JP6774301B2 - Thermosetting resin film and first protective film forming sheet - Google Patents

Description

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

Conventionally, when a multi-pin LSI package used for MPU, gate array, etc. is mounted on a printed wiring board, as a semiconductor chip, a convex electrode (bump) made of eutectic solder, high temperature solder, gold, etc. is attached to the connection pad portion. ) Has been formed, and a flip chip mounting method has been adopted in which these bumps are brought into face-to-face contact with the corresponding terminal portions on the chip mounting substrate and melted / diffused bonded by a so-called face-down method. ..

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

Japanese Unexamined Patent Publication No. 2005-028734

By the way, the portion near the circuit surface of the bump, that is, the base portion is a portion that is easily damaged due to cracks in the process of manufacturing the semiconductor chip from the semiconductor wafer as described above, and even after the semiconductor chip is formed. It is also a part that is easily damaged by applying pressure in the process of mounting this semiconductor chip on a substrate and by applying a load such as exposure to high temperature and high humidity conditions. Therefore, if at least the base portion of the bump and the region near the bump on the circuit surface of the bump forming surface of the semiconductor wafer are protected by covering with a protective film, a sufficient protective effect can be obtained.

Further, as described above, on the bump forming surface, a protective film is formed on the base of the bump and the region in the vicinity thereof, and the circuit surface is exposed without forming the protective film on the other regions, so that the circuit surface is highly selective. By forming a protective film, the following advantageous effects are obtained.
That is, the amount of the curable resin film used for forming the protective film can be significantly reduced, and a sufficient protective effect on the bump-forming surface can be obtained at low cost. In addition, the exposed circuit surfaces of the semiconductor wafer and the semiconductor chip can be easily inspected. Further, when the protective film is formed or the semiconductor wafer after formation is heat-treated, the warp of the semiconductor wafer is suppressed. Further, in the region exposed on the circuit surface of the semiconductor wafer, the dicing line of the semiconductor wafer can be directly observed instead of through the protective film during dicing, and the dicing line can be easily recognized correctly.

However, the protective film disclosed in Patent Document 1 is for forming a protective film on the entire circuit surface of the semiconductor wafer, like other conventional protective films, and as described above, the protective film of the semiconductor wafer On the bump forming surface, the protective film cannot be highly selectively formed in the base of the bump and the region in the vicinity thereof.

Therefore, the present invention provides a thermosetting resin film capable of highly selectively forming a protective film on the bump base and a region in the vicinity thereof on the bump forming surface of the semiconductor wafer, and a protective film forming sheet using the same. The purpose is to do.

In order to solve the above problems, the present invention is a thermosetting resin film for forming a first protective film around the bumps by attaching the semiconductor wafer to a surface having bumps and heat-curing the film. The average viscosity of the thermosetting resin film when melted at 70 to 90 ° C. is 1 to 20000 Pa · s, and the surface free energy of the thermosetting resin film at 23 ° C. is 30 to 40 mJ / m ² . Provided is a thermosetting resin film.
By attaching the thermosetting resin film of the present invention to a surface of a semiconductor wafer having bumps, melting the film, and heat-curing the film, a protective film can be highly selectively formed at the base of the bumps and a region in the vicinity thereof.
The present invention also provides a first protective film forming sheet in which the thermosetting resin film is provided on one surface of the first support sheet.

According to the present invention, there is provided a thermosetting resin film capable of highly selectively forming a protective film on a bump base portion and a region in the vicinity thereof on a bump forming surface of a semiconductor wafer, and a protective film forming sheet using the same. Will be done.

It is a figure which shows typically one Embodiment of the semiconductor wafer provided with the 1st protective film formed by using the thermosetting resin film of this invention, (a) is a plan view, (b) is a sectional view. .. It is a figure which shows typically an example of the semiconductor wafer provided with the protective film formed by using the conventional thermosetting resin film, (a) is a plan view, (b) is a sectional view. FIG. 5 is a plan view schematically showing another example of a semiconductor wafer provided with a protective film formed by using a conventional thermosetting resin film. It is sectional drawing which shows typically one Embodiment of the 1st protective film formation sheet of this invention. It is sectional drawing which shows typically the other embodiment of the 1st protective film forming sheet of this invention. It is sectional drawing which shows still the other embodiment of the 1st protective film formation sheet of this invention schematically. 3 is a graph showing the temperature dependence of the melt viscosity of the thermosetting resin film in Examples 1 and 2 and Comparative Example 1.

The thermosetting resin film of the present invention is a thermosetting resin film for forming a first protective film around the bumps by sticking it on a surface of a semiconductor wafer having bumps and heat-curing the film. A thermosetting resin film having an average viscosity of 1 to 20000 Pa · s when melted at 70 to 90 ° C. and a surface free energy of the thermosetting resin film at 23 ° C. of 30 to 40 mJ / m ² . Is.
By attaching the thermosetting resin film of the present invention to a surface of a semiconductor wafer having bumps, melting the film, and heat-curing the film, a protective film can be highly selectively formed at the base of the bumps and a region in the vicinity thereof.
Further, the first protective film forming sheet of the present invention is provided with the above-mentioned thermosetting resin film of the present invention on one surface of the first support sheet. In the first protective film forming sheet, the "thermosetting resin film" may also 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 its thermosetting resin layer (thermosetting resin film). Then, the thermosetting resin layer after sticking increases in fluidity by heating, spreads between the bumps so as to cover the bumps, and while flowing on the circuit surface, covers the surface of the bumps and embeds the bumps. .. The thermosetting resin layer in this state is further melted by heating, aggregated in the base of the bump and its vicinity, and further heat-cured, and finally is highly selectively selected in the base of the bump and its vicinity. 1 Form a protective film. The first protective film protects the bumps on the circuit surface in close contact with the surface.
After the first protective film forming sheet is attached and the bumps are embedded in the thermosetting resin layer by thermal lamination, the semiconductor wafer has the first support sheet after the surface opposite to the circuit surface is ground. The curable resin layer that has been removed and then melted by heating aggregates at the base of the bump and its vicinity, and subsequent curing forms a highly selective first protective film at the base of the bump and its vicinity. The semiconductor wafer in this state is made into a semiconductor chip with the first protective film provided by dicing, and is finally incorporated into the semiconductor device.

As described above, the thermosetting resin film of the present invention highly selectively forms the first protective film on the bump forming surface in the portion near the circuit surface of the bump, that is, the base portion and the region near the bump on the circuit surface. Form. In this way, by forming the first protective film on the bump forming surface in a region where protection is highly necessary, the amount of the thermosetting resin film used can be significantly reduced, and the bump forming surface can be inexpensively formed. A sufficient protective effect can be obtained, and an exposed circuit surface can be easily inspected.
In the present specification, the “bump forming surface” means a surface in which the surface of the bump and the circuit surface of the semiconductor wafer are combined.

In other words, the thermosetting resin film of the present invention suppresses the formation of the first protective film in a region other than the vicinity of the bump on the circuit surface, so that the semiconductor wafer during or after the formation of the first protective film is formed. When the semiconductor wafer is heat-treated, the warp of the semiconductor wafer is suppressed.
Further, normally, a semiconductor wafer having a protective film formed on a bump forming surface is cut together with the protective film by dicing, and when the semiconductor wafer is formed, the semiconductor wafer is observed from the circuit surface side through the protective film with a camera. It is necessary to recognize the position of the dicing line (that is, the line indicating the part to be diced) existing on the surface of the semiconductor wafer and specify the cutting part of the semiconductor wafer. On the other hand, when the thermosetting resin film of the present invention is used, the formation of the first protective film is suppressed in a region other than the vicinity of the bump on the circuit surface, so that in the region where the circuit surface is exposed. Can directly observe the dicing line of the semiconductor wafer instead of through the first protective film, and it becomes easy to correctly recognize the dicing line.

Since the thermosetting resin film of the present invention has fluidity during heating such that the average viscosity when melted at 70 to 90 ° C. is 1 to 20000 Pa · s, the bump forming surface of the semiconductor wafer After being attached to the wafer, the fluidity is increased by thermal laminating, the top of the bump and its vicinity are penetrated to cover the other surface and the circuit surface of the semiconductor wafer, and the bump is embedded.
Further, the thermosetting resin film of the present invention has a surface free energy of 30 to 40 mJ / m ² at 23 ° C., so that after the bumps are embedded as described above and the first support sheet is removed, the thermosetting resin film has a surface free energy of 30 to 40 mJ / m ² . It melts by continuous heating, aggregates in the base of the bump and the region near the bump on the circuit surface, is further thermoset, and finally is highly selectively first protected in the base of the bump and the region in the vicinity thereof. Form a film.

