KR20210130696A - A sheet for forming a thermosetting resin film and a first protective film - Google Patents

Abstract

The thermosetting resin film of this embodiment is a thermosetting resin film for forming a first protective film on the surface by affixing and thermosetting a surface having a projecting electrode of a work, wherein the thermosetting resin film is other than an acrylic resin having an epoxy group of, containing two or more types of thermosetting components, and in the thermosetting resin film, the ratio of the total content of the above thermosetting components of all types to the total mass of the thermosetting resin film is 40 mass % or more, and the thermosetting resin film contains About the said thermosetting component, when the X value is calculated|required for each type, and the sum total value of the X value in the said thermosetting component of all types is calculated|required, the said total value will be 400 g/eq or less.

Description

A sheet for forming a thermosetting resin film and a first protective film

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

This application claims priority based on Japanese Patent Application No. 2019-032828 for which it applied to Japan on February 26, 2019, and uses the content here.

Conventionally, when a multi-pin LSI package used for an MPU or a gate array is mounted on a printed wiring board, a workpiece (eg, a semiconductor wafer, etc.) provided with protruding electrodes (eg, bumps, pillars, etc.) A flip chip that uses a so-called face-down method to bring a protruding electrode in a workpiece (eg, a semiconductor chip, which is a divided part of a semiconductor wafer) into contact with a corresponding terminal on the substrate, thereby melting/diffusion bonding. A mounting method has been employed.

When this mounting method is employed, for the purpose of protecting the circuit surface and the protruding electrode of the work, a curable resin film is affixed to the surface of the protruding electrode and the circuit surface of the work, the film is cured, and the A protective film may be formed.

In addition, in this specification, the combination of the surface of a protrusion-shaped electrode and the circuit surface of a workpiece|work or a workpiece|work processed may be called "protrusion-shaped electrode formation surface".

A curable resin film is affixed to the protruding electrode formation surface of a workpiece|work in the state softened by heating normally. By doing in this way, the upper part including the top of the protruding electrode penetrates the curable resin film and protrudes from the curable resin film. On the other hand, the curable resin film spreads between the protruding electrodes so as to cover the protruding electrode of the work, and while adhering to the circuit surface, it covers the surface of the protruding electrode, particularly the surface of the region near the circuit surface, to form the protruding electrode. buy Thereafter, the curable resin film is further cured to form a protective film that covers the circuit surface of the work and the surface of the portion in the vicinity of the circuit surface of the protruding electrode to protect these regions.

When a semiconductor wafer is used, the semiconductor chip used in this mounting method is obtained, for example, by grinding or dicing and dividing the surface of a semiconductor wafer in which the protruding electrode is formed on the circuit surface, opposite to the circuit surface.

In the process of obtaining such a semiconductor chip, in order to protect the circuit surface and protrusion electrode of a semiconductor wafer normally, a curable resin film is affixed to the protrusion electrode formation surface, this film is hardened, and the protrusion electrode formation surface is affixed. to form a protective film on

Further, the semiconductor wafer is divided into semiconductor chips, and finally, a semiconductor chip having a protective film on the protruding electrode formation surface (in this specification, it is sometimes referred to as a "semiconductor chip with a protective film") (patent document) see 1).

A workpiece (in this specification, sometimes referred to as a "workpiece with a protective film") provided with a protective film on the surface on which the protruding electrode is formed is further mounted on a substrate to form a package, and the package is further Using it, the target device is constructed. When the semiconductor chip with a protective film is mounted on a board|substrate, the target semiconductor device is comprised using the semiconductor package obtained by this.

Japanese Patent No. 5515811

In the case of using a conventional curable resin film, including those disclosed in Patent Document 1, division of a work (eg, division of a semiconductor wafer into semiconductor chips) is usually performed by blade dicing using a dicing blade, there was. However, although this method is the most widely used, it is not suitable for, for example, the production of a workpiece having a small size or a workpiece having a thin thickness. This is because cracks or defects are likely to occur in such a workpiece.

Accordingly, the present invention is a resin film capable of forming a protective film for protecting the protruding electrode formation surface of a work or workpiece, and by using the resin film, a resin film that enables a novel method for dividing a work to be applied. intended to provide In particular, when this novel method is applied, the residual at the top of the protruding electrode is suppressed when sticking to the surface on which the protruding electrode is formed, and the protective film as a cured product can be cut satisfactorily when dividing the work. It aims at providing a resin film.

The present invention is a thermosetting resin film for forming a first protective film on a surface of a work by attaching it to a surface having a protruding electrode and thermosetting it, wherein the thermosetting resin film is two or more types other than an acrylic resin having an epoxy group. It contains a thermosetting component, and in the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting component to the total mass of the thermosetting resin film is 40 mass% or more, and the thermosetting resin film contains the thermosetting resin film. For ingredients, for each type, the following formula:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

Obtaining the X value calculated by , and obtaining the sum of the X values in all kinds of the thermosetting components contained in the thermosetting resin film, the total value is 400 g / eq or less, providing a thermosetting resin film do.

Further, the present invention provides a sheet for forming a first protective film including a first supporting sheet and having the thermosetting resin film on one side of the first supporting sheet.

According to the present invention, there is provided a resin film capable of forming a protective film for protecting a projecting electrode formation surface of a work or workpiece, and by using the resin film, a resin film enabling a novel method for dividing a work to be applied. is provided In particular, when this novel method is applied, the residual at the top of the protruding electrode is suppressed when sticking to the surface on which the protruding electrode is formed, and the protective film as a cured product can be cut satisfactorily when dividing the work. A resin film is provided.

1 is a cross-sectional view schematically showing an example of a state in which a first protective film is formed on a protruding electrode formation surface using a curable resin film according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing an example of a sheet for forming a first protective film according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing another example of a sheet for forming a first protective film according to an embodiment of the present invention.
4 is a cross-sectional view schematically showing another example of the sheet for forming a first protective film according to an embodiment of the present invention.
Fig. 5A is an enlarged cross-sectional view schematically illustrating a method for manufacturing a workpiece on which a first protective film is formed when the sheet for forming a first protective film according to an embodiment of the present invention is used.
Fig. 5B is an enlarged cross-sectional view schematically illustrating a method for manufacturing a workpiece on which a first protective film is formed when the sheet for forming a first protective film according to an embodiment of the present invention is used.
5C is an enlarged cross-sectional view schematically illustrating a method for manufacturing a workpiece on which a first protective film is formed when the sheet for forming a first protective film according to an embodiment of the present invention is used.
6A is an enlarged cross-sectional view schematically illustrating a method for manufacturing a workpiece on which a first protective film is formed, when the sheet for forming a first protective film according to an embodiment of the present invention is used.
6B is an enlarged cross-sectional view schematically illustrating a method for manufacturing a workpiece on which a first protective film is formed when the sheet for forming a first protective film according to an embodiment of the present invention is used.

◇Thermosetting resin film, sheet for forming the first protective film

A thermosetting resin film according to an embodiment of the present invention is adhered to a surface having a projecting electrode of a work (that is, a surface on which the projecting electrode is formed) and thermosetted to form a first protective film on the surface. As, the thermosetting resin film contains two or more types of thermosetting components other than the acrylic resin having an epoxy group, and in the thermosetting resin film, the total content of all types of the thermosetting components with respect to the total mass of the thermosetting resin film The ratio of is 40 mass % or more, and with respect to the said thermosetting component which the said thermosetting resin film contains, the following formula for each type:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

When the value of X calculated by is calculated|required and the total value of the said X value in all the types of the said thermosetting component contained in the said thermosetting resin film is calculated|required, the said total value becomes 400 g/eq or less.

Moreover, the 1st sheet|seat for protective film formation which concerns on one Embodiment of this invention is equipped with the 1st support sheet, The said thermosetting resin film is provided on one side of the said 1st support sheet. The said "thermosetting resin film" is also called a "thermosetting resin layer" in the said 1st sheet|seat for protective film formation.

In this embodiment, as a workpiece|work, a semiconductor wafer etc. are mentioned, for example.

As a workpiece|work object, the semiconductor chip etc. which are a division|segmentation of a semiconductor wafer are mentioned, for example.

The processing of the workpiece includes, for example, division.

As a protruding electrode, a bump, a pillar, etc. are mentioned, for example. The protruding electrode is formed in the connection pad portion of the work, and is made of eutectic solder, high temperature solder, gold, copper, or the like.

The first sheet for forming a protective film is used by being affixed to the protruding electrode forming surface of the work (that is, the surface of the protruding electrode and the circuit face of the work) with the thermosetting resin film (thermosetting resin layer) interposed therebetween. And the thermosetting resin film after affixing increases fluidity|liquidity by heating, and the upper part including the top part of a protruding electrode penetrates the thermosetting resin film and protrudes from the thermosetting resin film. In addition, the thermosetting resin film spreads between the protruding electrodes so as to cover the protruding electrode, and is in close contact with the circuit surface and covers the surface of the protruding electrode, particularly the surface of the portion near the circuit surface, to form the protruding electrode buy The thermosetting resin film in this state is further cured by heating, finally forming a first protective film, and protecting the circuit surface and the protruding electrode in a state in close contact with them. In this way, by using the thermosetting resin film of the present embodiment, the circuit surface of the work and the portion in the vicinity of the circuit surface of the protruding electrode, ie, the base, are sufficiently protected by the first protective film.

The work after affixing the 1st protective film formation sheet is, for example, after grinding the surface on the opposite side to the said circuit surface as needed, removes a 1st support sheet, Then, the protrusion shape by heating of a thermosetting resin film The electrodes are embedded and the first protective film is formed. Further, the workpiece is divided (that is, divided into pieces) and the first protective film is cut, and the workpiece is provided with the first protective film after cutting on the protruding electrode formation surface (in this specification, A substrate device for the purpose of a semiconductor device or the like is manufactured using the "workpiece with the first protective film formed thereon" in some cases). These steps will be described in detail later.

On the other hand, in this specification, unless otherwise specified, the description of a simple "curable resin film" means "curable resin film before curing", and the description of a simple "curable resin layer" refers to "curable resin layer before curing". it means. For example, "thermosetting resin film" means "thermosetting resin film before hardening", and "1st protective film" means hardened|cured material of a thermosetting resin film.

The thermosetting resin film of the present embodiment is suitable for applying a method different from the conventional one as a method for dividing a work into workpieces (that is, into pieces). Here, as "a method different from the conventional one", the following method is mentioned, for example.

That is, by irradiating a laser beam with respect to the workpiece|work provided with the 1st protective film formed from the said thermosetting resin film on the protrusion-shaped electrode formation surface, a modified layer is formed in the inside of a workpiece|work. Next, a force is applied to the workpiece after the formation of the modified layer. More specifically, in the present embodiment, the work is expanded in a direction parallel to the circuit surface thereof. Thereby, the said workpiece|work is divided|segmented in the site|part of the said modified layer. At this time, the first protective film is also cut at the same time by applying a force to the first protective film, more specifically, by expanding the first protective film in a direction parallel to the surface to be adhered to the work. At this time, the first protective film is cut along the divided portion of the work. As described above, the workpiece and the workpiece in which the first protective film provided with the first protective film after cutting formed on the protruding electrode formation surface of the workpiece is formed are manufactured. In the production of such a workpiece, when the first protective film is a cured product of the thermosetting resin film, the workpiece can be satisfactorily divided into the workpiece. Moreover, since the 1st protective film itself is also a hardened|cured material of the said thermosetting resin film, at the time of division|segmentation of a workpiece|work, it can cut|disconnect easily along the division|segmentation location of a workpiece|work.

A method of dividing a work that involves the formation of such a modified layer is called stealth dicing (registered trademark), and by irradiating the work with laser light, a laser cuts the work from the surface while cutting the work at the irradiation site. It is essentially completely different from dicing.

<<Ratio of Total Content of All Types of Thermosetting Components>>

The said thermosetting resin film WHEREIN: The "thermosetting component" which prescribes|regulates the ratio of the above-mentioned total content is a component which shows hardening reaction by heating. However, the acrylic resin which has an epoxy group is not included in this thermosetting component. As a thermosetting component, the thermosetting component (B) mentioned later is mentioned, for example.

As a thermosetting component (B), an epoxy type thermosetting resin, polyimide resin, unsaturated polyester resin, etc. are mentioned, for example. An epoxy-type thermosetting resin consists of an epoxy resin (B1) and a thermosetting agent (B2), and both these two types become the regulation object of the ratio of the above-mentioned total content.

On the other hand, as an acrylic resin which has an epoxy group which is not included in a thermosetting component, what has an epoxy group is mentioned among the acrylic resins in the polymer component (A) mentioned later, for example. For example, the acrylic resin which has a glycidyl group is contained in the acrylic resin which has an epoxy group.

The thermosetting component contained in the thermosetting resin film is two or more, and combinations and ratios thereof may be arbitrarily selected.

Ratio of the total content of the thermosetting components of all kinds to the total mass of the thermosetting resin film in the thermosetting resin film ([total content of all kinds of thermosetting components in the thermosetting resin film (parts by mass)]/[ The total mass (parts by mass)] x 100) of the thermosetting resin film is 40 mass % or more as described above. Here, the total content (parts by mass) of all types of thermosetting components means the total content (parts by mass) of two or more types of thermosetting components of all types.

By satisfying such a condition for the ratio of the total content, the thermosetting resin film can suppress the remaining in the upper part including the top of the protruding electrode when the work is pasted to the protruding electrode formation surface, and the first protective film It has suitable properties as a resin film for forming In this way, when the thermosetting resin film is pasted to the protruding electrode forming surface, the thermosetting resin film does not remain on the protruding electrode, that is, the upper portion of the protruding electrode penetrates the affixed thermosetting resin film. and projecting, the finally obtained workpiece can be sufficiently electrically coupled to the substrate by the protruding electrode when flip-chip mounted. That is, unless the thermosetting resin film can suppress the residual in the upper part of the protruding electrode, the workpiece cannot be put to practical use.

From the point where the above-mentioned advantageous effect is obtained more significantly, in the said thermosetting resin film, the ratio of the total content of the said thermosetting component of all types with respect to the total mass of the said thermosetting resin film is, for example, 50 mass % or more, Any one of 60 mass % or more, 70 mass % or more, and 80 mass % or more may be sufficient.

The upper limit of the ratio of the said total content is not specifically limited. For example, it is preferable that the ratio of the said total content is 90 mass % or less at the point from which the film-forming property of a thermosetting resin film becomes more favorable.

