, the viscosity of the sample at a shear rate of 1 s ⁻¹ in the process from softening to curing by heating of this sample was measured, and Δt1 was determined to be 550 seconds. The results are shown in Table 3. In Table 3, the heating time after starting the heating of the sample at a set temperature of 130 ° C. and the temperature of the sample at that time are extracted and shown together. Moreover, the relationship of the said heating time of the sample at this time, temperature, and shear viscosity (V1) is shown in FIG. In this heating process, as time passes, powder spills out of the sample installation location, and this phenomenon confirms that the sample is fully cured and finally gelled. did it.

(Confirmation of the bubble-containing suppression effect of the first protective film)
Using a pressure and heat curing apparatus (“RAD-9100” manufactured by Lintec Corporation), the thermosetting resin layer (thermosetting resin film) of the first protective film forming sheet obtained above was set to 0.00. Heating was performed at a set temperature of 130 ° C. for 2 hours while applying a pressure of 5 MPa to soften the thermosetting resin layer (thermosetting resin film), and then cured to form a first protective film.
Next, the first protective film-forming sheet having the cured thermosetting resin layer was taken out from the pressure heat curing apparatus, and the first protective film was observed using an optical microscope. As a result, the first protective film did not contain any bubbles. The results are shown in Table 3.

<Manufacture of sheet for forming first protective film, evaluation of thermosetting resin film>
[Examples 2-7, Comparative Examples 1-3]
A first protective film-forming sheet was produced in the same manner as in Example 1 except that the components and content of the thermosetting resin layer-forming composition were as shown in Table 1 or 2, and thermosetting The resin film was evaluated.
As a result, in Examples 2 to 7, Δt1 of the sample was 520 to 1780 seconds and the first protective film did not contain any bubbles, but in Comparative Examples 1 to 3, Δt1 of the sample was 0 or 320 seconds. The first protective film contained bubbles. These results are shown in Table 3 or 4, and the results of Examples 1 and 2 and Comparative Example 1 are separately shown in FIG.

As is clear from the above results, in Examples 1 to 7 in which Δt1 of the thermosetting resin film was 520 seconds or longer (520 to 1780 seconds), the first protective film contained no bubbles. In these examples, a time zone in which the shear viscosity (V1) of the thermosetting resin film is low is ensured long enough until the end of the curing of the thermosetting resin film. During this period, bubbles in the thermosetting resin film are , All thought to have gone outside.
In contrast, in Comparative Examples 1 to 3, the first protective film contained bubbles. In these comparative examples, until the end of the curing of the thermosetting resin film, the shear viscosity (V1) of the thermosetting resin film was either not at all or short, and during this time, in the thermosetting resin film It was thought that some of the bubbles remained.

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

  1, 2, 3... First protective film forming sheet, 11... First substrate, 11a... Surface of first substrate, 12. Film), 12 '... first protective film, 13 ... first adhesive layer, 13a ... surface of the first adhesive layer, 14 ... first intermediate layer, 101, 102, 103. .... First support sheet, 101a, 102a, 103a ... surface of first support sheet, 90 ... semiconductor wafer, 90a ... circuit surface of semiconductor wafer, 91 ... bump, 91a ... bump Surface of

Claims (3)

A thermosetting resin film for forming a first protective film on the surface by sticking to a surface having bumps of a semiconductor wafer and thermosetting,
When the thermosetting resin film before curing is heated at a heating rate of 10 ° C./min, the time at which the viscosity at the shear rate of 1 s ⁻¹ is 100,000 Pa · s or less is 500 seconds or more. , Thermosetting resin film.   A sheet for forming a first protective film, comprising the thermosetting resin film according to claim 1 on one surface of the first support sheet.   A method for forming a first protective film, wherein the first protective film is formed by thermosetting the thermosetting resin film according to claim 1 at a pressure of 0.1 Pa or more.