The average viscosity and surface free energy of the thermosetting resin film of the present invention can be adjusted, for example, by the type and amount of the components contained in the thermosetting resin film described later.

FIG. 1 is a diagram schematically showing an embodiment of a semiconductor wafer provided with a first protective film formed by using the thermosetting resin film of the present invention, and FIG. 1A is a diagram schematically showing an embodiment above the first protective film. It is a plan view when viewed from above, and (b) is a cross-sectional view taken along line I-I of (a).
In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio of each component is the same as the actual one. Is not always the case.
A plurality of bumps 91 are provided on the circuit surface 90a of the semiconductor wafer 90 shown here. The bump 91 has a shape in which a part of the sphere is cut off by a flat surface, and the flat surface corresponding to the cut and exposed portion is in contact with the circuit surface 90a of the semiconductor wafer 90.
The shape of the bump 91 is only an example when the thermosetting resin film of the present invention is applied, and the shape of the bump is not limited to this in the present invention.

The first protective film 12'is formed by using the thermosetting resin film of the present invention, and has a base portion 910 which is a portion of the bump 91 near the circuit surface 90a and a vicinity of the bump 91 of the circuit surface 90a. It is provided in the area 900 and. The top 911 of the bump 91 and its vicinity are projected from the first protective film 12'and are exposed so that they can be electrically connected to other members.
As described above, the first protective film 12'is provided around the bump 91 in close contact with the region other than the top 911 and its vicinity on the surface 91a of the bump 91, and is provided on the semiconductor wafer. With respect to the circuit surface 90a of 90, the area 900 near the bump 91 is provided so that the exposed area 900a of the circuit surface 90a exists between the adjacent bumps 91. Such a substantially spherical shape of the bump 91 is particularly advantageous for highly selectively forming the first protective film in the base of the bump and the region in the vicinity thereof.

The shape of the first protective film 12'is usually determined depending on the shape of the bump 91.
The outer shape of the first protective film 12'when viewed from above is not particularly limited, and as shown in FIG. 1A, the peripheral edge portion in contact with the circuit surface 90a is circular, elliptical, or the like. It may have a specific shape, or the peripheral edge thereof may have an irregular shape. The outer shape and size of the first protective film 12'when viewed from above may be all the same, all may be different, or only a part may be the same. Good. Normally, the outer shape and the size of the first protective film 12'are likely to be different from each other. Further, between the first protective films 12'provided around the adjacent bumps 91, when the outer shapes are different, the outer shapes may be similar or completely different. The tendency of the outer shape depends on the formation conditions of the first protective film 12'and the like.

The semiconductor wafer to which the thermosetting resin film of the present invention is used is not limited to the one shown in FIG. 1, and some configurations are changed, deleted or added within a range not impairing the effect of the present invention. It may be the one that has been done. For example, FIG. 1 shows a bump having a substantially spherical shape (a shape in which a part of the sphere is cut off by a plane) as described above, but such a substantially spherical shape is shown in the height direction (). In FIG. 1, a shape elongated in a direction orthogonal to the circuit surface 90a of the semiconductor wafer 90, that is, a shape of a spheroid that is substantially an oblate spheroid (in the major axis direction of the spheroid that is a prolate spheroid). A bump with a part including one end cut out by a plane) or a shape obtained by crushing the above-mentioned almost spherical shape in the height direction, that is, a spheroid shape (oblate spheroid) A bump having a shape in which a portion including one end in the minor axis direction of a spheroid is cut off by a plane is also mentioned as a bump having a preferable shape. Such a bump having a substantially spheroidal shape is also particularly advantageous for forming the first protective film in a highly selective manner in the base of the bump and the region in the vicinity thereof, similarly to the substantially spherical bump described above. ..

On the other hand, FIG. 2 is a diagram schematically showing an example of a semiconductor wafer provided with a protective film formed by using a conventional thermosetting resin film, and FIG. 2A is a plan view when viewed from above the protective film. It is a figure, (b) is a sectional view in line II-II of (a). In FIG. 2, the same components as those shown in FIG. 1 are designated by the same reference numerals as those in FIG. 1, and detailed description thereof will be omitted. This also applies to the figures after FIG.

The protective film 92'shown here is formed by using a conventional thermosetting resin film. The protective film 92'covers the circuit surface 90a of the semiconductor wafer 90, and further covers a region of the surface 91a of the bump 91 other than the top 911 and its vicinity. In this way, the protective film 92'is in close contact with the region other than the top 911 and its vicinity of the surface 91a of the bump 91, and is also in close contact with the circuit surface 90a of the semiconductor wafer 90 to embed the bump 91. .. As described above, the protective film 92'is different from the first protective film 12'in FIG. 1 in that the protective film 92'is provided so that the exposed region of the circuit surface 90a does not exist between the adjacent bumps 91. That is, the protective film 92'covers the entire surface of the circuit surface 90a of the semiconductor wafer 90 where the bumps 91 are not provided.

FIG. 3 is a diagram schematically showing another example of a semiconductor wafer provided with a protective film formed by using a conventional thermosetting resin film, and is a plan view when viewed from above the protective film.
The protective film 92'shown here has an exposed region 900a of the circuit surface 90a between adjacent bumps 91, but is provided so that the proportion of the exposed region 900a is low. It is different from the first protective film 12'. That is, the protective film 92'is different from the protective film 92'shown in FIG. 2 in that it has a gap so that the exposed region 900a of the circuit surface 90a is partially present. The shape of the exposed region 900a when viewed from above the protective film 92'is not particularly limited.

The average viscosity of the thermosetting resin film of the present invention when melted at 70 to 90 ° C. is 1 to 20000 Pa · s, preferably 10 to 19000 Pa · s, and is 100 to 18000 Pa · s. Is more preferable, and 1000 to 17500 Pa · s is particularly preferable. Further, the average viscosity may be, for example, any one of 10 to 15000 Pa · s, 100 to 10000 Pa · s and 1000 to 10000 Pa · s. When the average viscosity at the time of melting at 70 to 90 ° C. is in such a range, the thermosetting resin film at the time of softening easily forms a surface other than the top of the bump and its vicinity and the circuit surface of the semiconductor wafer. It is possible to cover and embed the bump, and finally to form the first protective film in the base of the bump and the region in the vicinity thereof.

Unless otherwise specified, the "viscosity" in the present specification, such as the viscosity of the thermosetting resin film at the time of melting (hereinafter, may be abbreviated as "melt viscosity"), is referred to by a thin tube rheometer. Means the measured value.

The average viscosity of the thermosetting resin film of the present invention when melted at 70 to 90 ° C. changes the temperature of the thermosetting resin film from 70 ° C. to 90 ° C., at which time 70 ° C., 71 ° C., 72 ° C. The melt viscosity of the thermosetting resin film was measured at intervals of 1 ° C., 88 ° C., 89 ° C., 90 ° C., and the average of the 21 measured values obtained. It is obtained by calculating the value.

The surface free energy of at 23 ° C. of the thermosetting resin film of the present invention is a 30~40mJ / ^{m 2,} is preferably 30.5~39.5mJ / ^{m 2,} in 31~39mJ / ^{m 2} More preferably. Further, the surface free energy may be, for example, any of 33 to 39.5 mJ / m ² , 35 to 39 mJ / m ^2, and 36 to 38.5 mJ / m ² . When the surface free energy is in such a range, the effect that the melted thermosetting resin film after embedding the bump is aggregated around the bump is enhanced.
The surface free energy of the thermosetting resin film of the present invention at 23 ° C. matches or approximates the surface free energy of the bump to be formed of the first protective film at 23 ° C. within the above range. It is preferable to adjust so as to.

For the surface free energy of the thermosetting resin film of the present invention at 23 ° C., the contact angles of water, 1-bromonaphthalene and diiodomethane with respect to the thermosetting resin film at 23 ° C. were measured, and the measured values were used. It is required by applying the Kitazaki-Hata method. The contact angle can be measured, for example, by placing the thermosetting resin film to be measured in an environment of 23 ° C. and stabilizing it at that temperature.

In the semiconductor wafer to which the thermosetting resin film of the present invention is attached, the pitch of the plurality of bumps provided on the circuit surface is not particularly limited, but is preferably 50 to 1000 μm, preferably 100 to 700 μm. It is more preferably present, and particularly preferably 200 to 500 μm. When the bump pitch is at least the lower limit value, the effect of forming the first protective film on the bump forming surface with high selectivity becomes higher as described above. Further, when the bump pitch is equal to or less than the upper limit value, a semiconductor device having the desired performance can be obtained more easily.
In addition, in this specification, "bump pitch" is a part where the height of one bump is the highest when the circuit surface is looked down from above, and the part where the height of a bump adjacent to this bump is the highest. Means the distance between and.