The ratio of the said total content can be suitably adjusted within the range set by combining the above-mentioned lower limit and upper limit arbitrarily. For example, in one embodiment, even if the ratio of the said total content is any one of 40-90 mass %, 50-90 mass %, 60-90 mass %, 70-90 mass %, and 80-90 mass %, do.

<<Sum of X values>>

The said X value is computed by the said Formula with respect to 1 type of thermosetting component which the said thermosetting resin film contains.

The "thermosetting component" which is the calculation object of the said X value is the same as the "thermosetting component" which prescribes|regulates the ratio of the above-mentioned total content in the said thermosetting resin film.

The "functional group related to the thermosetting reaction of the thermosetting component" for calculating the X value is, for example, an epoxy group in the case of an epoxy resin (B1) described later, and in the case of a thermosetting agent (B2) described later, phenolic a hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anhydrideized, and the like. However, these are examples of the functional group.

The case where the said thermosetting resin film contains the thermosetting component of p type (p is an integer of 2 or more) is considered. Let these thermosetting components be M ₁ and M _p for each type. And the equivalent of the functional group of the thermosetting component M _{1 is m 1} (g/eq), the equivalent of the functional group of the _{thermosetting component M p is m p} (g/eq), and the thermosetting component M _{1 of the thermosetting resin film} Let the content of C ₁ (parts by mass) be C 1 (parts by mass), and let content _{of the thermosetting component M p of the thermosetting resin film be C p} (parts by mass).

At this time, the thermosetting component to the M _1, the X value (hereinafter referred to as "X ₁ value") is calculated by the following equation.

Likewise, even for a thermosetting component M _p, the X value (hereinafter referred to as "X _p value") is calculated by the following equation.

Then, the total value of the thermosetting resin film containing the entire kinds of the thermosetting component _{(M 1, ..., M P} ) wherein the value of X (X _1, ..., X _p) of the are as follows:

_{If the equivalent (m 1} , m _p (g/eq)) of the functional group of the thermosetting component is not specified as a constant value but has a width and is specified in a numerical range, the average value calculated from the lower and upper limits of the numerical range What is necessary is just to employ|adopt as an equivalent of a functional group.

The said thermosetting resin film WHEREIN: The total value of the said X value is 400 g/eq or less.

By satisfying the condition of the sum of the X values, the first protective film, which is a cured product of the thermosetting resin film, can be easily cut when dividing the work. As a result, a workpiece having the first protective film after cutting on the protruding electrode formation surface can be manufactured with high efficiency.

From the viewpoint that the above-described advantageous effect is more significantly obtained, in the thermosetting resin film, the total value of the X values may be, for example, any one of 375 g/eq or less, 350 g/eq or less, and 325 g/eq or less.

The lower limit of the sum of the said X values is not specifically limited. For example, in the said thermosetting resin film, it is preferable that the total value of the said X value is 100 g/eq or more from the point which the fall of the softness|flexibility resulting from an excessive crosslinking reaction is suppressed.

The total value of the X values can be appropriately adjusted within a range set by arbitrarily combining the above-described lower limit value and upper limit value. For example, in one embodiment, any one of 100-400 g/eq, 100-375 g/eq, 100-350 g/eq, and 100-325 g/eq may be sufficient as the total value of the said X value.

<<Light transmittance of thermosetting resin film>>

It is preferable that the light transmittance of the said thermosetting resin film of a 200-micrometer-thick one-layer wavelength 1342nm is 50 % or more.

Moreover, it is preferable that the light transmittance of wavelength 1342nm of the laminated|multilayer film with a total thickness of 200 micrometers formed by laminating|stacking two or more layers of the said thermosetting resin film less than 200 micrometers in thickness is 50 % or more.

When the method involving the formation of a modified layer inside the work described above is applied as a method of dividing a work to produce a work piece, the work is irradiated with laser light having a wavelength of 1342 nm to form a modified layer can do. At this time, the laser beam may be irradiated to the work from the circuit surface side, or may be irradiated from the back surface side. However, when irradiating a laser beam to a workpiece|work from the circuit surface side, the laser beam is irradiated through the 1st protective film formed in the circuit surface.

On the other hand, the light transmittance of the same wavelength of a thermosetting resin film and its hardened|cured material (for example, 1st protective film) becomes substantially or completely the same. Therefore, when the one-layer thermosetting resin film having a thickness of 200 µm has a light transmittance at a wavelength of 1342 nm of 50% or more, the light transmittance of the cured product at a wavelength of 1342 nm is also 50% or more. Similarly, when the light transmittance of the 1342 nm wavelength of the said laminated|multilayer film is 50 % or more, the light transmittance of the wavelength 1342 nm of the hardened|cured material will also be 50 % or more. That is, the 1st protective film formed using the thermosetting resin film of the same composition as that which satisfy|fills the conditions of such light transmittance allows the laser beam with a wavelength of 1342 nm to transmit favorably. Accordingly, a work having such a first protective film on a circuit surface is preferable for forming a modified layer inside the work by irradiating laser light from the circuit surface side thereof.

From the point where the above-mentioned effect becomes more remarkable, the light transmittance of the one-layer thermosetting resin film with a thickness of 200 micrometers, or the laminated|multilayer film whose total thickness is 200 micrometers is, for example, 60% or more, Any one of 70 % or more, 80 % or more, and 85 % or more may be sufficient.

The upper limit of the light transmittance of the one-layer thermosetting resin film with a thickness of 200 micrometers or the laminated|multilayer film whose total thickness is 200 micrometers is not specifically limited, It is so preferable that it is high. For example, it is preferable that the said light transmittance is 95 % or less at the point which manufacture of a thermosetting resin film is comparatively easy.

The light transmittance may be appropriately adjusted within a range set by arbitrarily combining the above-described lower limit value and upper limit value. In one embodiment, it is preferable that the said light transmittance is 50-95%, for example, any one of 60-95%, 70-95%, 80-95%, and 85-95% may be sufficient.

In the one-layer thermosetting resin film having a thickness of 200 µm and the laminated film having a total thickness of 200 µm, if these components are the same, the light transmittance of these (one-layer thermosetting resin film and laminated film) is the wavelength of light It is not limited to the case of this 1342 nm, and mutually becomes equal.

Although the number of layers of the thermosetting resin film whose thickness is less than 200 micrometers which comprises the said laminated|multilayer film is not specifically limited, It is preferable that it is 2-6. If it is such a number of layers, the said laminated|multilayer film can be produced more easily.

The thickness of the thermosetting resin film whose thickness is less than 200 micrometers which comprises the said laminated|multilayer film may be all the same, may be all different, and may be same only partially.

In the present embodiment, in the one-layer thermosetting resin film or laminated film, which is a specific object of the light transmittance, the reason for defining the thickness as 200 µm is by using a thermosetting resin film or laminated film having such a thickness. This is because the light transmittance can be measured more accurately and easily.

In this embodiment, the thickness of the thermosetting resin film of one layer and the thermosetting resin film consisting of two or more layers is not all limited to 200 micrometers so that it may mention later.

The light transmittance can be adjusted, for example, by adjusting the type and content of components contained in the thermosetting resin film, such as a colorant (I) and a filler (D), which will be described later, and the surface state of the thermosetting resin film.

<<breaking strength of the first protective film>>

It is preferable that the breaking strength of the first protective film having a size of 20 mm x 130 mm and a thickness of 40 µm, measured by the following method, is 55 MPa or less. The first protective film having the same composition as the first protective film having the breaking strength equal to or less than the upper limit is more easily cut by expand, which will be described later.

As the breaking strength of the first protective film, the distance between the grippers in the first protective film was set to 80 mm, the tensile speed of the first protective film was set to 200 mm/min, and the first protective film was applied to the surface by the gripper. The maximum stress measured when tension is applied in a direction parallel to the surface can be employed.

As a 1st protective film which is the measurement object of maximum stress, what was obtained by thermosetting by heating a thermosetting resin film at 130 degreeC for 2 hours can be used.

In the point where the above-mentioned effect becomes more remarkable, the said breaking strength of a 1st protective film may be any one of 52.5 MPa or less, 50 MPa or less, and 47.5 MPa or less, for example.

The lower limit of the breaking strength of the first protective film is not particularly limited. It is preferable that the said breaking strength of a 1st protective film is 0.1 MPa or more at the point which the protective ability of a 1st protective film becomes higher.

The breaking strength of the first protective film can be appropriately adjusted within a range set by arbitrarily combining the above-described lower limit value and upper limit value. In one embodiment, the breaking strength of the first protective film is preferably 0.1 to 55 MPa, and for example, any one of 0.1 to 52.5 MPa, 0.1 to 50 MPa, and 0.1 to 47.5 MPa may be sufficient.

The breaking strength of the first protective film is, for example, a component contained in the composition for forming a thermosetting resin layer described later, in particular, the type and content of the polymer component (A), the coupling agent (E), the filler (D), and the like, and , by adjusting the thickness of the first protective film (that is, the thickness of the thermosetting resin film), and the like.

In a workpiece and a workpiece having a protruding electrode on a circuit surface, the surface (rear surface) opposite to the circuit surface may be exposed. For this reason, on this back surface, the protective film (In this specification, in order to distinguish from a 1st protective film, it may call a "2nd protective film") containing an organic material may be formed. The second protective film is used to prevent cracks from occurring in the workpiece after division or packaging of the workpiece. The workpiece in which the second protective film having the second protective film on its back surface is formed is finally mounted on a target substrate device such as a semiconductor device.

On the other hand, in some cases, the second protective film is required to have a function of enabling information on the workpiece to be marked with a laser or hiding the back surface of the workpiece. As what satisfies such a request|requirement, the curable resin film in which the transmission characteristic of the light which can form a 2nd protective film can be formed by hardening was adjusted is known.

However, the second protective film for protecting the back surface of the workpiece and the first protective film for protecting the protruding electrode formation surface of the workpiece are formed at different positions in the workpiece, and therefore required properties are also different from each other. . Therefore, it is usually difficult to directly use the thermosetting resin film capable of forming the second protective film for forming the first protective film.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the state in which the 1st protective film was formed in the protrusion-shaped electrode formation surface using the thermosetting resin film of this embodiment. On the other hand, in the drawings used in the following description, in order to make the characteristics of the present invention easy to understand, there are cases where the main parts are enlarged for convenience, and the dimensional ratio of each component is limited to the same as in reality. doesn't happen

A plurality of protruding electrodes 91 are formed on the circuit surface 90a of the work 90 shown here. In Fig. 1, reference numeral 90b denotes a surface (rear surface) opposite to the circuit surface 90a of the workpiece 90 .

The protruding electrode 91 has a shape in which a part of the sphere is cut off by a plane, and a plane corresponding to the cut and exposed portion is in a state in which the circuit surface 90a of the work 90 is in contact.

The shape of the protruding electrode 91 is substantially spherical.

The first protective film 12' is formed using the thermosetting resin film of the present embodiment, and covers the circuit surface 90a of the work 90, and further among the surface 91a of the protruding electrode 91, The top portion 910 of the protruding electrode 91 and a region other than its vicinity are covered. In this way, the first protective film 12 ′ is in close contact with the top 910 of the protruding electrode 91 and the surface 91a other than its vicinity, and also closely adheres to the circuit surface 90a of the workpiece 90 . Thus, the protruding electrode 91 is embedded.

The substantially spherical shape of the protruding electrode 91 is particularly advantageous in forming the first protective film using the curable resin film.

The height (H ₉₁ ) of the protruding electrode 91 is not particularly limited, but is preferably 50 to 500 μm. When the height H ₉₁ of the protruding electrode 91 is equal to or greater than the lower limit, the function of the protruding electrode 91 can be further improved. _{When the height H 91} of the protruding electrode 91 is equal to or less than the upper limit, the protruding electrode formation surface of the work 90 (that is, the surface 91a of the protruding electrode 91 , and the work 90 ) When the thermosetting resin film is pasted to the circuit surface 90a), the effect of suppressing the residual of the thermosetting resin film in the upper portion including the top portion 910 of the protruding electrode 91 is higher, as a result, The effect of suppressing the formation of the first protective film 12' on the protruding electrode 91 is further enhanced.

In addition, in this specification, the "height of a protruding electrode" means the height at the site|part (ie, the top part) which exists in the highest position from the circuit surface of a workpiece|work or a workpiece|work among the protruding electrodes.

The width (W ₉₁ ) of the protruding electrode 91 is not particularly limited, but is preferably 50 to 600 μm. When the width W ₉₁ of the protruding electrode 91 is equal to or greater than the lower limit, the function of the protruding electrode 91 can be further improved. _{When the width W 91} of the protruding electrode 91 is equal to or less than the upper limit, the surface 91a of the protruding electrode forming surface of the work 90 (that is, the surface 91a of the protruding electrode 91 and the work 90 ) When the thermosetting resin film is pasted to the circuit surface 90a), the effect of suppressing the residual of the thermosetting resin film in the upper portion including the top portion 910 of the protruding electrode 91 is higher, as a result, The effect of suppressing the formation of the first protective film 12' on the protruding electrode 91 is further enhanced.

On the other hand, in this specification, the "width of the protruding electrode" refers to a distance between two different points on the surface of the protruding electrode when viewed in a plan view from a direction perpendicular to the circuit surface of the work or workpiece. It means the maximum value of a line segment obtained by connecting a straight line.

_{The distance D 91} between the adjacent protruding electrodes 91 is not particularly limited, but is preferably 100 to 800 μm. _{When the distance D 91} between the protruding electrodes 91 is equal to or greater than the lower limit, the protruding electrode formation surface of the work 90 (that is, the surface 91a of the protruding electrode 91 , and the circuit of the work 90 ) When the thermosetting resin film is pasted to the surface 90a), the effect of suppressing the residual of the thermosetting resin film in the upper portion including the top portion 910 of the protruding electrode 91 is higher, and as a result, the protrusion The effect of suppressing the formation of the first protective film 12 ′ on the upper electrode 91 is further enhanced. _{When the distance D 91} between the protruding electrodes 91 is equal to or less than the upper limit, the degree of freedom in the arrangement of the protruding electrodes 91 is higher.

In addition, in this specification, "distance between mutually adjacent protruding electrodes" means the minimum value of the distance between the surfaces of mutually adjacent protruding electrodes.

_{The thickness T 90} of the portion of the work 90 excluding the protruding electrode 91 may be appropriately selected according to the purpose of use of the work 90 , and is not particularly limited.

For example, it is preferable that the said thickness T90 after grinding the back surface 90b of the workpiece|work _{90 is 50-500 micrometers. Since the thickness T 90} of the workpiece 90 after grinding the back surface 90b is equal to or greater than the lower limit, damage to the workpiece is suppressed when the workpiece 90 is divided (that is, divided into pieces). The effect is higher. _{When the thickness T 90} of the workpiece 90 after grinding the back surface 90b is equal to or less than the upper limit, a thin workpiece is obtained.

Work the thickness (T ₉₀₎ prior to grinding the back surface (90b) of (90) is preferably, 250~1500㎛.

The workpiece which is the object of use of the thermosetting resin film of this embodiment is not limited to what is shown in FIG. 1, Within the range which does not impair the effect of this invention, a part of structure may be changed, deleted, or added.

For example, in Fig. 1, the protruding electrode has a substantially spherical shape as described above (a shape in which a part of the sphere is cut by a plane), but this substantially spherical shape is shown in the height direction (in Fig. 1, the workpiece The shape formed by stretching in the direction perpendicular to the circuit surface 90a of (90), that is, the shape of a substantially elongated spheroid (in other words, the portion including one end in the long axis direction of the elongated spheroid) is on the plane A protruding electrode of a shape cut by a spheroid) or a shape formed by pressing the substantially spherical shape as described above in the height direction, that is, the shape of a substantially spheroidal spheroid (that is, one end of the short axis of the spheroidal spheroid) A protruding electrode having a shape in which the portion to be included is cut off by a plane) is also mentioned as a protruding electrode having a preferable shape. This substantially spheroid-shaped protruding electrode is also particularly advantageous in forming the first protective film using the thermosetting resin film of the present embodiment, similarly to the substantially spherical protruding electrode.

Examples of the protruding electrode include, in addition to these, those having a cylindrical shape, an elliptical cylindrical shape, a prismatic shape, an elliptical cone shape, a pyramidal shape, a truncated cone shape, an elliptical truncated cone shape, or a truncated pyramid shape; Those having a shape in which a cylinder, an elliptical cylinder, a prism, a truncated cone, an ellipsoidal truncated cone, or a truncated pyramid and the above-described approximately sphere or approximately spheroid are combined are also mentioned.

In addition, the shape of the protrusion-shaped electrode demonstrated so far is only a preferable example at the time of application of the thermosetting resin film of this embodiment, In this invention, the shape of the protrusion-shaped electrode is not limited to these.

Hereinafter, the structure of this invention is demonstrated in detail.

◎First support sheet

The said 1st support sheet may consist of one layer (single layer), and may consist of multiple layers of two or more layers. When a support sheet consists of multiple layers, the constituent material and thickness of these multiple layers may be mutually the same or different, and the combination of these multiple layers is not specifically limited unless the effect of this invention is impaired.

In addition, in this specification, it is not limited to the case of a 1st support sheet, "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, and only some layers may be may be the same", and further, "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is mutually different."

A preferred first support sheet includes, for example, a first substrate and a first pressure-sensitive adhesive layer formed on the first substrate (that is, the first substrate and the first pressure-sensitive adhesive layer are disposed in the thickness direction thereof). laminated), a first substrate, a first intermediate layer formed on the first substrate, and a first pressure-sensitive adhesive layer formed on the first intermediate layer (that is, a first substrate, a first intermediate layer) and what consists of 1st adhesive layer laminated|stacked in these thickness direction in this order), what consists only of a 1st base material, etc. are mentioned.

An example of the sheet|seat for 1st protective film formation of this embodiment is demonstrated for every kind of such a 1st support sheet below, referring drawings.

It is sectional drawing which shows typically an example of the sheet|seat for 1st protective film formation of this embodiment.

The 1st sheet|seat 1 for protective film formation shown here uses what is formed by laminating|stacking in these thickness directions in these thickness directions as a 1st support sheet. That is, the sheet 1 for forming a first protective film is made of a first base material 11 , a first pressure-sensitive adhesive layer 13 formed on one surface of the first base material 11 , and a first pressure-sensitive adhesive layer 13 . 1 The thermosetting resin layer (thermosetting resin film) 12 formed on the surface 13a opposite to the side of the base material 11 is provided and comprised.

The first support sheet 101 is a laminate of the first base material 11 and the first pressure-sensitive adhesive layer 13 . Then, the first protective film forming sheet 1 is formed on the first supporting sheet 101 and on one side 101a of the first supporting sheet 101, that is, on one side of the first pressure-sensitive adhesive layer 13 ( It can be said that the thermosetting resin layer 12 formed on 13a) was provided.

In the thermosetting resin layer 12 in the 1st sheet|seat 1 for protective film formation, the ratio of the total content of the above-mentioned thermosetting component is 40 mass % or more, and the sum total value of the above-mentioned X value is 400 g/eq or less.

It is sectional drawing which shows typically the other example of the sheet|seat for 1st protective film formation of this embodiment.

In addition, in the drawings after FIG. 3, the same code|symbol as the case of the case of the illustrated figure is attached|subjected to the component same as that shown in the figure already demonstrated, and the detailed description is abbreviate|omitted.

The sheet 2 for forming a first protective film shown here is used as a first supporting sheet in which the first base material, the first intermediate layer, and the first pressure-sensitive adhesive layer are laminated in this order in the thickness direction. . That is, the 1st sheet|seat 2 for protective film formation is the 1st base material of the 1st base material 11, the 1st intermediate|middle layer 14 formed on one side of the 1st base material 11, and the 1st intermediate|middle layer 14. The first pressure-sensitive adhesive layer 13 formed on the surface opposite to the (11) side, and a thermosetting resin layer (thermosetting) formed on the surface 13a opposite to the first intermediate layer 14 side of the first pressure-sensitive adhesive layer 13 A resin film) 12 is provided.

The first support sheet 102 is a laminate of the first base material 11 , the first intermediate layer 14 , and the first pressure-sensitive adhesive layer 13 . And the 1st sheet|seat 2 for protective film formation is provided with the 1st support sheet 102, On the one side 102a of the 1st support sheet 102, in other words, one side of the 1st adhesive layer 13 It can be said that the thermosetting resin layer 12 is provided on the surface 13a.

In other words, in the sheet|seat 1 for 1st protective film formation shown in FIG. 2, the 1st sheet|seat 2 for protective film formation WHEREIN: Between the 1st base material 11 and the 1st adhesive layer 13, Furthermore, the 1st The intermediate layer 14 is provided.

In the thermosetting resin layer 12 in the 1st sheet|seat 2 for protective film formation, the ratio of the total content of the above-mentioned thermosetting component is 40 mass % or more, and the sum total value of the above-mentioned X value is 400 g/eq or less.

It is sectional drawing which shows typically still another example of the sheet|seat for 1st protective film formation of this embodiment.

The sheet|seat 3 for 1st protective film formation shown here uses what consists only of a 1st base material as a 1st support sheet. That is, the 1st sheet|seat 3 for protective film formation is provided with the 1st base material 11 and the thermosetting resin layer (thermosetting resin film) 12 formed on the 1st base material 11, and is comprised.

The 1st support sheet 103 is comprised only with the 1st base material 11. As shown in FIG. And the 1st sheet|seat 3 for protective film formation is provided with the 1st support sheet 103, On the one side 103a of the 1st support sheet 103, in other words, on the one side of the 1st base material 11, It can be said that the thermosetting resin layer 12 is provided on (11a).

In other words, in the sheet|seat 1 for 1st protective film formation shown in FIG. 2, the 1st sheet|seat 3 for protective film formation WHEREIN: The 1st adhesive layer 13 is abbreviate|omitted.

In the thermosetting resin layer 12 in the sheet|seat 3 for 1st protective film formation, the ratio of the sum total content of the above-mentioned thermosetting component is 40 mass % or more, and the sum total value of the above-mentioned X value is 400 g/eq or less.

Next, the structure of a 1st support sheet is demonstrated.

In this embodiment, as a 1st support sheet, a well-known thing may be used and can select a 1st support sheet suitably according to the objective.

○First mention

The said 1st base material is a sheet form or a film form, and various resin is mentioned as the constituent material, for example.

The number of resins constituting the first substrate may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

One layer (single layer) may be sufficient as a 1st base material, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

It is preferable that the thickness of a 1st base material is 50-200 micrometers.

Here, "thickness of a 1st base material" means the thickness of the whole 1st base material, For example, the thickness of the 1st base material which consists of multiple layers means the total thickness of all the layers which comprise a 1st base material. .

The 1st base material may contain well-known various additives, such as a filler, a coloring agent, an antistatic agent, antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer), in addition to the main constituent materials, such as the said resin.

The 1st base material may be transparent, may be opaque, may be colored according to the objective, and another layer may be vapor-deposited.

When a 1st adhesive layer or thermosetting resin layer mentioned later has energy-beam sclerosis|hardenability, it is preferable that the 1st base material permeate|transmits an energy-beam.

The first substrate may be, for example, a release film in which one surface of a resin film described later in Examples is subjected to a release treatment by silicone treatment or the like.

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

○ 1st adhesive layer

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

As said adhesive, adhesive resins, such as an acrylic resin, a urethane resin, a rubber-type resin, a silicone resin, an epoxy resin, polyvinyl ether, polycarbonate, are mentioned, for example, An acrylic resin is preferable.

On the other hand, in the present invention, "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 other additives such as additives. Resin which shows adhesiveness by combined use with a component, resin etc. which show adhesiveness by presence of triggers, such as heat or water, are also included.

Only one layer (single layer) may be sufficient as a 1st adhesive layer, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

It is preferable that the thickness of a 1st adhesive layer is 3-40 micrometers.

Here, the "thickness of a 1st adhesive layer" means the thickness of the whole 1st adhesive layer, for example, the thickness of the 1st adhesive layer which consists of multiple layers is the sum total of all the layers which comprise a 1st adhesive layer. means thickness.

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

In this specification, an "energy beam" means having an energy proton in an electromagnetic wave or a charged particle beam, and an ultraviolet-ray, a radiation, an electron beam, etc. are mentioned as an example.

Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, etc. as an ultraviolet-ray source. The electron beam can irradiate what was generated by an electron beam accelerator or the like.

In the present invention, "energy ray sclerosis" means a property to harden|cure by irradiating an energy ray, and "non-energy ray sclerosis|hardenability" means a property which does not harden even if it irradiates an energy ray.

<1st adhesive composition>

The first pressure-sensitive adhesive layer may be formed by using the first pressure-sensitive adhesive composition containing the pressure-sensitive adhesive. For example, the 1st adhesive composition can be coated on the formation target surface of a 1st adhesive layer, and a 1st adhesive layer can be formed in the target site|part by drying as needed. A more specific method of forming the first pressure-sensitive adhesive layer will be described later in detail along with a method of forming another layer.

Coating of the first pressure-sensitive adhesive composition may be performed 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, a screen coater, The method of using various coaters, such as a Mayer bar coater and a kiss coater, is mentioned.

Although the drying conditions of a 1st adhesive composition are not specifically limited, When the 1st adhesive composition contains a solvent, it is preferable to heat-dry. You may dry the 1st adhesive composition containing a solvent on conditions for 10 second - 5 minutes at 70-130 degreeC, for example.

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

<1st adhesive composition other than 1st adhesive composition (I-1) - (I-3)>

The components contained in the first pressure-sensitive adhesive composition (I-1), the first pressure-sensitive adhesive composition (I-2), or the first pressure-sensitive adhesive composition (I-3) are the overall first pressure-sensitive adhesive composition other than these three types of the first pressure-sensitive adhesive composition. (In this specification, it is also called "1st adhesive composition other than 1st adhesive composition (I-1) - (I-3)"), and it can use similarly.

As 1st adhesive composition other than 1st adhesive composition (I-1) - (I-3), a non-energy-ray-curable adhesive composition is also mentioned other than energy-beam curable adhesive composition.

As a non-energy-ray-curable 1st adhesive composition, the 1st adhesive composition (I-4) containing the said adhesive resin (I-1a) is mentioned, for example.

It is preferable to contain an acrylic resin as said adhesive resin (I-1a), and, as for the 1st adhesive composition (I-4), it is more preferable to contain 1 type(s) or 2 or more types of crosslinking agents.

<The manufacturing method of a 1st adhesive composition>

The said 1st adhesive compositions, such as 1st adhesive composition (I-1) - (I-4), each component for constituting the first adhesive composition, such as the said adhesive and components other than the said adhesive as needed, It is obtained by mixing.

The order of addition at the time of mixing|blending each component is not specifically limited, You may add 2 or more types of components simultaneously.

When using a solvent, you may use by mixing a solvent with any compounding component other than a solvent, and diluting this compounding component beforehand, without diluting any compounding component other than a solvent beforehand, a solvent is mixed with these compounding components. You may use by mixing with.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not specifically limited unless each compounding component deteriorates, What is necessary is just to adjust suitably, It is preferable that the temperature is 15-30 degreeC.

○ 1st middle floor

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 of suppressing deformation of the first protective film by reflecting the shape of the protruding electrode existing on the circuit surface in the first protective film formed on the protruding electrode formation surface, the first protective film As a preferable structural material of an intermediate|middle layer, since the sticking property of a 1st intermediate|middle layer improves more, urethane (meth)acrylate etc. are mentioned.

One layer (single layer) may be sufficient as a 1st intermediate|middle layer, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

The thickness of the first intermediate layer may be appropriately adjusted according to the height of the protruding electrode existing on the surface of the workpiece or the workpiece to be protected. For example, it is preferable that the thickness of a 1st intermediate|middle layer is 50-600 micrometers from the point which can also easily absorb the influence of a comparatively high protrusion-shaped electrode.

Here, the “thickness of the first intermediate layer” means the entire thickness of the first intermediate layer, for example, the thickness of the first intermediate layer comprising a plurality of layers means the total thickness of all the layers constituting the first intermediate layer. .

<<The composition for forming a 1st intermediate|middle layer>>

A 1st intermediate|middle layer can be formed using the composition for 1st intermediate|middle layer formation containing the constituent material. For example, the first intermediate layer can be formed on the target site by coating the composition for forming the first intermediate layer on the surface to be formed of the first intermediate layer, drying if necessary, or curing by irradiation with energy rays. . A more specific method of forming the first intermediate layer, along with a method of forming another layer, will be described later in detail.

The composition for forming the first intermediate layer may be coated, for example, in the same manner as in the case of the first pressure-sensitive adhesive composition.