In the semiconductor wafer to which the thermosetting resin film of the present invention is attached, the height of the bumps provided on the circuit surface is not particularly limited, but is preferably 50 to 600 μm, preferably 70 to 500 μm. Is more preferable, and 80 to 400 μm is particularly preferable. When the height of the bump is at least the lower limit value, it becomes easier to form the first protective film highly selectively on the bump forming surface as described above. Further, when the bump height is equal to or less than the upper limit value, it is possible to prevent the bump height from becoming excessive.

The heating temperature at which the thermosetting resin film of the present invention is softened, melted and cured by heating may be appropriately adjusted according to the type of the thermosetting resin film and the like, but is preferably 60 to 200 ° C. ..
Hereinafter, the configuration of the present invention will be described in more detail.

(1) 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 the 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 in the case of the first support sheet, "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. ”Furthermore,“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and the thickness of each layer is different from each other. It means that.

Preferred first support sheets include, for example, one in which a first pressure-sensitive adhesive layer is laminated on a first base material, a first intermediate layer is laminated on a first base material, and a first intermediate layer is laminated on the first intermediate layer. Examples thereof include those in which one pressure-sensitive adhesive layer is laminated and those in which only the first base material is used.

An example of the first protective film forming sheet of the present invention will be described below with reference to the drawings for each type of such first support sheet.
FIG. 4 is a cross-sectional view schematically showing an embodiment of the first protective film forming sheet of the present invention. As the first protective film forming sheet 1 shown here, a sheet obtained by laminating a first pressure-sensitive adhesive layer on a first base material is used as the first support sheet. That is, the first protective film forming sheet 1 includes a first pressure-sensitive adhesive layer 13 on the first base material 11, and a thermosetting resin layer (thermosetting resin film) 12 on the first pressure-sensitive adhesive layer 13. It is configured in preparation. 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 101a of the first support sheet 101, that is, on one surface 13a of the first pressure-sensitive adhesive layer 13. Is provided with a thermosetting resin layer 12.
In the first protective film forming sheet 1, the thermosetting resin layer 12 has an average viscosity of 1 to 20000 Pa · s when melted at 70 to 90 ° C. and surface free energy at 23 ° C. as described above. Is 35-40 mJ / m ² .

FIG. 5 is a cross-sectional view schematically showing another embodiment of the first protective film forming sheet of the present invention. In FIG. 5, the same components as those shown in FIG. 4 are designated by the same reference numerals as those in FIG. 4, and detailed description thereof will be omitted. This also applies to the figures after FIG.
The first protective film forming sheet 2 shown here is formed by laminating a first intermediate layer on a first base material and laminating a first adhesive layer on the first intermediate layer as a first support sheet. I am using something. That is, the first protective film forming sheet 2 is provided with the first intermediate layer 14 on the first base material 11, the first adhesive layer 13 on the first intermediate layer 14, and on the first adhesive layer 13. Is provided with a thermosetting resin layer (thermosetting resin film) 12 and is configured. 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 is on one surface 102a of the first support sheet 102, that is, A thermosetting resin layer 12 is provided on one surface 13a of the first pressure-sensitive adhesive layer 13.
In other words, the first protective film forming sheet 2 is, in other words, in the first protective film forming sheet 1 shown in FIG. 4, between the first base material 11 and the first adhesive layer 13, and further the first intermediate layer 14 It is equipped with.
In the first protective film forming sheet 2, the thermosetting resin layer 12 has an average viscosity of 1 to 20000 Pa · s when melted at 70 to 90 ° C. and surface free energy at 23 ° C. as described above. Is 35-40 mJ / m ² .

FIG. 6 is a cross-sectional view schematically showing still another embodiment of the first protective film forming sheet of the present invention.
As the first protective film forming sheet 3 shown here, a sheet made of only the first base material is used as the first support sheet. That is, the first protective film forming sheet 3 is configured by providing the thermosetting resin layer (thermosetting resin film) 12 on the first base material 11. The first support sheet 103 is composed of only the first base material 11, and the thermosetting resin layer 12 is formed on one surface 103a of the first support sheet 103, that is, on one surface 11a of the first base material 11. It is provided in direct contact.
In other words, the first protective film forming sheet 3 is formed by removing the first adhesive layer 13 from the first protective film forming sheet 1 shown in FIG.
In the first protective film forming sheet 3, the thermosetting resin layer 12 has an average viscosity of 1 to 20000 Pa · s when melted at 70 to 90 ° C. and surface free energy at 23 ° C. as described above. Is 35-40 mJ / m ² .
Next, the configuration of the first support sheet will be described in detail.

○ First base material The first base material is in the form of a sheet or a film, and examples of the constituent materials thereof include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylenes such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer) (Copolymers obtained using); Vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefins; Polyethylene terephthalate, polyethylene Polymers such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all aromatic polyesters in which all constituent units have an aromatic cyclic group; co-polymers of two or more of the above polymers. Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
The resin may be, for example, a crosslinked resin obtained by cross-linking one or more of the resins exemplified above; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

In addition, 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 that includes both "acrylate" and "methacrylate", and is a "(meth) acryloyl group". Is a concept that includes both an "acryloyl group" and a "methacryloyl group".

The resin constituting the first base material may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The first base material may be only one layer (single layer), may be a plurality of layers of two or more layers, and when there are a plurality of layers, the plurality of layers may be the same or different from each other, and a combination of the plurality of layers may be used. Is not particularly limited.

The thickness of the first base material is preferably 5 to 1000 μm, more preferably 10 to 500 μm, further 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, and for example, the thickness of the first base material composed of a plurality of layers is all that constitute the first base material. Means the total thickness of the layers of.

The first base material preferably has a high thickness accuracy, that is, a material in which variation in thickness is suppressed regardless of the site. Among the above-mentioned constituent materials, as a material that can be used to construct a first base material having such a high accuracy of thickness, for example, polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate co-weight. Coalescence and the like can be mentioned.

The first base material contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the resin. You may be doing it.

The first base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.
When the first pressure-sensitive adhesive layer or the curable resin layer, which will be described later, has energy ray curability, the first base material preferably transmits energy rays.

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

○ First Adhesive Layer The first adhesive layer is in the form of a sheet or a film and contains an adhesive.
Examples of the pressure-sensitive adhesive include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane-based resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber-based resin (a resin having a rubber structure). (Adhesive made of), silicone resin (adhesive made of resin having siloxane bond), epoxy resin (adhesive made of resin having epoxy group), polyvinyl ether, adhesive resin such as polycarbonate, etc. Based resin is preferable.

In the present invention, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness. For example, not only the resin itself has adhesiveness but also the resin itself has adhesiveness. It also includes a resin that exhibits adhesiveness when used in combination with other components such as additives, and a resin that exhibits 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), may be a plurality of layers of two or more layers, and when there are a plurality of layers, the plurality of layers may be the same as or different from each other, and the plurality of layers The combination is not particularly limited.

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

The first pressure-sensitive adhesive layer may be formed by using an energy ray-curable pressure-sensitive adhesive or may be formed by using a non-energy ray-curable pressure-sensitive adhesive. The first pressure-sensitive adhesive layer formed by using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
In the present invention, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, 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 source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present invention, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. ..

<< First Adhesive Composition >>
The first pressure-sensitive adhesive layer can be formed by using a first pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the first pressure-sensitive adhesive layer can be formed on a target portion by applying the first pressure-sensitive adhesive composition to the surface to be formed of the first pressure-sensitive adhesive layer and drying it if necessary. A more specific method for forming the first pressure-sensitive adhesive layer will be described in detail later together with a method for forming the other layers. The ratio of the contents of the components that do not vaporize at room temperature in the first pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the first pressure-sensitive adhesive layer. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

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

The drying conditions of the first pressure-sensitive adhesive composition are not particularly limited, but when the first pressure-sensitive adhesive composition contains a solvent described later, it is preferably heat-dried. In this case, for example, 70 to 130 ° C. It is preferable to dry under the condition of 10 seconds to 5 minutes.

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 linearly curable adhesive resin (I-1a) (hereinafter, may be 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, "adhesive"). The first pressure-sensitive adhesive composition (I-2) containing (sometimes abbreviated as "resin (I-2a)"); the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low-molecular-weight compound. Examples thereof include the first pressure-sensitive adhesive composition (I-3) contained therein.

<First 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.
Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from (meth) acrylic acid alkyl ester.
The structural unit of the acrylic resin may be only one type, may be two or more types, and when there are 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 preferable.
More specifically, as the (meth) acrylic acid alkyl ester, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, (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, 2-Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl acrylate (meth), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, ( Hexadecyl acrylate ((meth) palmityl acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecil (meth) acrylate, icosyl (meth) acrylate, etc. Can be mentioned.