The drying conditions of the composition for 1st intermediate|middle layer formation are not specifically limited, For example, it may be the same as the drying conditions of the 1st adhesive composition.

When the composition for forming a 1st intermediate|middle layer has energy-beam sclerosis|hardenability, you may harden it by irradiation of an energy-beam after drying.

<The manufacturing method of the composition for 1st intermediate|middle layer formation>

The composition for forming the first intermediate layer may be prepared, for example, in the same manner as in the case of the first pressure-sensitive adhesive composition, except that the mixing components are different.

◎Thermosetting resin film (thermosetting resin layer)

The thermosetting resin film (thermosetting resin layer) is a film (layer) for protecting the circuit surface of the workpiece and the workpiece, and the protruding electrode formed on the circuit surface.

The thermosetting resin film forms a first protective film by thermosetting.

Meanwhile, in the present specification, even after the thermosetting resin film is cured (that is, after forming the first protective film), the cured product of the first support sheet and the thermosetting resin film (that is, the first support sheet and the first As long as the laminated structure of the protective film) is maintained, this laminated structure is called a "sheet for forming a first protective film”.

The said thermosetting resin film may have the characteristic of energy-beam curability other than a thermosetting characteristic, and does not need to have it.

However, when the thermosetting resin film has energy ray curing properties, the contribution of the thermosetting of the thermosetting resin film to the formation of the first protective film from the thermosetting resin film is larger than the contribution of the energy ray curing.

The said thermosetting resin film may consist of one layer (single layer), and may consist of two or more layers, irrespective of the presence or absence of energy-beam sclerosis|hardenability. When a thermosetting resin film consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

The thickness of the thermosetting resin film is preferably 1 to 100 µm, more preferably 3 to 80 µm, particularly preferably 5 to 60 µm, regardless of the presence or absence of energy ray curability. When the thickness of a thermosetting resin film is more than the said lower limit, the 1st protective film with a higher protective ability can be formed. When the thickness of the thermosetting resin film is equal to or less than the upper limit, the effect of suppressing the residual of the thermosetting resin film in the upper part of the protruding electrode at the time of sticking the thermosetting resin film to the protruding electrode formation surface of the work is higher. Moreover, when the thickness of a thermosetting resin film is below the said upper limit, at the time of division|segmentation of a workpiece|work, a 1st protective film can be cut|disconnected more favorably.

Here, "thickness of the thermosetting resin film" means the thickness of the whole thermosetting resin film, for example, the thickness of the thermosetting resin film consisting of multiple layers means the total thickness of all the layers constituting the thermosetting resin film. .

<<The composition for forming a thermosetting resin layer>>

A thermosetting resin film can be formed using the composition for thermosetting resin layer formation containing the constituent material. For example, a thermosetting resin film can be formed by coating the composition for thermosetting resin layer formation on the formation target surface, and drying it as needed. The ratio of content of components which do not vaporize at normal temperature in the composition for thermosetting resin layer formation becomes the same as the ratio of content of the said components in a thermosetting resin film normally.

Coating of the composition for forming a thermosetting resin layer may be performed 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, a screen A method using various coaters, such as a coater, a Mayer bar coater, and a kiss coater, is mentioned.

The drying conditions of the composition for thermosetting resin layer formation are not specifically limited, regardless of the presence or absence of energy-beam curability of a thermosetting resin film. However, when the composition for thermosetting resin layer formation contains the solvent mentioned later, it is preferable to heat-dry. You may dry the composition for thermosetting resin layer formation containing a solvent on the conditions for 10 second - 5 minutes at 70-130 degreeC, for example. However, it is preferable to heat-dry the composition for thermosetting resin layer formation so that this composition itself and the thermosetting resin film formed from this composition may not thermoset.

The curing conditions at the time of thermosetting the thermosetting resin film to form the first protective film are not particularly limited, as long as the degree of curing is such that the first protective film sufficiently exhibits its function. Depending on the type of the thermosetting resin film, it is appropriate you just have to choose

For example, it is preferable that it is 100-200 degreeC, as for the heating temperature at the time of thermosetting of a thermosetting resin film, it is more preferable that it is 110-180 degreeC, It is especially preferable that it is 120-170 degreeC. And, as for the heating time at the time of the said thermosetting, it is preferable that it is 0.5 to 5 hours, It is more preferable that it is 0.5 to 4 hours, It is especially preferable that it is 1 to 3 hours.

As a preferable thermosetting resin film, the thing containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component capable of curing (polymerization) reaction by using heat as a trigger of the reaction. In addition, in this specification, a polycondensation reaction is also included in a polymerization reaction.

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

As a preferable composition for thermosetting resin layer formation, for example, the composition (III-1) for thermosetting resin layer formation containing the said polymer component (A) and a thermosetting component (B) (in this specification, simply "composition ( III-1)"), etc. are mentioned.

[Polymer component (A)]

A polymer component (A) is a polymer compound for providing film-forming property, flexibility, etc. to a thermosetting resin film. The polymer component (A) has thermoplasticity and does not have thermosetting properties.

The number of polymer components (A) which the composition (III-1) and the thermosetting resin film contain may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

As a polymer component (A), an acrylic resin, a urethane resin, a phenoxy resin, a silicone resin, saturated polyester resin etc. are mentioned, for example.

Among these, it is preferable that a polymer component (A) is polyvinyl acetal or an acrylic resin.

As said polyvinyl acetal in a polymer component (A), a well-known thing is mentioned.

Especially, as a preferable polyvinyl acetal, polyvinyl formal, polyvinyl butyral, etc. are mentioned, for example, Polyvinyl butyral is more preferable.

Examples of polyvinyl butyral include those having structural units represented by the following formulas (i)-1, (i)-2, and (i)-3.

(Wherein, l, m, and n are each independently an integer of 1 or more)

It is preferable that it is 5000-20000, and, as for the weight average molecular weight (Mw) of polyvinyl acetal, it is more preferable that it is 8000-100000. When the weight average molecular weight of polyvinyl acetal is within such a range, the effect of suppressing the residual of the thermosetting resin film in the upper part of the protruding electrode when the thermosetting resin film is affixed to the protruding electrode formation surface becomes higher.

It is preferable that it is 40-80 degreeC, and, as for the glass transition temperature (Tg) of polyvinyl acetal, it is more preferable that it is 50-70 degreeC. When Tg of polyvinyl acetal is such a range, when a thermosetting resin film is affixed on the said protrusion-shaped electrode formation surface, the effect of suppressing the residual|survival of the thermosetting resin film in the upper part of a protrusion-shaped electrode becomes higher.

The ratio of three or more kinds of monomers constituting the polyvinyl acetal can be arbitrarily selected.

The acrylic resin in the polymer component (A) means a resin having a structural unit derived from (meth)acrylic acid or a derivative thereof.

In addition, in this specification, let "(meth)acrylic acid" be a concept including both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group", and "(meth) An acrylate" is a concept including both an "acrylate" and a "methacrylate".

In addition, in this specification, the "derivative" of a specific compound means that it has a structure in which one or more hydrogen atoms of the compound were substituted with groups (substituents) other than a hydrogen atom. For example, (meth)acrylic acid ester is a derivative of (meth)acrylic acid.

As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.

It is preferable that it is 10000-200000, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 100000-150000. When the weight average molecular weight of an acrylic resin is more than the said lower limit, the shape stability (temporal stability at the time of storage) of a thermosetting resin film improves. When the weight average molecular weight of the acrylic resin is equal to or less than the upper limit, the thermosetting resin film tends to follow the uneven surface of the adherend, and the occurrence of voids between the adherend and the thermosetting resin film is more suppressed.

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

It is preferable that it is -60-70 degreeC, and, as for the glass transition temperature (Tg) of an acrylic resin, it is more preferable that it is -30-50 degreeC. When Tg of an acrylic resin is more than the said lower limit, the adhesive force of the hardened|cured material of a thermosetting resin film, and a support sheet is suppressed, for example, and the peelability of a support sheet improves suitably. When Tg of an acrylic resin is below the said upper limit, the adhesive force with a to-be-adhered body of a thermosetting resin film and its hardened|cured material improves.

As an acrylic resin, For example, 1 type(s) or the polymer of 2 or more types (meth)acrylic acid ester; and copolymers of two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.

As the (meth)acrylic acid ester constituting the acrylic resin, for example, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)acrylate isopropyl, (meth)acrylic acid n -Butyl, (meth) acrylate isobutyl, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylic acid 2- Ethylhexyl, (meth)acrylic acid isooctyl, (meth)acrylic acid n-octyl, (meth)acrylic acid n-nonyl, (meth)acrylic acid isononyl, (meth)acrylic acid decyl, (meth)acrylic acid undecyl, (meth) Dodecyl acrylate ((meth) acrylate lauryl), (meth) acrylic acid tridecyl, (meth) acrylic acid tetradecyl ((meth) acrylate myristyl), (meth) acrylic acid pentadecyl, (meth) acrylate hexadecyl ((meth) acrylate The alkyl group constituting the alkyl ester, such as palmityl acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate) has a chain structure having 1 to 18 carbon atoms, ( meth)acrylic acid alkyl ester;

(meth)acrylic acid cycloalkyl esters, such as (meth)acrylic acid isobornyl and (meth)acrylic acid dicyclopentanyl;

(meth)acrylic acid aralkyl esters, such as (meth)acrylic acid benzyl;

(meth)acrylic acid cycloalkenyl esters, such as (meth)acrylic acid dicyclopentenyl ester;

(meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester;

(meth)acrylic acid imide;

glycidyl group-containing (meth)acrylic acid esters such as (meth)acrylic acid glycidyl;

(meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylate ) hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylic acid;

Substituted amino group containing (meth)acrylic acid ester, such as (meth)acrylic-acid N-methylaminoethyl, etc. are mentioned. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

The acrylic resin is, for example, in addition to the (meth)acrylic acid ester, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide 1 type or 2 or more types of monomers selected from may be formed by copolymerization.

The number of monomers constituting the acrylic resin may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The acrylic resin may have a functional group bondable with 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 said functional group of an acrylic resin may couple|bond with another compound through the crosslinking agent (F) mentioned later, and may couple|bond directly with another compound without passing through a crosslinking agent (F). When an acrylic resin bonds with another compound by the said functional group, there exists a tendency for the reliability of the package obtained using the 1st sheet|seat for protective film formation to improve.

In the present invention, for example, as the polymer component (A), a thermoplastic resin other than polyvinyl acetal and acrylic resin (hereinafter, it may be simply abbreviated as "thermoplastic resin"), polyvinyl acetal and acrylic resin It may be used independently, without using it, and may be used together with polyvinyl acetal or an acrylic resin. By using the above-mentioned thermoplastic resin, the peelability of the first protective film from the first supporting sheet is improved, or the thermosetting resin film tends to follow the uneven surface of the adherend, and voids or the like are generated between the adherend and the thermosetting resin film. In some cases, this is more suppressed.

It is preferable that it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

It is preferable that it is -30-150 degreeC, and, as for the glass transition temperature (Tg) of the said thermoplastic resin, it is more preferable that it is -20-120 degreeC.

As said thermoplastic resin, a polyester resin, a polyurethane resin, a phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The number of the thermoplastic resins contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, in the thermosetting resin film, the polymer component ( The ratio of the content of A) is, for example, any of 5 to 60 mass%, 5 to 45 mass%, 5 to 30 mass%, and 5 to 15 mass%, regardless of the type of the polymer component (A). It may be one.

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

[thermosetting component (B)]

A thermosetting component (B) is a component for having thermosetting property, thermosetting a thermosetting resin film, and forming a hard 1st protective film.

In addition, in a thermosetting resin film, the thermosetting component (B) corresponds to both the "thermosetting component" which prescribes|regulates the ratio of the above-mentioned total content, and the "thermosetting component" which is the calculation object of the said X value.

The number of the thermosetting component (B) contained in the composition (III-1) and the thermosetting resin film may be one, or two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

As a thermosetting component (B), an epoxy type thermosetting resin, polyimide resin, unsaturated polyester resin, etc. are mentioned, for example.

Among these, it is preferable that a thermosetting component (B) is an epoxy type thermosetting resin.

(epoxy thermosetting resin)

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

In the thermosetting resin film, the epoxy resin (B1) and the thermosetting agent (B2) correspond to both the "thermosetting component" that defines the ratio of the above-mentioned total content and the "thermosetting component" which is the calculation object of the X value. .

The number of the epoxy-based thermosetting resins contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

・Epoxy resin (B1)

As an epoxy resin (B1), a well-known thing is mentioned, For example, polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, orthocresol novolac epoxy resin, dicyclopenta Bifunctional or more than bifunctional epoxy compounds, such as a diene-type epoxy resin, a biphenyl-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, and a phenylene skeleton-type epoxy resin, are mentioned.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. The epoxy resin which has an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than the epoxy resin which does not have an unsaturated hydrocarbon group. For this reason, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the workpiece|work processed with the 1st protective film obtained using the 1st protective film formation sheet|seat improves.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by conversion into the group which has an unsaturated hydrocarbon group in a part of the epoxy group of a polyfunctional epoxy resin is mentioned, for example. Such a compound is obtained, for example, by addition-reacting (meth)acrylic acid or its derivative(s) to an epoxy group.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple|bonded with the aromatic ring which comprises an epoxy resin etc. are mentioned, for example.

The unsaturated hydrocarbon group is an unsaturated group having polymerizability, and specific examples thereof include an ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth)acrylamide group, etc. , an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 300 to 10000, from the viewpoint of curability of the thermosetting resin film and the strength and heat resistance of the resin film after curing, It is especially preferable that it is 300-3000.

It is preferable that the epoxy equivalent of an epoxy resin (B1) is 100-1000 g/eq, It is more preferable that it is 150-970 g/eq, It is still more preferable that it is 200-600 g/eq.

An epoxy resin (B1) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, these combinations and a ratio can be selected arbitrarily.

· Thermosetting agent (B2)

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

As a thermosetting agent (B2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group in which an acid group is anhydride, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrideized is preferable, and phenol It is more preferable that they are a sexual hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl-type phenol resins, and the like. can be heard

Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide.

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

As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin, etc. can be heard

The said unsaturated hydrocarbon group in a thermosetting agent (B2) is the same thing as the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.

When using a phenol-type hardening|curing agent as a thermosetting agent (B2), it is preferable that the softening point or glass transition temperature of a thermosetting agent (B2) is high from the point which the peelability of a 1st protective film from the 1st support sheet improves.

Among the thermosetting agents (B2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolak type phenol resin, a dicyclopentadiene type phenol resin, and an aralkyl type phenol resin is preferably 300 to 30000. And it is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Although the molecular weight of non-resin components, such as a biphenol and dicyandiamide, among thermosetting agents (B2) is not specifically limited, For example, it is preferable that it is 60-500.

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

In the composition (III-1) and the thermosetting resin film, the content of the thermosetting agent (B2) is, for example, 0.1 to 500 parts by mass, 1 to 250 parts by mass, with respect to 100 parts by mass of the content of the epoxy resin (B1), Any one of 1-150 mass parts, 1-100 mass parts, 1-75 mass parts, and 1-50 mass parts may be sufficient. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of a thermosetting resin film advances more easily. When the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption of a thermosetting resin film reduces and the reliability of the package obtained using the 1st sheet|seat for protective film formation improves more.

In the composition (III-1) and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is 100 mass of the content of the polymer component (A) With respect to a part, any one of 300-1400 mass parts, 400-1300 mass parts, 500-1100 mass parts, 600-1000 mass parts, and 700-900 mass parts may be sufficient, for example. When the said content of a thermosetting component (B) is such a range, the 1st protective film and 1st support sheet adhesive force is suppressed, for example, and the peelability of a 1st support sheet improves.

[curing accelerator (C)]

The composition (III-1) and the thermosetting resin film may contain the hardening accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).

Preferable examples of the curing accelerator (C) include 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 -imidazoles such as hydroxymethylimidazole (imidazole in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine (phosphine in which at least one hydrogen atom is substituted with an organic group); Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. are mentioned.

The number of curing accelerators (C) contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When using a hardening accelerator (C), in a composition (III-1) and a thermosetting resin film, content of a hardening accelerator (C) with respect to content of 100 mass parts of thermosetting component (B), for example, 0.01- Any one of 10 mass parts and 0.1-7 mass parts may be sufficient. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) is acquired more remarkably. When the content of the curing accelerator (C) is equal to or less than the upper limit, for example, the high polar curing accelerator (C) moves to the bonding interface side with the adherend in the thermosetting resin film under high temperature and high humidity conditions to prevent segregation the effect is increased As a result, the reliability of the workpiece|workpiece with a 1st protective film obtained using the 1st protective film formation sheet|seat improves more.

[Filling material (D)]

The composition (III-1) and the thermosetting resin film may contain the filler (D). When a thermosetting resin film contains a filler (D), adjustment of a thermal expansion coefficient becomes easy for the 1st protective film obtained by hardening|curing a thermosetting resin film. And, by optimizing this coefficient of thermal expansion for the object to be formed of the first protective film, the reliability of the workpiece with the first protective film obtained by using the first protective film forming sheet is further improved. Moreover, when a thermosetting resin film contains a filler (D), the moisture absorption of a 1st protective film can be reduced or heat dissipation can also be improved.

Although any of an organic filler and an inorganic filler may be sufficient as a filler (D), it is preferable that it is an inorganic filler.

Preferable inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned.

Among these, it is preferable that it is a silica or an alumina, and, as for an inorganic filler, it is more preferable that it is a silica.

What is necessary is just to select the average particle diameter of a filler (D) suitably according to the objective, It does not specifically limit, For example, 0.02-2 micrometers may be sufficient.

On the other hand, indicates the value of the "average particle diameter" means a particle diameter (D ₅₀₎ of from, integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method in particular there is no mention in the specification .

The number of fillers (D) which the composition (III-1) and the thermosetting resin film contain may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

In the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, in the thermosetting resin film, the filler (D) with respect to the total mass of the thermosetting resin film ) may be, for example, any one of 3 to 60 mass%, 4 to 40 mass%, 5 to 30 mass%, 5 to 20 mass%, and 5 to 15 mass%. When the ratio is within such a range, adjustment of the coefficient of thermal expansion of the first protective film becomes easier.

[Coupling agent (E)]

The composition (III-1) and the thermosetting resin film may contain the coupling agent (E). As a coupling agent (E), the adhesiveness and adhesiveness with respect to the to-be-adhered body of a thermosetting resin film can be improved by using what has a functional group which can react with an inorganic compound or an organic compound. Moreover, by using a coupling agent (E), the hardened|cured material of a thermosetting resin film does not impair heat resistance, but water resistance improves.

It is preferable that it is a compound which has a functional group which can react with the functional group which a polymer component (A), a thermosetting component (B), etc. have, and, as for a coupling agent (E), it is more preferable that it is a silane coupling agent.

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-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyl Triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

The number of coupling agents (E) which the composition (III-1) and the thermosetting resin film contain may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

When using a coupling agent (E), composition (III-1) and a thermosetting resin film WHEREIN: Content of a coupling agent (E) with respect to 100 mass parts of total content of a polymer component (A) and a thermosetting component (B) , for example, any one of 0.03 to 20 parts by mass, 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass may be sufficient. When the said content of a coupling agent (E) is more than the said lower limit, the effect by using the coupling agent (E), such as the improvement of the dispersibility with respect to resin of a filler (D), and the improvement of adhesiveness with a to-be-adhered body of a thermosetting resin film is obtained more significantly. When the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of an outgas is suppressed more.

[Crosslinking agent (F)]

As the polymer component (A), when using a polymer component (A) having a functional group such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxyl group, and isocyanate group capable of bonding to other compounds, such as the above-mentioned acrylic resin, composition (III) -1) and the thermosetting resin film may contain the crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking by bonding the functional group in the polymer component (A) with another compound, and by crosslinking in this way, the initial adhesive force and cohesive force of the thermosetting resin film can be adjusted.

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

As said organic polyhydric isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (Hereinafter, these compounds may be abbreviated as "aromatic polyvalent isocyanate compound etc." collectively.) ; a trimer, an isocyanurate body, and an adduct body, such as the said aromatic polyhydric isocyanate compound; The terminal isocyanate urethane prepolymer etc. which are obtained by making the said aromatic polyhydric isocyanate compound etc. react with a polyol compound are mentioned. The "adduct body" is the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. means the reactants of As an example of the said adduct body, the xylylene diisocyanate adduct of trimethylol propane mentioned later, etc. are mentioned. In addition, "terminal isocyanate urethane prepolymer" means a prepolymer which has an isocyanate group in the terminal part of a molecule|numerator while having a urethane bond.

As said organic polyhydric isocyanate compound, More specifically, For example, 2, 4- tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate were added to all or some hydroxyl groups of polyols such as trimethylolpropane; Lysine diisocyanate etc. are mentioned.

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

When using an organic polyvalent isocyanate compound as a crosslinking agent (F), as a polymer component (A), it is preferable to use a hydroxyl-containing polymer. When a crosslinking agent (F) has an isocyanate group and a polymer component (A) has a hydroxyl group, a crosslinked structure can be easily introduce|transduced into a thermosetting resin film by reaction of a crosslinking agent (F) and a polymer component (A).

The number of crosslinking agents (F) contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When using a crosslinking agent (F), in composition (III-1), content of a crosslinking agent (F) is 0.01-20 mass parts with respect to 100 mass parts of content of a polymer component (A), 0.1-20 mass parts, for example. Any one of 10 mass parts and 0.5-5 mass parts may be sufficient. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is acquired more remarkably. When the said content of a crosslinking agent (F) is below the said upper limit, excessive use of a crosslinking agent (F) is suppressed.

[Energy-ray-curable resin (G)]

The composition (III-1) and the thermosetting resin film may contain the energy ray-curable resin (G). Since the thermosetting resin film contains energy-beam curable resin (G), a characteristic can be changed by irradiation of an energy-beam.

Energy-beam curable resin (G) is obtained by superposing|polymerizing (hardening) an energy-beam curable compound.

As said energy-beam-curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, for example, The acrylate type compound which has a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di ( chain aliphatic skeleton-containing (meth)acrylates such as meth)acrylate; cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylate; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylate; polyether (meth)acrylates other than the polyalkylene glycol (meth)acrylate; Itaconic acid oligomer etc. are mentioned.

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said energy-beam curable compound, it is more preferable that it is 300-10000.

The number of the said energy-ray-curable compound used for superposition|polymerization may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The number of energy ray-curable resins (G) contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

When using the energy ray-curable resin (G), in the composition (III-1), the ratio of the content of the energy ray-curable resin (G) to the total mass of the composition (III-1) is, for example, Any one of 1-95 mass %, 5-90 mass %, and 10-85 mass % may be sufficient.

[Photoinitiator (H)]

When the composition (III-1) and the thermosetting resin film contain the energy ray-curable resin (G), in order to efficiently advance the polymerization reaction of the energy ray-curable resin (G), the photopolymerization initiator (H) may be contained. .

As the photoinitiator (H) in the composition (III-1), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoin compounds such as methyl benzoate and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; 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 etc. are mentioned.

Moreover, as said photoinitiator, For example, quinone compounds, such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. are mentioned.

The number of photoinitiators (H) contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

When using a photoinitiator (H), in composition (III-1), content of a photoinitiator (H) is 0.1-20 mass with respect to content of 100 mass parts of energy-beam curable resin (G), for example. part, 1-10 mass parts, and any one of 2-5 mass parts may be sufficient.

[Colorant (I)]

The composition (III-1) and the thermosetting resin film may contain the coloring agent (I).

As a coloring agent (I), well-known things, such as an inorganic type pigment, an organic type pigment, and organic type dye, are mentioned, for example.

Examples of the organic pigments and organic dyes include aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squarylium pigments, azrenium pigments, polymethine pigments, and naphthoquinone pigments. Pigment, pyrylium pigment, phthalocyanine pigment, naphthalocyanine pigment, naphtholactam pigment, azo pigment, condensed azo pigment, indigo pigment, perinone pigment, perylene pigment, dioxazine pigment, quinacridone pigment , isoindolinone pigment, quinophthalone pigment, pyrrole pigment, thioindigo pigment, metal complex pigment (metal complex dye), dithiol metal complex pigment, indole phenol pigment, triarylmethane pigment, and anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazolone dyes, pyranthrone dyes, and srene dyes.

Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO ( Indium tin oxide) type pigment|dye, ATO (antimony tin oxide) type pigment|dye, etc. are mentioned.

The number of colorants (I) contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When using a coloring agent (I), what is necessary is just to adjust content of the coloring agent (I) of a thermosetting resin film suitably according to the objective. For example, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, in the thermosetting resin film, relative to the total mass of the thermosetting resin film , the ratio of the content of the coloring agent (I)) may be 0.1 to 5 mass%. When the said ratio is more than the said lower limit, the effect by using a coloring agent (I) is acquired more remarkably. When the said ratio is below the said upper limit, the excessive fall of the light transmittance of a thermosetting resin film is suppressed.

[Universal Additive (J)]

The composition (III-1) and the thermosetting resin film may contain the general-purpose additive (J) within the range which does not impair the effect of this invention.

The general-purpose additive (J) may be a well-known one, can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of the general-purpose additive (J) include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, and the like.

The number of general-purpose additives (J) contained in the composition (III-1) and the thermosetting resin film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

Content of the composition (III-1) and the general-purpose additive (J) of a thermosetting resin film is not specifically limited, What is necessary is just to select suitably according to the objective.

[menstruum]

The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent becomes favorable in handling property.

The solvent is not particularly limited, but is preferably, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The number of solvents contained in the composition (III-1) may be one, or two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint of more uniformly mixing the components contained in the composition (III-1).

Content of the solvent of a composition (III-1) is not specifically limited, For example, what is necessary is just to select suitably according to the kind of components other than a solvent.

As an example of a preferable thermosetting resin film of this embodiment, a thermosetting resin film for forming a first protective film on the surface by attaching and thermosetting the work to a surface having a protruding electrode,

The thermosetting resin film contains two or more types of thermosetting components other than the acrylic resin having an epoxy group,

In the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film is 40% by mass or more,

About the said thermosetting component contained in the said thermosetting resin film, the following formula for each type:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

When the X value calculated by

The light transmittance at a wavelength of 1342 nm of the laminated film having a total thickness of 200 µm formed by laminating two or more layers of the thermosetting resin film having a thickness of 200 µm or the thermosetting resin film having a thickness of less than 200 µm is 50% or more , and a thermosetting resin film.

As another example of a preferable thermosetting resin film of this embodiment, a thermosetting resin film for forming a first protective film on the surface by attaching and thermosetting the work to a surface having a protruding electrode,

The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D),

The thermosetting component consists of an epoxy resin (B1) and a thermosetting agent (B2),

In the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film (that is, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is 40 mass% or more,

The ratio of content of the said polymer component (A) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-30 mass %,

The ratio of content of the said filler (D) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-20 mass %,

About the said thermosetting component contained in the said thermosetting resin film, the following formula for each type:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

When the X value calculated by is obtained and the sum of the X values in all kinds of the thermosetting components contained in the thermosetting resin film is obtained, the total value is 400 g / eq or less, the thermosetting resin film can

As another example of a preferable thermosetting resin film of this embodiment, a thermosetting resin film for forming a first protective film on the surface by attaching and thermosetting the work to a surface having a protruding electrode,

The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D),

The thermosetting component consists of an epoxy resin (B1) and a thermosetting agent (B2),

In the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film (that is, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is 40 mass% or more,

The ratio of content of the said polymer component (A) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-30 mass %,

The ratio of content of the said filler (D) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-20 mass %,

About the said thermosetting component contained in the said thermosetting resin film, the following formula for each type:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

When the X value calculated by

The light transmittance at a wavelength of 1342 nm of the laminated film having a total thickness of 200 µm formed by laminating two or more layers of the thermosetting resin film having a thickness of 200 µm or the thermosetting resin film having a thickness of less than 200 µm is 50% or more , and a thermosetting resin film.

As another example of a preferable thermosetting resin film of this embodiment, a thermosetting resin film for forming a first protective film on the surface by attaching and thermosetting the work to a surface having a protruding electrode,

The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D),

The thermosetting component consists of an epoxy resin (B1) and a thermosetting agent (B2),

In the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film (that is, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is 40 mass% or more,

The ratio of content of the said polymer component (A) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-30 mass %,

The ratio of content of the said filler (D) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-20 mass %,

About the said thermosetting component contained in the said thermosetting resin film, the following formula for each type:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

When the X value calculated by

Using the first protective film having a size of 20 mm × 130 mm and a thickness of 40 μm, obtained by thermosetting the thermosetting resin film by heating at 130° C. for 2 hours, the distance between the grippers is 80 mm, and the tension and a thermosetting resin film, wherein the breaking strength of the first protective film is 55 MPa or less when the first protective film is pulled in a direction parallel to the surface by the gripper at a speed of 200 mm/min. .