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 having 4 or more carbon atoms in the alkyl group. The alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms, from the viewpoint of further improving the adhesive strength of the first pressure-sensitive adhesive layer. Further, 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 the (meth) acrylic acid alkyl ester.
The functional group-containing monomer may be, for example, a starting point of cross-linking when the functional group reacts with a cross-linking agent described later, or when the functional group reacts with an unsaturated group in an unsaturated group-containing compound. Examples thereof include those capable of introducing an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
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, and (meth). (Meta) hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citracon. Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.

As the functional group-containing monomer, a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.

The functional group-containing monomer constituting the acrylic polymer may be only one type, may be two or more types, 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, more preferably 3 to 32% by mass, based on the total amount of the structural units. , 5 to 30% by mass is particularly preferable.

The acrylic polymer may further have a structural unit derived from another monomer 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 other monomer is not particularly limited as long as it can be copolymerized with a (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The other monomer constituting the acrylic polymer may be only one kind, may be two or more kinds, and when there are two or more kinds, 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, a product obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) has the above-mentioned energy ray-curable adhesiveness. It can be used as a resin (I-2a).
In the present invention, "energy ray-polymerizable" means the property of polymerizing by irradiating with energy rays.

The pressure-sensitive adhesive resin (I-1a) contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

In the first pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and 15 It is particularly preferably ~ 90% by 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 trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4. Polyvalent (meth) acrylates such as −butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) Acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.
Urethane (meth) acrylate and urethane (meth) acrylate oligomer are preferable as the energy ray-curable compound in that the molecular weight is relatively large and the storage elastic modulus of the first pressure-sensitive adhesive layer is unlikely to be lowered.

The energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) may be only one kind, two or more kinds, and when two or more kinds, 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, and 10 to 10% by mass. It is particularly preferably 85% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a) in addition to the structural unit derived from the (meth) acrylic acid alkyl ester, the first pressure-sensitive adhesive composition is used. The product (I-1) preferably further contains a cross-linking agent.

The cross-linking agent, for example, reacts with the functional group to cross-link the adhesive resins (I-1a) with each other.
Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; and epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (crosslinking agents). Crosslinking agent having a glycidyl group); Aziridine-based crosslinking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (crosslinking agent having an aziridinyl group); Metal chelate-based crosslinking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanurate skeleton) and the like.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive force of the first pressure-sensitive adhesive layer and being easily available.

The cross-linking agent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the first pressure-sensitive adhesive composition (I-1), the content of the cross-linking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is preferably 0.1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass.

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

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy. Acetphenone compounds such as -2-methyl-1-phenyl-propane-1-one, 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; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketor compounds such as 1-hydroxycyclohexylphenylketone; azo Azo compounds such as bisisobutyronitrile; titanosen compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane 2-Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
Further, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

The photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

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

[Other additives]
The first pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust preventives, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).
The reaction delaying agent is used in the first pressure-sensitive adhesive composition (I-1) during storage due to the action of the catalyst mixed in the first pressure-sensitive adhesive composition (I-1). It suppresses the progress of the cross-linking reaction. Examples of the reaction retarder include those that form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

The other additives contained in the first pressure-sensitive adhesive composition (I-1) may be only one kind, two or more kinds, and when there are two or more kinds, their combinations and ratios can be arbitrarily selected. ..

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

[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 coating suitability on 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, n-hexane and the like. Hydrocarbons; aromatic hydrocarbons such as toluene and xylene; 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 as that 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).

The solvent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

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

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

In addition to the energy ray-polymerizable unsaturated group, the unsaturated group-containing compound can further bond with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

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

The pressure-sensitive adhesive resin (I-2a) contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

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, and 10 It is particularly preferably ~ 90% by 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 pressure-sensitive adhesive composition. The product (I-2) may further contain a cross-linking agent.

Examples of the cross-linking agent in the first pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the first pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the first pressure-sensitive adhesive composition (I-2), the content of the cross-linking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferably 0.1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass.

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

Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiators in the first pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected. ..

In the first pressure-sensitive adhesive composition (I-2), the content of the photopolymerization initiator is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). 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 first pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive in the first pressure-sensitive adhesive composition (I-2) include the same as the other additives in the first pressure-sensitive adhesive composition (I-1).
The other additives contained in the first pressure-sensitive adhesive composition (I-2) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. ..

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

[solvent]
The first pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the first pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the first pressure-sensitive adhesive composition (I-2) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
The solvent contained in the first pressure-sensitive adhesive composition (I-2) may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof can be arbitrarily selected.
In the first pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited and may be appropriately adjusted.

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

In the first pressure-sensitive adhesive composition (I-3), the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and 15 It is particularly preferably ~ 90% by 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 having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. , The same as the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) can be mentioned.
The energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are It can be selected arbitrarily.

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 content of the pressure-sensitive resin (I-2a). It is preferably parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]
The first pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The first pressure-sensitive adhesive composition (I-3) containing the photopolymerization initiator sufficiently promotes the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators in the first pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

In the first pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is based on 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable low molecular weight 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 first pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive include the same as the other additive in the first pressure-sensitive adhesive composition (I-1).
The other additives contained in the first pressure-sensitive adhesive composition (I-3) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. ..

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

[solvent]
The first pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the first pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the first pressure-sensitive adhesive composition (I-3) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
The solvent contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
In the first pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited and may be appropriately adjusted.

<First pressure-sensitive adhesive compositions 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, but the components contained therein. What has been described as is a general first pressure-sensitive adhesive composition other than these three types of first pressure-sensitive adhesive compositions (in the present specification, "first pressure-sensitive adhesive compositions (I-1) to (I-). It can also be used in the same manner with the first pressure-sensitive adhesive composition other than 3).

The first pressure-sensitive adhesive compositions other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to energy ray-curable pressure-sensitive adhesive compositions. Can also be mentioned.
Examples of the non-energy ray-curable pressure-sensitive adhesive composition include acrylic resin (resin having a (meth) acryloyl group), urethane resin (resin having a urethane bond), and rubber resin (resin having a rubber structure). , Silicone-based resin (resin having a siloxane bond), epoxy-based resin (resin having an epoxy group), polyvinyl ether, or a resin containing an adhesive resin such as polycarbonate, and those containing an acrylic resin are preferable. ..

The first pressure-sensitive adhesive compositions other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content thereof is the above-mentioned content. The same can be applied to the case of the first pressure-sensitive adhesive composition (I-1) and the like.

<< Manufacturing method of the first pressure-sensitive adhesive composition >>
The first pressure-sensitive adhesive compositions such as the first pressure-sensitive adhesive compositions (I-1) to (I-3) are the first pressure-sensitive adhesives such as 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 of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
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 appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

○ First Intermediate Layer The first intermediate layer is in the form of a sheet or a film, and the constituent material thereof may be appropriately selected according to the purpose and is not particularly limited.
For example, when the purpose is to prevent the protective film from being deformed by reflecting the shape of the bumps existing on the semiconductor surface on the protective film covering the semiconductor surface, a preferable constituent material of the first intermediate layer is used. Examples thereof include urethane (meth) acrylate and the like from the viewpoint of further improving the adhesiveness of the first intermediate layer.

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

The thickness of the first intermediate layer can be appropriately adjusted according to the height of bumps on the surface of the semiconductor to be protected, but is 50 to 600 μm because the influence of bumps having a relatively high height can be easily absorbed. It is preferably 70 to 500 μm, more preferably 80 to 400 μm.
Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer, and for example, the thickness of the first intermediate layer composed of a plurality of layers is all that constitute the first intermediate layer. Means the total thickness of the layers of.

<< Composition for forming the first intermediate layer >>
The first intermediate layer can be formed by using a composition for forming a first intermediate layer containing the constituent material. For example, the composition for forming the first intermediate layer is applied to the surface to be formed of the first intermediate layer, dried as necessary, or cured by irradiation with energy rays, so that the target portion is first intermediate. Layers can be formed. A more specific method for forming the first intermediate layer will be described in detail later together with a method for forming the other layers. The ratio of the contents of the components that do not vaporize at room temperature in the composition for forming the first intermediate layer is usually the same as the ratio of the contents of the components in the first intermediate layer. Here, "normal temperature" is as described above.

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

The drying conditions of the composition for forming the first intermediate layer are not particularly limited, but the composition for forming the first intermediate layer is preferably heat-dried when it contains a solvent described later, and in this case, for example, for example. It is preferable to dry 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 preferable that the composition is further cured by irradiation with energy rays after drying.

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

<Composition for forming the first intermediate layer (II-1)>
The composition for forming the first intermediate layer (II-1) contains urethane (meth) acrylate as described above.