As another example of a preferable thermosetting resin film of this embodiment, a thermosetting resin film for forming a first protective film on the surface by attaching and thermosetting the work to a surface having a protruding electrode,

The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D),

The thermosetting component consists of an epoxy resin (B1) and a thermosetting agent (B2),

In the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film (that is, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is 40 mass% or more,

The ratio of content of the said polymer component (A) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-30 mass %,

The ratio of content of the said filler (D) with respect to the gross mass of the said thermosetting resin film in the said thermosetting resin film is 5-20 mass %,

About the said thermosetting component contained in the said thermosetting resin film, the following formula for each type:

X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]

When the X value calculated by

The light transmittance at a wavelength of 1342 nm of the laminated film having a total thickness of 200 µm formed by laminating two or more layers of the thermosetting resin film having a thickness of 200 µm or the thermosetting resin film having a thickness of less than 200 µm is 50% or more is,

Using the first protective film having a size of 20 mm × 130 mm and a thickness of 40 μm, obtained by thermosetting the thermosetting resin film by heating at 130° C. for 2 hours, the distance between the grippers is 80 mm, and the tension and a thermosetting resin film, wherein the breaking strength of the first protective film is 55 MPa or less when the first protective film is pulled in a direction parallel to the surface by the gripper at a speed of 200 mm/min. .

<<The manufacturing method of the composition for thermosetting resin layer formation>>

The composition for forming a thermosetting resin layer, such as composition (III-1), is obtained by mix|blending each component for constituting this.

The order of addition at the time of mixing|blending each component is not specifically limited, You may add 2 or more types of components simultaneously.

When using a solvent, you may use by mixing a solvent with any compounding component other than a solvent, and diluting this compounding component beforehand, without diluting any compounding component other than a solvent beforehand, a solvent is mixed with these compounding components. You may use by mixing with.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

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.

◇The manufacturing method of the sheet|seat for 1st protective film formation

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

For example, in the case of laminating the first pressure-sensitive adhesive layer or the first intermediate layer on the first substrate when manufacturing the first support sheet, the above-described first pressure-sensitive adhesive composition or composition for forming a first intermediate layer on the first substrate A 1st adhesive layer or a 1st intermediate|middle layer can be laminated|stacked by coating, drying as needed, or irradiating an energy ray.

On the other hand, for example, when a thermosetting resin layer (thermosetting resin film) is further laminated on the first adhesive layer laminated on the first substrate, the composition for forming a thermosetting resin layer is coated on the first adhesive layer, , it is possible to directly form the thermosetting resin layer. Similarly, in the case of further laminating the first pressure-sensitive adhesive layer on the first intermediate layer laminated on the first substrate, it is possible to directly form the first pressure-sensitive adhesive layer by coating the first pressure-sensitive adhesive composition on the first intermediate layer. do. As described above, in the case of forming a continuous two-layer laminate structure using a certain composition, it is possible to form a new layer by further coating another composition on the layer formed from the composition. However, the layer to be laminated later among these two layers is previously formed using the above composition on another release film, and the exposed surface of this formed layer opposite to the side in contact with the release film is exposed to the remaining layers already formed. It is preferable to form the laminated structure of two continuous layers by bonding together with a surface. At this time, it is preferable to apply the said composition to the peeling process surface of a peeling film. What is necessary is just to remove a peeling film after formation of a laminated structure as needed.

For example, a first adhesive layer is laminated on a first substrate, and a thermosetting resin layer is laminated on the first adhesive layer. When manufacturing the sheet for forming a first protective film that is a laminate of layers), the first pressure-sensitive adhesive composition is coated on the first substrate and dried as necessary, whereby the first pressure-sensitive adhesive layer is laminated on the first substrate, Separately, a composition for forming a thermosetting resin layer is coated on a release film and, if necessary, dried to form a thermosetting resin layer on the release film, and the exposed surface of the thermosetting resin layer is laminated on the first substrate. The sheet for 1st protective film formation is obtained by bonding together with the exposed surface of an adhesive layer and laminating|stacking a thermosetting resin layer on a 1st adhesive layer.

Moreover, for example, when manufacturing the 1st support sheet in which a 1st intermediate|middle layer is laminated|stacked on a 1st base material, and the 1st adhesive layer is laminated|stacked on the said 1st intermediate|middle layer, a 1st intermediate|middle layer on a 1st base material By coating the composition for formation, drying as needed, or irradiating an energy ray, the 1st intermediate|middle layer is laminated|stacked on the 1st base material, and the 1st adhesive composition is separately coated on the peeling film, and if necessary The 1st adhesive layer is formed on the peeling film by drying by drying, the exposed surface of this 1st adhesive layer is bonded together with the exposed surface of the 1st intermediate|middle layer laminated|stacked on the 1st base material, The 1st adhesive layer is a 1st intermediate|middle layer By laminating|stacking on it, a 1st support sheet is obtained. In this case, for example, a curable resin layer is formed on the release film by separately coating the composition for forming a thermosetting resin layer on the release film and drying as necessary, and the exposed surface of the curable resin layer is The sheet for 1st protective film formation is obtained by bonding together with the exposed surface of the 1st adhesive layer laminated|stacked on the 1st intermediate|middle layer, and laminating|stacking a thermosetting resin layer on a 1st adhesive layer.

On the other hand, when laminating the first pressure-sensitive adhesive layer or the first intermediate layer on the first substrate, as described above, instead of the method of coating the first pressure-sensitive adhesive composition or the composition for forming the first intermediate layer on the first substrate, peeling The first pressure-sensitive adhesive composition or the composition for forming the first intermediate layer is coated on the film, dried as needed, or irradiated with energy rays to form the first pressure-sensitive adhesive layer or the first intermediate layer on the release film, and these layers You may laminate|stack a 1st adhesive layer or a 1st intermediate|middle layer on a 1st base material by bonding together the exposed surface of a 1st base material with one surface.

In any method, what is necessary is just to remove the peeling film at arbitrary timings after formation of the target laminated structure.

In this way, since all layers other than the first base material constituting the first sheet for forming a protective film can be laminated by a method of forming in advance on the release film and bonding them to the surface of the target layer, such What is necessary is just to select suitably the layer employ|adopting a process, and to manufacture the sheet|seat for 1st protective film formation.

On the other hand, the 1st sheet|seat for protective film formation is normally stored in the state by which the peeling film was pasted to the surface of the outermost layer (for example, thermosetting resin layer) opposite to the 1st support sheet. Therefore, on this release film (preferably, the release treatment surface thereof), a composition for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting resin layer, is coated and, if necessary, dried to form a release film. A layer constituting the outermost layer is formed on the surface, and the remaining respective layers are laminated on the exposed surface opposite to the side in contact with the release film of this layer by any of the methods described above, and the release film is bonded without removing it. Also by setting it as it is, the 1st sheet|seat for protective film formation is obtained.

As a 1st support sheet, you may use a commercial item.

◇Manufacturing method of workpiece on which the first protective film is formed

In the case of using the thermosetting resin film or the sheet for forming a first protective film according to an embodiment of the present invention, the method for manufacturing a workpiece on which the first protective film is formed is a surface having a protruding electrode of the work (that is, forming a protruding electrode) A step of affixing a thermosetting resin film to the side) (in this specification, it may be abbreviated as a “sticking step”), and a step of thermosetting the thermosetting resin film after affixing to form a first protective film (this specification) In this case, it may be abbreviated as "a first protective film forming step") and by irradiating a laser beam through the first protective film from the side provided with the first protective film to the work. a step of forming a modified layer inside of 1 By expanding together with the protective film, the workpiece is divided in the portion of the modified layer, and the first protective film is cut, and the workpiece and the surface having the protruding electrode of the workpiece (i.e., protruding) It has a process (in this specification, abbreviated as "division/cutting process" sometimes abbreviated as "division/cutting process") of obtaining the workpiece|work with a 1st protective film provided with the 1st protective film formed on the upper electrode formation surface).

Hereinafter, the manufacturing method will be described in detail with reference to the drawings.

5A to 5C and FIGS. 6A to 6B are enlarged cross-sectional views for schematically explaining a method of manufacturing the workpiece on which the first protective film is formed. Here, the manufacturing method at the time of using the 1st sheet|seat 1 for protective film formation shown in FIG. 2 is demonstrated.

<<pasting process>>

In the pasting step, as shown in FIG. 5A , on the protruding electrode formation surface of the work 90 (that is, the surface 91a of the protruding electrode 91 and the circuit surface 90a of the work 90 ). A thermosetting resin film 12 is affixed. By performing this process, the thermosetting resin film 12 spreads between the protruding-shaped electrodes 91 which exist in multiple numbers, closely_contact|adheres to the protrusion-shaped electrode formation surface, and the surface 91a of the protruding-shaped electrode 91. , in particular, it is possible to cover the surface 91a of the portion in the vicinity of the circuit surface 90a of the work 90 to embed the protruding electrode 91 to cover these regions. In addition, by performing this step, the upper portion including the top portion 910 of the protruding electrode 91 penetrates the thermosetting resin film 12 and protrudes from the thermosetting resin film 12 .

In the pasting step, for example, the thermosetting resin film 12 may be used alone, but as shown here, the first supporting sheet 101 and the thermosetting resin film formed on the first supporting sheet 101 . It is preferable to use the sheet|seat 1 for 1st protective film formation provided with (12) and comprised. As mentioned later, when grinding the back surface 90b of the workpiece|work 90, the surface protection tape for back grinding can be used for the 1st support sheet 101.

In the pasting process, when using the 1st sheet|seat 1 for protective film formation as shown here, the thermosetting resin film 12 in the 1st sheet|seat 1 for protective film formation is the protruding electrode of the workpiece|work 90. What is necessary is just to stick 1st sheet|seat 1 itself for protective film formation to the protrusion-shaped electrode formation surface of the workpiece|work 90 by sticking to a formation surface.

In addition, in this specification, the 1st protective film formation sheet|seat affixed on the protruding electrode formation surface of a work as shown here, and what was comprised may be called a "1st laminated structure". In FIG. 5A, as the 1st laminated structure 201, the 1st sheet|seat 1 for protective film formation was affixed on the protruding electrode formation surface of the workpiece|work 90, and it has shown that it was comprised.

In the pasting step, the exposed surface (in this specification, it may be referred to as a "first surface") 12a of the thermosetting resin film 12 on the side facing the work 90 is applied to the work 90 . The thermosetting resin film 12 is affixed to the protruding electrode formation surface by pressing on the protruding electrode formation surface of can do.

In a sticking process, it is preferable to stick to the protruding electrode formation surface, heating the thermosetting resin film 12. By doing in this way, between the thermosetting resin film 12 and the protruding electrode formation surface, that is, between the thermosetting resin film 12 and the circuit surface 90a of the workpiece 90, and the thermosetting resin film 12, In any of between the surfaces 91a of the protruding electrodes 91, the generation of voids can be further suppressed. In addition, in the upper portion including the top portion 910 of the protruding electrode 91, the remaining of the thermosetting resin film 12 can be further suppressed, and finally, the remaining of the first protective film in this upper portion is more can be suppressed

The heating temperature of the thermosetting resin film 12 at the time of sticking should just not be an excessively high temperature, for example, it is preferable that it is 60-100 degreeC. Here, "excessive high temperature" means a temperature at which an action other than the intended purpose is expressed in the thermosetting resin film 12, for example, at which thermosetting of the thermosetting resin film 12 proceeds.

When the thermosetting resin film 12 is affixed to the surface on which the protruding electrode is formed, the pressure applied to the thermosetting resin film 12 (in this specification, it may be referred to as “sticking pressure”) is 0.3 to 1 MPa. desirable.

After forming the 1st laminated structure 201 by the sticking process, you may use this 1st laminated structure 201 as it is in the next process. However, if necessary, the back surface 90b of the workpiece|work 90 is ground. By doing so, the thickness of the work 90 may be adjusted. The 1st laminated structure 201 after grinding the back surface 90b of the workpiece|work 90 will also be in the state shown to FIG. 5A except the point from which the thickness of the workpiece|work 90 differs.

Grinding of the back surface 90b of the workpiece 90 can be performed by a known method, such as a method using a grinder.

Before and after grinding the back surface 90b of the workpiece 90 , the thickness of the portion of the workpiece 90 excluding the protruding electrode 91 is as described above.

After forming the 1st laminated structure 201 by a pasting process, the 1st support sheet 101 is removed from the thermosetting resin film 12 in the 1st laminated structure 201 . When the back surface 90b of the workpiece|work 90 is ground, it is preferable to remove the 1st support sheet 101 after this grinding.

By performing such a process, as shown in FIG. 5B, the 2nd lamination|stacking comprised with the thermosetting resin film 12 provided on the protruding electrode formation surface of the workpiece|work 90, but not provided with the 1st support sheet 101. A structure (that is, a workpiece on which a thermosetting resin film is formed) 202 is obtained.

In the second laminated structure 202 , the upper portion including the top portion 910 of the protruding electrode 91 penetrates and protrudes through the thermosetting resin film 12 , and is exposed.

When the first pressure-sensitive adhesive layer 13 is energy-beam curable, the first pressure-sensitive adhesive layer 13 is cured by irradiation with energy rays to reduce the adhesiveness of the first pressure-sensitive adhesive layer 13, and then a thermosetting resin film ( It is preferable to remove the first support sheet 101 from 12).

<<1st protective film formation process>>

In the said 1st protective film formation process, the thermosetting resin film 12 after sticking is thermosetted, and as shown to FIG. 5C, the 1st protective film 12' is formed.

When the first laminated structure 201 is formed, the first protective film forming step can be performed after removing the first supporting sheet 101 .

In addition, when the back surface 90b of the workpiece|work 90 is ground, the 1st protective film formation process can be performed after grinding the said back surface 90b.

By performing this step, the third laminated structure (that is, the work on which the first protective film is formed) 203 constituted by providing the first protective film 12 ′ on the protruding electrode formation surface of the work 90 is obtained. In Fig. 5C, reference numeral 12a' denotes the contact surface of the first protective film 12' with the work 90 (in this specification, it may be referred to as a "first surface").