[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 polymerization property.
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). (Those having two or more), that is, a polyfunctional one, but at least a monofunctional one is preferable.

The urethane (meth) acrylate contained in the product for forming the first intermediate layer includes, for example, a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound with a polyvalent isocyanate compound, and further having a hydroxyl group and Examples thereof include those obtained by reacting a (meth) acrylic compound having a (meth) acryloyl group. Here, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

The urethane (meth) acrylate contained in the composition for forming the first intermediate layer (II-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof 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.
As the polyol compound, 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, the combination and ratio thereof can be arbitrarily selected.

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

-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). Be done.

（式中、ｎは２以上の整数であり；Ｒは２価の炭化水素基であり、複数個のＲは互いに同一であっても異なっていてもよい。）

(In the formula, n is an integer of 2 or more; R is a divalent hydrocarbon group, and a plurality of Rs 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 "-RO-", and is not particularly limited as long as it is an integer of 2 or more. Among them, n is preferably 10 to 250, more preferably 25 to 205, and particularly preferably 40 to 185.

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

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 with the polyhydric isocyanate compound, a terminal isocyanate urethane prepolymer having an ether bond portion represented by the following general formula (1a) can be obtained. Then, by using such a terminal isocyanate urethane prepolymer, the urethane (meth) acrylate has the ether bond portion, that is, the constituent unit derived from the polyether type diol. ..

（式中、Ｒ及びｎは前記と同じである。）

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

-Polyester-type polyol The polyester-type polyol is not particularly limited, and examples thereof include those obtained by carrying out an esterification reaction using a polybasic acid or a derivative thereof. In the present specification, the term "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.

Examples of the polybasic acid and its derivative include polybasic acid and its derivative which are usually used as a raw material for producing polyester.
Examples of the polybasic acid include saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid, aromatic polybasic acid, and the like, and dimer acid corresponding to any of these may be used.

Examples of the saturated aliphatic dibasic 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 dibasic 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; and pyromellitic acid. Aromatic tetrabasic acid and the like.

Examples of the derivative of the polybasic acid include the above-mentioned saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid and acid anhydride of aromatic polybasic acid, hydrogenated dimer acid and the like.

As for the polybasic acid or a derivative thereof, 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, 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 a polyester-type polyol, a known catalyst may be used if necessary.
Examples of the catalyst include tin compounds such as dibutyltin oxide and stannous octylate; alkoxytitanium 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 a glycol similar to the compound represented by the above formula (1) with an alkylene carbonate.
Here, as the glycol and the alkylene carbonate, 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, the combination and ratio thereof can be arbitrarily selected. ..

The number average molecular weight calculated from the hydroxyl value of the polyol compound is preferably 1000 to 10000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000. When the number average molecular weight is 1000 or more, excessive formation of urethane bonds is suppressed, and it becomes easier to control the viscoelastic properties of the first intermediate layer. Further, when the number average molecular weight is 10,000 or less, excessive softening of the first intermediate layer is suppressed.
The number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.
[Number average molecular weight of polyol compound] = [Number of functional groups of polyol compound] × 56.11 × 1000 / [Hydroxy group value of polyol compound (unit: mgKOH / g)]

The polyol compound is preferably a polyether-type polyol, and more preferably a polyether-type diol.

(Multivalent isocyanate compound)
The multivalent isocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.
As the polyisocyanate compound, 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, the combination and ratio thereof can be arbitrarily selected.

Examples of the polyvalent isocyanate compound include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornan diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and dicyclohexylmethane-2. , 4'-diisocyanate, ω, ω'-diisocyanate Diisocyanate Diisocyanate such as dimethylcyclohexane; 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, trizine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1, Examples thereof include aromatic diisocyanates such as 5-diisocyanate.
Among these, the multivalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylylene diisocyanate from the viewpoint of handleability.

((Meta) 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.
As the (meth) acrylic compound, 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, the combination and ratio thereof can be arbitrarily selected.

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-hydroxycyclooxy (meth) acrylate Hydroxyl-containing (meth) acrylic acid esters such as hydroxy-3-phenyloxypropyl, pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; N-methylol (meth) acrylamide, etc. The hydroxyl group-containing (meth) acrylamide; a reaction product obtained by reacting vinyl alcohol, vinylphenol or bisphenol A diglycidyl ether with (meth) acrylic acid can be mentioned.
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-. Hydroxyethyl is particularly preferred.

The reaction between the terminal isocyanate urethane prepolymer and the (meth) acrylic compound may be carried out using a solvent, a catalyst or the like, if necessary.

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

The urethane (meth) acrylate may be any of an oligomer, a polymer, and a mixture of the oligomer and the 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. When the weight average molecular weight is 1000 or more, the first intermediate is caused by the intermolecular force between the structures derived from urethane (meth) acrylate in the polymer of urethane (meth) acrylate and the polymerizable monomer described later. It is easy to optimize the hardness of the layer.
In the present specification, the weight average molecular weight is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

[Polymerizable monomer]
The composition for forming the first intermediate layer (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 polymerizable properties, 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. Is preferable.

Examples of the polymerizable monomer include a (meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has 1 to 30 carbon atoms and is chain-like; a hydroxyl group, an amide group, an amino group, an epoxy group, or the like. Functional group-containing (meth) acrylic compound having a functional group of; (meth) acrylic acid ester having an aliphatic cyclic group; (meth) acrylic acid ester having an aromatic hydrocarbon group; having a heterocyclic group ( Meta) Acrylic acid ester; a compound having a vinyl group; a compound having an allyl group and the like can be mentioned.

Examples of the (meth) acrylic acid alkyl ester having a chain alkyl group having 1 to 30 carbon atoms include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and n-propyl (meth) acrylic acid. Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, n-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylate Isononyl, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate ((meth) acrylate) Myristyl), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), (meth) ) Isooctadecyl acrylate (isostearyl (meth) acrylate), nonadecil (meth) acrylate, icosyl (meth) acrylate and the like can be mentioned.

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. 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, (Meta) 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; (meth) acrylic acid ester having an amino group (hereinafter, may be referred to as "amino group-containing (meth) acrylic acid ester"); one hydrogen atom of the amino group is replaced with a group other than the hydrogen atom. (Meta) acrylic acid ester having a mono-substituted amino group (hereinafter, may be referred to as "mono-substituted amino group-containing (meth) acrylic acid ester"); the two hydrogen atoms of the amino group are other than hydrogen atoms. A (meth) acrylic acid ester having a disubstituted amino group substituted with a group (hereinafter, may be referred to as "disubstituted amino group-containing (meth) acrylic acid ester"); glycidyl (meth) acrylate, (meth). ) A (meth) acrylic acid ester having an epoxy group such as methylglycidyl acrylate (hereinafter, may be referred to as "epoxy group-containing (meth) acrylic acid ester") and the like.

Here, the "amino group-containing (meth) acrylic acid ester" means a compound in which one or more hydrogen atoms of the (meth) acrylic acid ester are substituted with an amino group (-NH ₂ ). .. Similarly, the "mono-substituted amino group-containing (meth) acrylic acid ester" means a compound in which one or more hydrogen atoms of the (meth) acrylic acid ester are substituted with a mono-substituted amino group. The "disubstituted amino group-containing (meth) acrylic acid ester" means a compound in which one or more hydrogen atoms of the (meth) acrylic acid ester are substituted with a disubstituted amino group.
Examples of the group other than the hydrogen atom (that is, the substituent) in which the hydrogen atom is substituted in the "mono-substituted amino group" and the "di-substituted amino group" include an alkyl group and the like.

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

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

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 and the like.

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

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

In the composition for forming the first intermediate layer (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. It is more preferably%, and particularly preferably 25 to 80% by mass.

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

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

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

In the composition for forming the first intermediate layer (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. It is preferably parts 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 composition for forming the first intermediate layer (II-1) may contain a resin component other than the urethane (meth) acrylate as long as the effects of the present invention are not impaired.
The type of the resin component and the content thereof in the composition for forming the first intermediate layer (II-1) may be appropriately selected depending on the intended 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 correspond to any of the above-mentioned components as long as the effects of the present invention are not impaired.
Known examples of the other additives include cross-linking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes) and the like. Additives can be mentioned.
For example, examples of the chain transfer agent include thiol compounds 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, and the like. Tetraethylene glycol-bis (3-mercaptopropionate), trimetylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetraxthioglucolate, dipentaerythritol hexa Kiss (3-mercaptopropionate), Tris [(3-mercaptopropioniroxy) -ethyl] -isocyanurate, 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobuty) Rate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like.

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

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

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

<< Method for Producing Composition for Forming First Intermediate Layer >>
The first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) can be obtained by blending each component for forming the first intermediate layer forming composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
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 appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◎ Thermosetting resin layer The thermosetting resin layer (thermosetting resin film) is a layer for protecting bumps on the surface of a semiconductor, and forms a first protective film by curing.

As described above, the thermosetting resin layer has an average viscosity of 1 to 20000 Pa · s when melted at 70 to 90 ° C. and a surface free energy of 35 to 40 mJ / m ² at 23 ° C. is there.
Further, the thermosetting resin layer can be formed by using a composition for forming a thermosetting resin layer containing the constituent material.
Therefore, the average viscosity and surface free energy of the thermosetting resin layer can be adjusted by adjusting either or both of the types and amounts of the components contained in the composition for forming the thermosetting resin layer.
The composition for forming a thermosetting resin layer and the method for producing the same will be described in detail later.

For example, among the components contained in the composition for forming a thermosetting resin layer, the average viscosity can be more easily adjusted to a preferable range by reducing the content of the component that increases the viscosity in the composition. .. Examples of the component that increases the viscosity include, but are not limited to, the filler (D) described later.
Further, for example, among the components contained in the composition for forming a thermosetting resin layer, by increasing the content of the component that reduces the viscosity in the composition, the average viscosity can be more easily adjusted to a preferable range. Can be adjusted. Examples of the component that reduces the viscosity include, but are not limited to, a thermoplastic resin described later.
Further, for example, among the components contained in the composition for forming a thermosetting resin layer, those having a mild effect as a thermosetting agent, such as reducing the content of the thermosetting agent in the composition, are used. Therefore, the average viscosity can be adjusted to a preferable range more easily. The thermosetting agent can be appropriately selected from, for example, the thermosetting agent (B2) described later, but is not limited thereto.

Preferred thermosetting resin layers include, for example, those containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component that can be regarded as being formed by a polymerization reaction of a polymerizable compound. Further, the thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction by using heat as a trigger for the reaction. In the present invention, the polymerization reaction also includes a polycondensation reaction.

The thermosetting resin layer may be only one layer (single layer), may be a plurality of layers of two or more layers, and when there are a plurality of layers, the plurality of layers may be the same or different from each other, and these plurality of layers may be used. The combination of is not particularly limited.
When the thermosetting resin layer is a plurality of layers, the entire thermosetting resin layer may satisfy the above-mentioned average viscosity and surface free energy conditions.

The thickness of the thermosetting resin layer is preferably 1 to 50 μm, more preferably 2 to 40 μm, and particularly preferably 3 to 25 μm. As described above, the thickness of the thermosetting resin layer is, for example, 3 to 20 μm, 3 to, in that the effect of forming the first protective film on the bump forming surface is higher. It may be 15 μm, 3 to 10 μm, or the like.
Here, the "thickness of the thermosetting resin layer" means the thickness of the entire thermosetting resin layer, and for example, the thickness of the thermosetting resin layer composed of a plurality of layers is the thermosetting resin layer. It means the total thickness of all the layers that make up.

<< Composition for forming a thermosetting resin layer >>
The thermosetting resin layer can be formed by using a composition for forming a thermosetting resin layer containing the constituent material. For example, a thermosetting resin layer can be formed at a target portion by applying a composition for forming a thermosetting resin layer to a surface to be formed of the thermosetting resin layer and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the composition for forming the thermosetting resin layer 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 composition for forming a thermosetting resin layer may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, and the like. Examples thereof include a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

The drying conditions of the composition for forming a thermosetting resin layer are not particularly limited, but the composition for forming a thermosetting resin layer is preferably heat-dried when it contains a solvent described later. For example, it is preferable to dry at 70 to 130 ° C. for 10 seconds to 5 minutes.

<Composition for forming a resin layer (III-1)>
The composition for forming a thermosetting resin layer includes, for example, a composition for forming a thermosetting resin layer (III-1) containing a polymer component (A) and a thermosetting component (B) (in the present specification). May be simply abbreviated as "resin layer forming composition (III-1)") and the like.

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming property, flexibility, etc. 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 kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

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

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 1000 to 2000000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (stability with time during storage) of the thermosetting resin layer is improved. Further, when the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the thermosetting resin layer easily follows the uneven surface of the adherend, and the thermosetting resin layer is between the adherend and the thermosetting resin layer. The generation of voids and the like is further suppressed.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved. Further, when the Tg of the acrylic resin is not more than the above upper limit value, the adhesive force between the thermosetting resin layer and the first protective film with the adherend is improved.

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-methylol acrylamide, and the like. Examples thereof include copolymers of two or more types of monomers.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth). ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , (Meta) undecyl acrylate, (meth) dodecyl acrylate ((meth) lauryl acrylate), (meth) tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), (meth) acrylate The alkyl groups constituting the alkyl ester, such as pentadecyl, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), (Meta) acrylic acid alkyl ester having a chain structure with 1 to 18 carbon atoms;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylate isobornyl, (meth) acrylate dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) acrylate imide;
A glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) ) 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 acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than the 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 copolymerized with each other.

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

The acrylic resin may have a functional group capable of binding 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 without a cross-linking agent (F). .. When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the first protective film forming sheet tends to be improved.

In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter, may be simply abbreviated as “thermoplastic resin”) is used alone without using the acrylic resin. 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, so that the adherend and the heat are generated. The generation of voids and the like may be further suppressed with the curable resin layer.

The weight average molecular weight of the thermoplastic resin is preferably 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, 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 type, two or more types, or a combination thereof and two or more types. The ratio can be selected arbitrarily.

In the resin layer forming composition (III-1), the ratio of the content of the polymer component (A) to the total content of all the 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). It may be any of ~ 60% by mass, 5 to 50% by mass, 5 to 40% by mass, and 5 to 30% by mass. However, these contents in the resin layer forming composition (III-1) are examples.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition for forming a resin layer (III-1) contains a component corresponding to both the polymer component (A) and the thermosetting component (B), it is used for forming a resin layer. The composition (III-1) is considered to contain the polymer component (A) and the thermosetting component (B).

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing the thermosetting resin layer to form a hard first protective film.
The composition for forming a resin layer (III-1) and the thermosetting component (B) contained in the thermosetting resin layer may be only one kind, two or more kinds, and when two or more kinds, they are used. The combination and ratio of are arbitrarily selectable.

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

(Epoxy thermosetting resin)
The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy-based thermosetting resin contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, and the like. Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher functional epoxy compounds can be mentioned.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the first protective film forming sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, and a (meth) group. Examples thereof include an acrylamide group, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000 from the viewpoint of the curability of the thermosetting resin layer and the strength and heat resistance of the first protective film after curing. , 400 to 10000, and particularly preferably 500 to 3000.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, 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, the combination and ratio thereof can be arbitrarily selected.

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. 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 is anhydrous, and the phenolic hydroxyl group, an amino group, or an acid group is anhydrous. 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 resin, biphenol, novolak type phenolic resin, dicyclopentadiene type phenolic resin, and aralkyl type phenolic resin. ..
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter, may be abbreviated as "DICY") and the like.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
The thermosetting agent (B2) having an unsaturated hydrocarbon group is, for example, a compound in which a part of the hydroxyl group of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, which is not suitable for 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.

When a phenolic curing agent is used as the thermosetting agent (B2), the thermosetting agent (B2) has a softening point or a glass transition temperature because the peelability of the first protective film from the first support sheet is improved. Higher ones are preferable.

Among the thermosetting agents (B2), the number average molecular weight of the resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30,000. , 400 to 10000, and particularly preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 to 500, for example.

As the thermosetting agent (B2), 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, the combination and ratio thereof can be arbitrarily selected.

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 with respect to 100 parts by mass of the content of the epoxy resin (B1). It is preferably parts by mass, more preferably 1 to 200 parts by mass, and may be, for example, any of 5 to 100 parts by mass, 10 to 80 parts by mass, and 20 to 60 parts by mass. When the content of the thermosetting agent (B2) is at least the lower limit value, the curing of the thermosetting resin layer becomes easier to proceed. Further, when the content of the thermosetting agent (B2) is not more than the upper limit value, the hygroscopicity of the thermosetting resin layer is reduced, and the package obtained by using the first protective film forming sheet is used. Greater reliability.

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 1400 parts by mass, more preferably 100 to 1300 parts by mass, and further preferably 150 to 1200 parts by mass with respect to 100 parts by mass. It is preferably 200 to 1150 parts by mass, and particularly preferably 200 to 1150 parts by mass. When the content of the thermosetting component (B) is in such a range, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[Curing accelerator (C)]
The 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 and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles (one or more hydrogen atoms other than hydrogen atoms) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Examples thereof include tetraphenylborone salts such as tetraphenylborate.