The curing conditions of the thermosetting resin film 12 are not particularly limited as long as the degree of curing of the first protective film 12 ′ is sufficient to exhibit its function, and depending on the type of the thermosetting resin film 12, if appropriately selected do.

For example, the heating temperature and heating time at the time of thermosetting of the thermosetting resin film 12 are as having demonstrated previously.

At the time of thermosetting of the thermosetting resin film 12, you may pressurize the curable resin film 12, and it is preferable that the pressurization pressure in that case is 0.3-1 Mpa.

In the second laminated structure (workpiece with a thermosetting resin film) 202 shown in FIG. 5B , in the upper portion including the top portion 910 of the protruding electrode 91, the residual of the thermosetting resin film 12 is is restrained. For this reason, the remaining of the first protective film 12' is also suppressed in the upper portion of the protruding electrode 91 after the completion of this process.

<<Reformed layer forming process>>

In the modified layer forming step, as shown in FIG. 6A , the laser beam R from the side provided with the first protective film 12' to the work 90 through the first protective film 12'. ) to form a modified layer 900 in the inside of the work 90 .

After the modified layer forming step, since division (i.e., dicing) of the work 90, which will be described later, is performed, the modified layer forming step is performed in the third laminated structure (workpiece with the first protective film) 203 in the work ( It is preferable to carry out after affixing a dicing sheet or the sheet|seat for 2nd protective film formation to the back surface 90b of 90).

In addition, in this specification, the 1st protective film is provided on the protruding electrode formation surface of a work in this way, and a dicing sheet or a 2nd protective film formation sheet is provided on the back surface of a work in this way, and what is constituted is "fourth laminated structure" It is sometimes called

Moreover, what has the structure in which the modified layer was formed inside the workpiece|work in a 4th laminated structure may be called "5th laminated structure".

In FIG. 6A , as the fifth laminated structure 205 , the first protective film 12 ′ is provided on the protruding electrode formation surface of the work 90 , and the second protective film is formed on the back surface 90b of the work 90 . It has shown that the sheet|seat 8 for use is provided, and the modified layer 900 is formed in the inside of the workpiece|work 90, and it is comprised.

The sheet 8 for forming a second protective film shown here includes a second base material 81 , a second pressure-sensitive adhesive layer 83 formed on the second base material 81 , and a number formed on the second pressure-sensitive adhesive layer 83 . A base layer (resin film) 82 is provided and constituted.

The laminate of the second base material 81 and the second pressure-sensitive adhesive layer 83 is a second support sheet 801 .

Accordingly, the second protective film forming sheet 8 is formed on the second supporting sheet 801 and on one side 801a of the second supporting sheet 801, that is, on one side of the second pressure-sensitive adhesive layer 83 ( It can be said that the resin layer (resin film) 82 formed on 83a) was provided.

The resin layer (resin film) 82 is for forming a second protective film on the back surface 90b of the work 90 . The second protective film covers and protects the back surface 90b of the work 90 . More specifically, the second protective film prevents cracks from occurring in the workpiece during division of the workpiece or between packaging the workpiece obtained by division of the workpiece and manufacturing the target substrate device.

The resin layer 82 may have only one characteristic of thermosetting and energy-beam sclerosis|hardenability, may have both characteristic, and does not need to have both characteristic. When the resin layer 82 is curable (that is, it has at least one characteristic of thermosetting and energy-beam curability), the hardened|cured material is a 2nd protective film. When the resin layer 82 is non-curable (that is, it does not have properties of both thermosetting and energy ray curability), in the step in which the resin layer 82 is pasted to the back surface 90b of the work 90 , the second It is assumed that a protective film has been formed.

As with the first pressure-sensitive adhesive layer 13 , the second pressure-sensitive adhesive layer 83 may be either energy ray curable or non-energy ray curable. The energy ray-curable second pressure-sensitive adhesive layer 83 can easily control physical properties before and after curing.

The second substrate 81 may be, for example, the same as the first substrate (eg, the first substrate 11 in the sheet 1 for forming a first protective film) in the first sheet for forming a protective film described above. .

In the said manufacturing method, you may use things other than the sheet|seat 8 for 2nd protective film formation as a sheet|seat for 2nd protective film formation.

In the said manufacturing method, it is not limited to the sheet|seat 8 for 2nd protective film formation, A well-known thing can be used as the sheet|seat for 2nd protective film formation.

Similarly, in the said manufacturing method, a well-known thing can be used as a dicing sheet.

In the modified layer forming step, a focus is set in a specific region to be a divided portion of the work 90 in the inside of the work 90 , and the laser beam R is irradiated so as to be focused on the focus. By the irradiation of the laser light R, the modified layer 900 is formed in the irradiation area.

The thermosetting resin film 12 and the first protective film 12' have light transmittance with a wavelength of 1342 nm, Preferably, the light transmittance of the thermosetting resin film 12 and the first protective film 12' with a wavelength of 1342 nm When this is high as described above, the laser light having a wavelength of 1342 nm passes through the first protective film 12' favorably. Therefore, even if the workpiece 90 is irradiated with laser light R through the first protective film 12' from the side provided with the first protective film 12', the inside of the workpiece 90 is modified. The layer 900 can be well formed.

<<division/cutting process>>

In the dividing/cutting step, the workpiece 90 after forming the modified layer 900 is placed together with the first protective film 12', in other words, the fifth laminated structure 205 is applied to the circuit surface 90a thereof. By expanding in a parallel direction (the direction of arrow E in FIG. 6A ), the work 90 is divided in the portion of the modified layer 900 , and the first protective film 12 ′ is cut. As a result, as shown in FIG. 6B , the circuit of the workpiece 9 and the projecting electrode formation surface of the workpiece 9 (that is, the surface 91a of the projecting electrode 91 and the workpiece 9 ) A workpiece 990 with a first protective film having a first protective film (first protective film after cutting 120') formed on the surface 9a) is obtained.

By performing this step, the workpiece 9 having the cut first protective film 120' on the protruding electrode formation surface (that is, the workpiece 990 with the first protective film formed thereon) becomes the second support sheet 801 ), the sixth laminated structure 206 in a state in which a plurality (many) are aligned is obtained. In Fig. 6B, reference numeral 120a' denotes the contact surface of the first protective film 120' after cutting with the workpiece 9 (in this specification, it may be referred to as a "first surface"), and reference numeral 9b denotes the workpiece. The back surface of the workpiece 9 is shown.

Since the first protective film 12' is formed of the thermosetting resin film 12 that satisfies the condition of the sum of the X values, in the division/cutting process, the first protective film 12' can be easily cut. can As a result, the workpiece 9 having the cut first protective film 120' on the protruding electrode formation surface can be manufactured with high efficiency. In this step, the first protective film 12 ′ is cut along the divided portion of the work 90 , and finally cut along the outer periphery of the workpiece 9 .

In the division/cutting step, the expanding is preferably performed under a temperature condition of -15 to 5°C. When the temperature at the time of expansion is equal to or less than the upper limit, the cutting of the first protective film 12' becomes easier. When the temperature at the time of expansion is more than the said lower limit, excessive cooling can be avoided.

Here, the case where the resin layer 82 in the sheet 8 for forming a second protective film is also cut by performing the above dividing/cutting step is shown. However, the cutting of the resin layer 82 is performed after the dividing/cutting step in a publicly known manner. You may carry out separately according to a method. In FIG. 6B, the code|symbol 820 is attached|subjected to the resin layer 82 after cut|disconnection. In addition, although the case where the resin layer 82 is cut|disconnected is shown here, you may cut|disconnect the 2nd protective film obtained by hardening this without cut|disconnecting in the step of the resin layer 82.

In the above manufacturing method, the resin layer 82 or the second protective film is cut along the divided portions of the work 90 in the same manner as in the case of the first protective film 12'.

In addition, in this specification, even after the said resin layer is cut|disconnected, as long as the laminated structure of the 2nd support sheet and the said resin layer (that is, the 2nd support sheet and the said resin layer after cutting) is maintained, this laminated structure is referred to as a “sheet for forming a second protective film”.

◇Manufacturing method of substrate device

After obtaining the workpiece on which the first protective film is formed (that is, the sixth laminated structure) by the above-described manufacturing method, the workpiece on which the first protective film is formed is flip-chip on the circuit surface of the substrate by a known method. After connection, it is set as a package, and the target board|substrate device can be manufactured by using this package (not shown). When the semiconductor chip with the 1st protective film is used, the target semiconductor device can be manufactured by using this semiconductor package after manufacturing a semiconductor package. Moreover, when the semiconductor chip provided with the 1st protective film and the 2nd protective film is used, the semiconductor chip with these protective films is flip-chip-connected, and the target semiconductor device can be manufactured.

Example

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

In addition, each target object manufactured in the comparative example shown below is given the same name as each target object manufactured in the Example for convenience.

The component used for manufacture of the composition for thermosetting resin layer formation is shown below.

[Polymer component (A)]

(A)-1: polyvinyl butyral ("S-Rec SV-10" manufactured by Sekisui Chemical Industry Co., Ltd., weight average molecular weight 65000, glass transition temperature 66°C)

(A)-2: polyvinyl butyral ("S-Rec BL-10" manufactured by Sekisui Chemical Industry Co., Ltd., weight average molecular weight 25000, glass transition temperature 59°C)

(A)-3: copolymerization of n-butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass), and 2-hydroxyethyl acrylate (15 parts by mass) acrylic resin (weight average molecular weight 800000, glass transition temperature -28°C).

[thermosetting component (B)]

・Epoxy resin (B1)

(B1)-1: bisphenol A epoxy resin ("EXA-4810-1000" manufactured by DIC, epoxy equivalent 404 to 412 g/eq)

(B1)-2: dicyclopentadiene type epoxy resin ("EPICLON HP-7200" manufactured by DIC, epoxy equivalent 265 g/eq)

(B1)-3: liquid modified epoxy resin (“YX7110” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 962 g/eq)

(B1)-4: mixture of liquid bisphenol A epoxy resin and acrylic rubber fine particles ("BPA328" manufactured by Nippon Shokubai, epoxy equivalent 235 g/eq)

(B1)-5: Solid bisphenol A epoxy resin ("Epicoat 1055" manufactured by Mitsubishi Chemical Corporation, molecular weight 1600, softening point 93°C, epoxy equivalent 800 to 900 g/eq)

(B1)-6: dicyclopentadiene type epoxy resin ("XD-1000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 248 g/eq)

· Thermosetting agent (B2)

(B2)-1: novolak-type phenol resin (Showa Denko Co., Ltd. "Shonol BRG-556", hydroxyl equivalent 104 g/eq)

(B2)-2: dicyandiamide ("ADEKA Hardner EH-3636AS" manufactured by ADEKA, solid dispersion latent curing agent, active hydrogen amount 21 g/eq)

[curing accelerator (C)]

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

[Filling material (D)]

(D)-1: Silica filler (“YA050C-MKK” manufactured by Admatex, average particle diameter of 0.05 μm)

(D)-2: Silica filler (“SC2050MA” manufactured by Admatex, silica filler surface-modified with an epoxy compound, average particle diameter of 500 nm)

(D)-3: silica filler ("SV-10" manufactured by Tatsumori, average particle diameter of 8 µm)

[Coupling agent (E)]

(E)-1: Silane coupling agent ("MKC silicate MSEP2" manufactured by Mitsubishi Chemical Corporation, silicate compound to which γ-glycidoxypropyltrimethoxysilane was added)

[Colorant (I)]

(I)-1: Carbon black (“MA-600B” manufactured by Mitsubishi Chemical Corporation)

[Example 1]

<<Manufacture of a thermosetting resin film and the sheet|seat for 1st protective film formation>>

<Production of the composition for forming a thermosetting resin layer>

Polymer component (A)-1 (9.9 mass parts), epoxy resin (B1)-1 (37.8 mass parts), epoxy resin (B1)-2 (25.0 mass parts), thermosetting agent (B2)-1 (18.1 mass parts) ), curing accelerator (C)-1 (0.2 parts by mass), and filler (D)-1 (9.0 parts by mass) were mixed, further diluted with methyl ethyl ketone, and stirred at 23 ° C. The composition (III-1) for thermosetting resin layer formation whose total density|concentration of six components other than a ketone is 55 mass % was prepared. Table 1 shows these components and their content. In addition, description with "-" in the column of containing components in Table 1 means that the composition for thermosetting resin layer formation does not contain the component. In addition, the "ratio (mass %) of the total content of all kinds of thermosetting components" in Table 1 means "the ratio of the total content of all kinds of thermosetting components with respect to the total mass of the thermosetting resin film in the thermosetting resin film" means

<Production of thermosetting resin film>

Using a release film (“SP-PET381031” manufactured by Lintec, 38 µm thick) in which one side of a polyethylene terephthalate film has been peeled off by silicone treatment, the thermosetting resin layer obtained above is formed on the peeling-treated surface A 30-micrometer-thick thermosetting resin film was produced by coating composition (III-1) and drying at 100 degreeC for 2 minutes.

<Manufacture of the sheet|seat for 1st protective film formation>

Next, by bonding one side of the surface protection tape for back grinding (“Adwill E-8180HR” manufactured by Lintec Co., Ltd.) to the exposed surface of the obtained thermosetting resin film (that is, the side opposite to the side provided with the release film), , a sheet for forming a first protective film was produced. The said surface protection tape corresponds to a 1st support sheet.

<<Manufacture of the semiconductor chip with a 1st protective film>>

The release film is removed from the thermosetting resin film in the sheet for forming a first protective film obtained above, and the resulting exposed surface of the thermosetting resin film (that is, the surface opposite to the side provided with the surface protection tape) is The sheet for forming a 1st protective film was affixed to the bump formation surface of a semiconductor wafer by crimping|bonding to the bump formation surface of a semiconductor wafer. At this time, sticking of the 1st sheet|seat for protective film formation uses a sticking apparatus (roller-type laminator, "RAD-3510 F/12" by Lintec Corporation), table temperature 90 degreeC, sticking speed 2 mm/sec, and sticking pressure 0.5 It performed while heating a thermosetting resin film on the conditions of MPa. As the semiconductor wafer, a bump having a height of 210 µm, a bump width of 250 µm, a distance between adjacent bumps of 400 µm, and a thickness excluding the bumps of 750 µm were used.

As mentioned above, the 1st laminated structure comprised by the 1st sheet|seat for protective film formation was affixed on the bump formation surface of a semiconductor wafer was obtained.