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

When the curing accelerator (C) is used, the content of the curing accelerator (C) in the resin layer forming composition (III-1) and the thermosetting resin layer is the content of the thermosetting component (B). It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass. When the content of the curing accelerator (C) is at least the lower limit value, the effect of using the curing accelerator (C) is more remarkable. Further, when 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 adhered in the thermosetting resin layer under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesion interface side with the body is enhanced, and the reliability of the package obtained by 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). Since the thermosetting resin layer contains the filler (D), the first protective film obtained by curing the thermosetting resin layer can easily adjust the coefficient of thermal expansion, and the coefficient of thermal expansion is set to the second. 1. By optimizing for the object to be formed of the protective film, the reliability of the package obtained by using the first protective film forming sheet is further improved. Further, when the thermosetting resin layer contains the filler (D), the hygroscopicity of the first protective film can be reduced and 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, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; 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 a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

When the filler (D) is used, the ratio of the content of the filler (D) to the total content of all the components other than the solvent in the resin layer forming composition (III-1) (that is, the thermosetting resin). The content of the filler (D) in the layer) is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 40% by mass. Further, the ratio may be, for example, any of 7 to 30% by mass and 7 to 25% by mass. When the content of the filler (D) is at least the above lower limit value, the effect of using the filler (D) is more remarkable, and the content of the filler (D) is at least the above upper limit value. This makes it easier to adjust the average viscosity of the thermosetting resin layer.

In the present invention, in the composition for forming a resin layer (III-1), a filler with respect to the total content of all components other than the solvent is used in terms of making it easier to adjust the average viscosity of the thermosetting resin layer. The ratio of the content of (D) (that is, the content of the filler (D) of the thermosetting resin layer) is preferably 40% by mass or less, for example, 30% by mass or less and 25% by mass or less. It may be either one, and it may be 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 adhesiveness 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 groups of the polymer component (A), the thermosetting component (B) and the like, and is preferably a silane coupling agent. More preferred.
Preferred silane coupling agents include, for example, 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-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

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

When the coupling agent (E) is used, the content of the coupling agent (E) in the resin layer forming composition (III-1) and the thermosetting resin layer is the polymer component (A) and the thermosetting resin layer. The total content of the component (B) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass. It is particularly preferable to have. 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 is improved and the adhesiveness of the thermosetting resin layer to the adherend is improved. The effect of using the coupling agent (E) is more remarkable. Further, when the content of the coupling agent (E) is not more than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (F)]
As the polymer component (A), a polymer component (A) having a vinyl group capable of binding to another compound such as the above-mentioned acrylic resin, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, an isocyanate group, or the like is used. When used, the resin layer forming composition (III-1) and the thermosetting resin layer may contain a cross-linking agent (F) for bonding the functional group with another compound to cross-link. By cross-linking with the cross-linking agent (F), the initial adhesive force and cohesive force of the thermosetting resin layer can be adjusted.

Examples of the cross-linking agent (F) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) and the like. Can be 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”. (May be abbreviated); trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the like with a polyol compound. And so on. The "adduct" is a low content of the aromatic polyhydric isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include a xylylene diisocyanate adduct of trimethylol propane as described later. Further, 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 , 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxyl groups of a polyol such as propane; lysine diisocyanate and the like can be mentioned.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic multivalent isocyanate compound is used as the cross-linking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction between the cross-linking agent (F) and the polymer component (A) causes the thermosetting resin layer to have a cross-linked structure. Can be easily introduced.

The cross-linking agent (F) contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one kind, two or more kinds, and when two or more kinds, a combination thereof. And the ratio can be selected arbitrarily.

When the cross-linking agent (F) is used, the content of the cross-linking agent (F) in the resin layer forming composition (III-1) is 0, based on 100 parts by mass of the content 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. When the content of the cross-linking agent (F) is at least the lower limit value, the effect of using the cross-linking agent (F) is more remarkable. Further, when the content of the cross-linking agent (F) is not more than the upper limit value, the excessive use of the cross-linking agent (F) is suppressed.

[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), its characteristics can be changed by irradiation with energy rays.

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

Examples of the acrylate-based compound include trimethyl propantri (meth) acrylate, tetramethylol methanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as meta) acrylates, dipentaerythritol hexa (meth) acrylates, 1,4-butylene glycol di (meth) acrylates, and 1,6-hexanediol di (meth) acrylates; Cyclic aliphatic skeleton-containing (meth) acrylate such as cyclopentanyldi (meth) acrylate; Polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; Oligoester (meth) acrylate; Urethane (meth) acrylate oligomer ; Epoxy-modified (meth) acrylate; polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; itaconic acid oligomer and the like.

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

The energy ray-curable compound used for the polymerization may be only one kind, two or more kinds, and when there are two or more kinds, 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, two or more types, and when two or more types, the combination and ratio thereof are It can be selected arbitrarily.

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

[Photopolymerization Initiator (H)]
When the resin layer forming composition (III-1) contains the energy ray-curable resin (G), the photopolymerization initiator (H) is used to efficiently proceed with the polymerization reaction of the energy ray-curable resin (G). ) May be contained.

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

The photopolymerization initiator (H) contained in the resin layer forming composition (III-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the resin layer forming composition (III-1) is 100 parts by mass of the content of the energy ray-curable resin (G). On the other hand, it 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 the general-purpose additive (I) as long as the effects of the present invention are not impaired.
The general-purpose additive (I) may be a known one, and may be arbitrarily selected depending on the intended purpose, and is not particularly limited, but preferred ones are, for example, plasticizers, antistatic agents, antioxidants, and colorants (dye). , Pigments), gettering agents and the like.

The general-purpose additive (I) contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.
The contents of the resin layer forming composition (III-1) and the general-purpose additive (I) of the thermosetting resin layer are not particularly limited and may be appropriately selected depending on the intended 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 ones are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples thereof include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the resin layer forming composition (III-1) may be only one type, may be two or more types, and when there are 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 or the like from the viewpoint that the components contained in the resin layer forming composition (III-1) can be mixed more uniformly.

<< Manufacturing method of composition for forming thermosetting resin layer >>
A thermosetting resin layer forming composition such as the resin layer forming composition (III-1) can be obtained by blending each component for forming the same.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
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 appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

-Method of manufacturing the first protective film forming sheet The first protective film forming sheet can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.
For example, when the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material when manufacturing the first support sheet, the above-mentioned first pressure-sensitive adhesive composition or the above-mentioned first pressure-sensitive adhesive composition or The first pressure-sensitive adhesive layer or the first intermediate layer can be laminated by applying the composition for forming the first intermediate layer and drying it if necessary, or by irradiating with energy rays.

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

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

When the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material, as described above, the first pressure-sensitive adhesive composition or the composition for forming the first intermediate layer is formed on the first base material. Instead of the method of coating an object, a first pressure-sensitive adhesive composition or a composition for forming a first intermediate layer is applied on a release film, and if necessary, dried or irradiated with energy rays. A first pressure-sensitive adhesive layer or a 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 to form the first pressure-sensitive adhesive layer or the first. The intermediate layer may be laminated on the first base material.
In either method, the release film may be removed at an arbitrary timing after the desired laminated structure is formed.

As described above, all the layers other than the first base material constituting the first protective film forming sheet can be laminated in advance by forming them on the release film and laminating them on the surface of the target layer. If necessary, a layer that employs such a process may be appropriately selected to produce the first protective film forming sheet.

The first protective film forming sheet is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, a thermosetting resin layer) on the opposite side of the first support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting resin layer, is applied onto the release film (preferably the release-treated surface thereof), 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 on the side opposite to the side in contact with the release film of this layer. The first protective film forming sheet can also be obtained by laminating by the method and leaving the release film in a bonded state without removing it.

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

The components used in the production of the composition for forming a thermosetting resin layer are 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) , 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 Corporation)
-Thermosetting agent Thermosetting agent (B2) -1: Novolac type phenol resin ("PAPS-PN4" manufactured by Asahi Organic Materials Industry Co., Ltd.)
-Curing accelerator Curing accelerator (C) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ-PW" manufactured by Shikoku Chemicals Corporation)
-Filler Filler (D) -1: Spherical silica modified with an epoxy group ("Admanano YA050C-MKK" manufactured by Admatex, average particle size 0.05 μm)

[Manufacturing Example 1]
(Manufacturing of adhesive resin (I-2a))
An 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. ..
2-Methacryloyloxyethyl isocyanate (hereinafter abbreviated as "MOI") (22 parts by mass, about 80 mol% with respect to HEA) was added to this acrylic polymer, and the mixture was added in an air stream at 50 ° C. for 48 hours. By carrying out the reaction, the desired adhesive resin (I-2a) was obtained.

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

(Manufacturing of First Adhesive Composition)
To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 1, a trimerizing isocyanate trimer addition of trimethylolpropane as an isocyanate-based cross-linking agent (“Coronate L” manufactured by Tosoh Corporation) ) (0.5 parts by mass) was added and stirred at 23 ° C. to obtain a first pressure-sensitive adhesive composition (I-2) having a solid content concentration of 30% by mass as the first pressure-sensitive adhesive composition. .. The number of parts to be blended in this "manufacturing of the first pressure-sensitive adhesive composition" is a solid content conversion value.

(Manufacturing of first protective film forming sheet)
The first pressure-sensitive adhesive composition obtained above is applied to the peeled surface of a peeled film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate film is peeled by a 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 base material, a polyolefin film (thickness 25 μm), an adhesive layer (thickness 2.5 μm), a polyethylene terephthalate film (thickness 50 μm), and an adhesive layer A first support sheet was obtained by laminating a laminated film having a thickness of 105 μm, which was formed by laminating a (2.5 μm thick) and a polyolefin film (25 μm thick) in this order.

The composition for forming a thermosetting resin layer obtained above on the peeled surface of a peeled film (“SP-PET38131” manufactured by Lintec Co., Ltd., thickness 38 μm) in which one side of a polyethylene terephthalate film was peeled by a silicone treatment. A thermosetting resin film (thermosetting resin layer) having a thickness of 20 μm was prepared by applying an object and drying it at 100 ° C. for 2 minutes.

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. A first protective film-forming sheet was obtained in which the first base material, the first pressure-sensitive adhesive layer, the thermosetting resin layer, and the release film were laminated in this order in the thickness direction thereof.

<Evaluation of thermosetting resin film>
(Evaluation of the first protective film film forming property of the thermosetting resin film)
Using a semiconductor wafer having the same shape as that shown in FIG. 1 and having a large number of bumps having a height of 210 μm from the circuit surface formed at a pitch of 400 μm, the bump-forming surface was obtained as described above. A sheet for forming the first protective film was attached. At this time, the first protective film forming sheet is bumped by removing the release film and attaching the exposed thermosetting resin layer under the conditions of a sticking pressure of 0.5 MPa, a sticking speed of 5 mm / sec, and a temperature of 80 ° C. Was pasted while embedding.
Next, the first pressure-sensitive adhesive layer was irradiated with ultraviolet rays under the conditions of a light intensity of 750 mJ / cm ² and an illuminance of 200 mW / cm ² , to cure the first pressure-sensitive adhesive layer, and then the cured first pressure-sensitive adhesive layer was applied. It was removed together with the first substrate.
Next, the thermosetting resin layer (thermosetting resin film) was melted by gradually raising the temperature from 70 ° C. at a heating rate of 5 ° C./min under a pressurized atmosphere at 0.5 MPa. A first protective film having a thickness of 20 μm was formed on the circuit surface by highly selectively aggregating the base of the bump and the region near the bump on the circuit surface, and then heating at 160 ° C. and curing for 1 hour. ..

Next, the appearance and shape of the first protective film on the bump-forming surface were observed using a laser microscope, and the first protective film film forming property was evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: The first protective film is highly selectively formed on the base of the bump and the region near the bump on the circuit surface, and the first protective film is formed on the circuit surface between adjacent bumps in a region other than the vicinity of the bump. Almost or no protective film is formed.
Δ: The first protective film is highly selectively formed on the base of the bump and the region near the bump on the circuit surface, and the first protective film is formed on the circuit surface between adjacent bumps in a region other than the vicinity of the bump. A slight protective film is formed.
X: The first protective film is formed in contact with the circuit surface, and there is almost or no exposed region of the circuit surface between adjacent bumps, or the first protective film is in contact with the circuit surface. Not formed.

(Measurement of average viscosity of thermosetting resin film when melted)
Using the thermosetting resin layer forming composition obtained above, a thermosetting resin film having a thickness of 20 μm was produced in the same manner as in the production of the first protective film forming sheet described above.
Next, the average viscosity of the thermosetting resin film when melted at 70 to 90 ° C. was measured using a thin tube rheometer (flow tester, "CFT-100D" manufactured by Shimadzu Corporation). The average viscosity was taken as the average value of 21 measured values obtained by measuring the melt viscosity of the thermosetting resin film at every 1 ° C. temperature of the thermosetting resin film from 70 ° C. to 90 ° C. The results are shown in Table 1 and FIG. In addition, in FIG. 7, the melt viscosity at a temperature outside the range of 70 to 90 ° C. is also shown. In the graph of FIG. 7, the vertical axis represents the melt viscosity of the thermosetting resin film, and the horizontal axis represents the temperature of the thermosetting resin film.

(Calculation of surface free energy of thermosetting resin film)
Using the thermosetting resin layer forming composition obtained above, a thermosetting resin film having a thickness of 20 μm was produced in the same manner as in the production of the first protective film forming sheet described above.
Then, using a contact angle measuring device (fully automatic contact angle meter, "DM-701" manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of water, 1-bromonaphthalene and diiodomethane with respect to the thermosetting resin film at 23 ° C. Was measured. The contact angle was measured 5 times for each of the above solvents (water, 1-bromonaphthalene, diiodomethane), and the average value of the obtained 5 measured values was adopted as the contact angle of the solvent. Then, using the value of this contact angle, the surface free energy of the thermosetting resin film at 23 ° C. was calculated by the Kitazaki-Hata method. The results are shown in Table 1.

<Manufacturing of first protective film forming sheet, evaluation of thermosetting resin film>
[Examples 2 to 4, Comparative Example 1]
A first protective film forming sheet was produced in the same manner as in Example 1 except that the components and contents of the thermosetting resin layer forming composition were as shown in Table 1, and the thermosetting resin film was produced. Was evaluated. The results are shown in Table 1. The results of Example 2 and Comparative Example 1 are also shown in FIG.

As is clear from the above results, the average viscosity at the time of melting at 70 to 90 ° C. is in the range of 1553 to 17370 Pa · s, and the surface free energy at 23 ° C. is 32.1 to 38.6 mJ / m ² . When the thermosetting resin films of Examples 1 to 4 within the range are used, the first protective film can be highly selectively formed at the base of the bump and the region near the bump on the circuit surface. 1 The protective film film forming property was good. That is, at the time of forming the first protective film, the first protective film was not formed at all in the region other than the vicinity of the bumps in the circuit surface between the adjacent bumps, and in Examples 2 to 4, the first protective film was formed. 1 A protective film was slightly formed. Then, in Examples 2 to 4, if a thermosetting resin film having a thinner thickness is used, the first protective film is completely formed in the region other than the vicinity of the bumps in the circuit surface between the adjacent bumps. It was judged that it is possible to prevent it from being done.

On the other hand, when the thermosetting resin film of Comparative Example 1 was used, the first protective film film forming property was inferior. That is, the first protective film could be formed in contact with the circuit surface by embedding bumps with a thermosetting resin film by thermal lamination, removing the first support sheet, and then heating the film. , The first protective film could not be formed highly selectively in the base of the bump and the region near the bump on the circuit surface. The thermosetting resin film of Comparative Example 1 has a low fluidity at the time of melting due to an excessive content of the filler (D) -1, and is further heated in a state where the bumps are embedded. However, it is presumed that this film did not highly selectively aggregate at the base of the bump and the region near the bump on the circuit surface, and the exposed region on the circuit surface was almost nonexistent between the adjacent bumps. .. It was determined that the thermosetting resin film of Comparative Example 1 could not have good first protective film film forming property even if the thickness was reduced.

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

1,2,3 ... 1st protective film forming sheet, 11 ... 1st base material, 11a ... surface of 1st base material, 12 ... thermosetting resin layer (thermosetting resin) Film), 12'... first protective film, 13 ... first pressure-sensitive adhesive layer, 13a ... surface of first pressure-sensitive 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, 900 ... Region near bump on circuit surface , 900a ... Exposed area of circuit surface, 91 ... Bump, 91a ... Bump surface, 910 ... Bump base, 911 ... Bump top

Claims (2)

A thermosetting resin film for forming a first protective film around bumps by affixing it to a surface of a semiconductor wafer having bumps and heat-curing it.
The average viscosity of the thermosetting resin film when melted at 70 to 90 ° C. is 1 to 20000 Pa · s.
A thermosetting resin film having a surface free energy of 30 to 40 mJ / m ² at 23 ° C. of the thermosetting resin film. A sheet for forming a first protective film, wherein the thermosetting resin film according to claim 1 is provided on one surface of the first support sheet.

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