Next, the surface (rear surface) opposite to the bump formation surface of the semiconductor wafer in the obtained 1st laminated structure was ground using the grinder ("DGP8760" by Disco Corporation). At this time, the said back surface was ground until the thickness of the site|part except the bump of a semiconductor wafer was set to 250 micrometers.

Next, the surface protection tape (that is, the first supporting sheet) was removed from the thermosetting resin film in the first laminated structure.

As mentioned above, the 2nd laminated structure (semiconductor wafer with a thermosetting resin film) comprised by equipping the bump formation surface of a semiconductor wafer with a thermosetting resin film was obtained.

Next, using a thermosetting device (“RAD-9100 m/12” manufactured by Lintec Co., Ltd.), the thermosetting resin film in the second laminated structure obtained above was subjected to a treatment temperature of 130° C., a treatment pressure of 0.5 MPa, and a treatment time of 2 hours. It was thermosetted by heat-pressing-processing in this, and the 1st protective film was formed.

Thus, the 3rd laminated structure (that is, the semiconductor wafer in which the 1st protective film was formed) comprised with the 1st protective film on the bump formation surface of a semiconductor wafer was obtained.

Next, in the obtained third laminated structure, a dicing tape (“Adwill D-841” manufactured by Lintec Co., Ltd.) is adhered to the back surface (that is, the grinding surface) of the semiconductor wafer, whereby the first protective film is formed on the bump formation surface of the semiconductor wafer. was provided, and the 4th laminated structure comprised with the dicing tape on the said back surface was obtained. The said dicing tape corresponds to a 2nd support sheet.

Next, using a dicing apparatus ("DFL7361" manufactured by Disco Corporation), the first protective film from the side provided with the first protective film so as to focus on the semiconductor wafer in the fourth laminated structure to a focal point set therein. By irradiating laser light therebetween, a modified layer was formed inside the semiconductor wafer. At this time, the wavelength of the laser light was 1342 nm, the output was 0.7 W, and the frequency was 90 kHz.

By the above, the 5th laminated structure which has the structure in which the modified layer was formed in the inside of the semiconductor wafer in the 4th laminated structure was obtained.

Next, in an environment of 0° C., the semiconductor wafer (that is, the fifth laminate structure) after the formation of the modified layer is expanded together with the first protective film in a direction parallel to the circuit surface thereof, whereby the portion of the modified layer is , while dividing the semiconductor wafer, the first protective film was cut along the division portion of the semiconductor wafer. At this time, using a die separator (“DDS2300” manufactured by Disco Corporation), the second support sheet in the fifth laminated structure is placed on the table in the die separator, and the periphery of the fifth laminated structure is fixed, and in this state The semiconductor wafer and the 1st protective film were expanded by pushing up a table on the conditions of 50 mm/sec of pushing speed|rate, and 20 mm of pushing amount. The size of the obtained semiconductor chip was 2 mm x 2 mm.

As described above, a plurality (many) of semiconductor chips having the first protective film after cutting on the bump formation surface (that is, the semiconductor chip on which the first protective film is formed) are aligned on the second support sheet (that is, the dicing tape) A sixth laminated structure in one state was obtained.

<<Evaluation of thermosetting resin film>>

<Confirmation of the residual suppression property of the thermosetting resin film in the upper part of the bump>

At the time of manufacturing the semiconductor chip on which the above-mentioned first protective film is formed, from the bump formation surface side of the semiconductor wafer, using a scanning electron microscope ("VE-9800" manufactured by Keyence Corporation), the acceleration voltage is 5 keV, and the first laminate structure observed And according to the following evaluation criteria, the residual suppression of the thermosetting resin film in the upper part of the bump in a 1st laminated structure was evaluated. A result is shown in Table 1.

(Evaluation standard)

A: The boundary between a bump and a thermosetting resin film can be confirmed, and it can confirm that the thermosetting resin film does not remain|survive on the upper part of a bump.

B: The boundary between the bump and the thermosetting resin film could not be confirmed, and it could be confirmed that the thermosetting resin film remained on the bump.

<Measurement of light transmittance of thermosetting resin film>

Five thermosetting resin films for testing (40 µm in thickness) were prepared in the same manner as in the production of the above-described thermosetting resin film except that the coating amount of the composition (III-1) for forming the thermosetting resin layer was changed.

Next, the laminated|multilayer film (200 micrometers in thickness) was obtained by laminating|stacking these five thermosetting resin films for a test in these thickness directions.

Next, the light transmittance with a wavelength of 1342 nm was measured about this laminated|multilayer film using the spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600 by SHIMADZU"). A result is shown in Table 1.

<<Evaluation of the first protective film>>

<Evaluation of the division property of a semiconductor wafer>

The 6th laminated structure obtained above was observed from the 1st protective film side using the digital microscope ("VH-Z100" by Keyence Corporation). At this time, the observation region is a first region corresponding to the central portion among the alignment surfaces of the semiconductor chip on which the first protective film is formed of the second support sheet, and a position on the periphery side that is point-symmetric with respect to the first region, In addition, a total of five regions of the second region, the third region, the fourth region, and the fifth region having the same distance from the first region were selected. All of these five regions were regions including semiconductor chips in which 25 first protective films were formed in 5 rows and 5 columns, assuming that the semiconductor wafer was normally divided. In addition, the first region is present in an approximately central portion of the first line segment connecting the second region and the third region, and the first region is present in an approximately central portion of the second line segment connecting the fourth region and the fifth region, in a clockwise direction. , these five regions were selected so that the second region, the fourth region, the third region, and the fifth region are located in this order. The first line segment and the second line segment are orthogonal to each other. Then, these five regions were observed, and the division property of the semiconductor wafer was evaluated according to the following evaluation criteria. A result is shown in Table 1.

(Evaluation standard)

A: In all five regions (all regions of the first to fifth regions), the semiconductor wafer is normally divided.

B: In at least one region (at least one of the first region to the fifth region), there is a location where the semiconductor wafer is not normally divided.

<Evaluation of the cutting property of the first protective film>

At the time of evaluation of the splitting property of the above-described semiconductor wafer, at the same time, the cutability of the first protective film was evaluated according to the following evaluation criteria. A result is shown in Table 1.

(Evaluation standard)

A: In all five regions (all regions of the first to fifth regions), the first protective film is normally cut.

B: In at least one region (at least one region of the first region to the fifth region), there is a portion where the first protective film is not normally cut.

<Measurement of breaking strength of the first protective film>

A thermosetting resin film for testing (40 µm in thickness) was prepared in the same manner as in the production of the above-described thermosetting resin film, except that the coating amount of the composition (III-1) for forming the thermosetting resin layer was changed.

Next, this thermosetting resin film for a test was thermosetted by heating at 130 degreeC for 2 hours.

Next, from this cured product (that is, the first protective film), a section having a size of 20 mm x 130 mm was cut out, and this was used as a test piece.

Using a universal tensile tester ("Autograph AG-IS" manufactured by Shimadzu Corporation), the distance between the grippers was 80 mm, the tensile speed was 200 mm/min, and the test piece was placed in a direction parallel to the surface. WHEREIN: It tensioned with the gripper, the maximum stress of the said test piece at this time was measured, and this was employ|adopted as breaking strength of the 1st protective film. A result is shown in Table 1.

[Comparative Example 1]

<<Manufacture of a thermosetting resin film and the sheet|seat for 1st protective film formation>>

<Production of the composition for forming a thermosetting resin layer>

Polymer component (A)-2 (10.0 parts by mass), epoxy resin (B1)-2 (30.0 parts by mass), epoxy resin (B1)-3 (33.0 parts by mass), thermosetting agent (B2)-1 (16.0 parts by mass) ), curing accelerator (C)-1 (0.2 parts by mass), and filler (D)-1 (11.0 parts by mass) were mixed, further diluted with methyl ethyl ketone, and stirred at 23 ° C. The composition for resin layer formation whose total density|concentration of six components other than ethyl ketone is 55 mass % was prepared. Table 1 shows these components and their content.

<Manufacture of a thermosetting resin film and the sheet|seat for 1st protective film formation>

As the composition for forming a resin layer, a thermosetting resin film and a sheet for forming a first protective film were prepared in the same manner as in Example 1 except that the composition obtained above was used.

<<Manufacture of the semiconductor chip with a 1st protective film>>

Production of the semiconductor chip (that is, the 6th laminated structure) on which the 1st protective film was formed was attempted in the same manner as in the case of Example 1 except that the one obtained above was used as the 1st protective film forming sheet|seat.

<<Evaluation of a thermosetting resin film and a 1st protective film>>

About the thermosetting resin film and 1st protective film manufactured by this comparative example, the method similar to the case of Example 1 evaluated. A result is shown in Table 1.

[Comparative Example 2]

<<Manufacture of a thermosetting resin film and the sheet|seat for 1st protective film formation>>

<Production of the composition for forming a thermosetting resin layer>

Polymer component (A)-3 (21.0 parts by mass), epoxy resin (B1)-4 (10.0 parts by mass), epoxy resin (B1)-5 (2.0 parts by mass), epoxy resin (B1)-6 (5.6 parts by mass) ), thermosetting agent (B2)-2 (0.5 parts by mass), curing accelerator (C)-1 (0.5 parts by mass), filler (D)-2 (6.0 parts by mass), filler (D)-3 (54.0 parts by mass) ), coupling agent (E)-1 (0.4 parts by mass), and colorant (I)-1 (1.9 parts by mass) were mixed, further diluted with methyl ethyl ketone, and stirred at 23 ° C. The composition for resin layer formation whose total density|concentration of 10 components other than ethyl ketone is 55 mass % was prepared. Table 1 shows these components and their content.

<Manufacture of a thermosetting resin film and the sheet|seat for 1st protective film formation>

As the composition for forming a resin layer, a thermosetting resin film and a sheet for forming a first protective film were prepared in the same manner as in Example 1 except that the composition obtained above was used.

<<Manufacture of the semiconductor chip with a 1st protective film>>

Production of the semiconductor chip (that is, the 6th laminated structure) on which the 1st protective film was formed was attempted in the same manner as in the case of Example 1 except that the one obtained above was used as the 1st protective film forming sheet|seat.

<<Evaluation of a thermosetting resin film and a 1st protective film>>

About the thermosetting resin film and 1st protective film manufactured by this comparative example, the method similar to the case of Example 1 evaluated. A result is shown in Table 1.

As is clear from the above results, the thermosetting resin film of Example 1 was able to suppress the residual in the upper part of the bumps when affixed to the bump formation surface of the semiconductor wafer, and had desirable characteristics.

In the thermosetting resin film of Example 1, the ratio of the total content of all kinds of thermosetting components with respect to the gross mass of the thermosetting resin film was 80.9 mass %.

Moreover, in Example 1, the division|segmentation property of a semiconductor wafer was favorable.

The light transmittance of the thermosetting resin film of Example 1 is high at a wavelength of 1342 nm, and as a result, the light transmittance of the first protective film formed from this film is also high, and when the semiconductor wafer is irradiated with laser light through the first protective film , it was possible to favorably form the modified layer on the inside of the semiconductor wafer.

Moreover, in Example 1, the cutability of the 1st protective film was favorable.

In Example 1, the sum of the X values is 296 (={408×37.8/(37.8+25.0+18.1)}+{265×25.0/(37.8+25.0+18.1)}+{104×18.1/ (37.8+25.0+18.1)}) g/eq, and the breaking strength of the first protective film was 45 MPa.

On the other hand, in Comparative Example 1, the cutability of the first protective film was poor.

In Comparative Example 1, the sum of the X values is 524 (={265×30.0/(30.0+33.0+16.0)}+{962×33.0/(30.0+33.0+16.0)}+{104×16.0/ (30.0+33.0+16.0)}) g/eq, and the breaking strength of the first protective film was 60 MPa.

The thermosetting resin film of Comparative Example 2 was not able to suppress the residual in the upper part of the bump when affixed to the bump-formed surface of the semiconductor wafer, and had poor properties.

In the thermosetting resin film of the comparative example 2, the ratio of the total content of all types of thermosetting components with respect to the gross mass of the thermosetting resin film was 17.8 mass %.

Moreover, in Comparative Example 2, the division property of the semiconductor wafer was poor.

The light transmittance of the thermosetting resin film of Comparative Example 2 was low at a wavelength of 1342 nm, and as a result, the light transmittance of the first protective film formed from this film was also low, and when the semiconductor wafer was irradiated with laser light through the first protective film , the modified layer could not be properly formed inside the semiconductor wafer. As a result, the semiconductor wafer could not be divided normally.

In Comparative Example 2, the first protective film could not be cut, but it could not be determined to what extent the characteristics of the first protective film itself had an influence on this result, and the cutability of the first protective film could not be evaluated. However, since the breaking strength of the 1st protective film was as small as 25 MPa, it was estimated that the 1st protective film could not be cut|disconnected mainly because the division property of a semiconductor wafer was inferior.

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

1, 2, 3… A sheet for forming a first protective film, 11... The first substrate, 11a... One side of the first substrate, 12 ... Thermosetting resin layer (thermosetting resin film), 12'... The first protective film, 120'... 1st protective film after cutting|disconnection, 13... 1st adhesive layer, 13a... One side of the first pressure-sensitive adhesive layer, 14 ... The first intermediate layer, 101, 102, 103... 1st support sheet, 101a, 102a, 103a... The surface of the first support sheet, 206 ... A sixth laminated structure, 90 ... Walk, 90a... The circuit surface of the workpiece, 91 ... The protruding electrode, 91a... The surface of the protruding electrode, 900 . . . Reformed layer, 990... A workpiece on which the first protective film is formed, R... laser light

Claims (2)

A thermosetting resin film for forming a first protective film on a surface of a work by attaching it to a surface having a protruding electrode and thermosetting it, comprising:
The thermosetting resin film contains two or more types of thermosetting components other than the acrylic resin having an epoxy group,
In the thermosetting resin film, the ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film is 40% by mass or more,
With respect to the thermosetting component contained in the thermosetting resin film, the following formula for each type:
X = [equivalent (g/eq) of functional group related to thermosetting reaction of thermosetting component] x [content (part by mass) of thermosetting component of thermosetting resin film] / [total content of thermosetting components of all types of thermosetting resin film ( parts by mass)]
A thermosetting resin film, wherein the total value is 400 g/eq or less when the X value calculated by A sheet for forming a first protective film, comprising a first support sheet and comprising the thermosetting resin film according to claim 1 on one side of the first support sheet.

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