JPWO2019008898A1 - Resin film forming film and resin film forming composite sheet - Google Patents

Abstract

This resin film forming film satisfies the following conditions (i) and (ii). (I) A first test piece prepared by using a first laminated body having a size of 50 mm×50 mm and a thickness of 200 μm, which is formed by laminating a plurality of the resin film forming films, is placed in 2 parts of pure water. When soaked for a time, the water absorption of the first test piece becomes 0.55% or less. (Ii) When the second test piece produced by using the second laminate in which the resin film forming film is attached to a silicon mirror wafer is aged for 30 minutes in an environment of 23° C. and 50% RH. The adhesive strength between the resin film-forming film or the cured product thereof and the silicon mirror wafer was measured before and after the second test piece was dipped in pure water for 2 hours after the aging. At this time, the adhesive force change rate is 60% or less.

Description

The present invention relates to a resin film forming film and a resin film forming composite sheet.
The present application claims priority based on Japanese Patent Application No. 2017-132980 filed in Japan on July 6, 2017, the content of which is incorporated herein.

In the process of manufacturing a semiconductor device, a semiconductor chip having a resin film containing an organic material (semiconductor chip with a resin film) or this resin film is formed on the surface (rear surface) opposite to the circuit surface of the semiconductor chip. A resin film-forming film (semiconductor chip with a resin film-forming film) is used. Examples of the resin film include a cured product of the resin film forming film. In this case, after the resin film forming film is attached to the surface (rear surface) opposite to the circuit surface of the semiconductor wafer, the semiconductor wafer is divided into semiconductor chips and the resin film forming film is cured. By doing so, a semiconductor chip with a resin film is manufactured.
On the other hand, examples of semiconductor chips to which the resin film forming film is used include those having bumps which are electrodes on the circuit surface and those not having bumps.

The semiconductor chip having no bumps on the circuit surface is the most widely used one, and the back surface of the semiconductor chip is usually used as the resin film forming film for die bonding the semiconductor chip to the circuit forming surface of the substrate. The film adhesive used is provided. That is, the resin film forming film in this case is a film adhesive.
On the other hand, a semiconductor chip having bumps on the circuit surface is flip-chip connected to the circuit formation surface of the substrate by the bumps. However, since the back surface of the semiconductor chip in this case is exposed as it is, the back surface is usually provided with a protective film as the resin film. That is, the resin film in this case is a protective film, and the resin film forming film is a protective film forming film.

  A semiconductor chip with a resin film and a semiconductor chip with a film for resin film formation are manufactured using, for example, a composite sheet for resin film formation, which comprises a support sheet and a film for resin film formation on the support sheet. To be done. More specifically, it is as follows. That is, first, the resin film forming composite sheet is attached to the back surface of the semiconductor wafer by the resin film forming film in the sheet. Next, if necessary, the resin film forming film is cured, and then the semiconductor wafer is diced together with the resin film forming film or a cured product thereof into individual semiconductor chips. Next, the semiconductor chip is separated from the support sheet and picked up with the resin film forming film after cutting or the cured product provided on the back surface thereof. By the above, a semiconductor chip with a resin film forming film or a semiconductor chip with a resin film is obtained. There are several methods for dicing, but the most widely used method is a method using a dicing blade (blade dicing). When performing blade dicing, the support sheet functions as a dicing sheet.

  Various composite sheets for forming a resin film have been disclosed so far. For example, a thermosetting resin film-forming film containing an inorganic filler in a specific range with respect to an organic resin component, having a melt viscosity before thermosetting within a specific range, and having excellent adhesion to an adherend ( A thermosetting die bond film) and a resin film forming composite sheet (dicing die bond film) including this film are disclosed (see Patent Documents 1 and 2).

  On the other hand, conventionally, after performing the blade dicing, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film is picked up by separating from the supporting sheet, the resin film forming film to be picked up together with the semiconductor chip or The problem that a part or all of the resin film remains on the support sheet, that is, the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film cannot be normally obtained, and a pickup defect is likely to occur. , There was a problem. Such a problem is remarkable in the case of a resin film forming film-equipped semiconductor chip or a resin film-equipped semiconductor chip having a small size such that the length of one side of the semiconductor chip is 4 mm or less.

  On the other hand, is the thermosetting resin film-forming film and the resin film-forming composite sheet including this film disclosed in Patent Documents 1 and 2 capable of solving such a problem? I'm not sure.

Japanese Patent No. 4732472 Japanese Patent No. 5390209

  The present invention comprises a resin film forming composite sheet together with a support sheet, and a resin film forming film for forming a resin film on the back surface of a semiconductor chip, wherein the blade is formed by using the resin film forming film. When a semiconductor chip with a resin film forming film or a semiconductor chip with a resin film having a small size obtained after dicing is picked up from a supporting sheet, it is possible to suppress the resin film forming film or the resin film from remaining on the supporting sheet. An object of the present invention is to provide a resin film forming film and a resin film forming composite sheet including the film.

  The present invention provides a resin film-forming film, which comprises a laminate of a plurality of the resin film-forming films, a first laminate having a size of 50 mm × 50 mm and a thickness of 200 μm. When the film for film formation is energy ray curable, the first cured product obtained by curing the first laminate with energy rays is used as a first test piece, and the resin film formation film is non-energy ray curable. In one case, when the first laminate is used as a first test piece and the first test piece is immersed in pure water for 2 hours, the water absorption rate of the first test piece is 0.55% or less, In addition, a second laminate is prepared by attaching the resin film forming film to a silicon mirror wafer, and when the resin film forming film is energy ray curable, the second laminate in the second laminate is formed. The cured second laminated body obtained by curing the resin film forming film with an energy beam to form a second cured product is used as a second test piece, and the second test piece is placed under an environment of a temperature of 23 ° C. and a relative humidity of 50%. The adhesive strength after aging between the second cured product and the silicon mirror wafer was measured when left standing for 30 minutes, and the second test piece after aging was immersed in pure water for 2 hours. When the adhesive strength after immersion between the second cured product and the silicon mirror wafer was measured, the adhesive strength change of the second test piece calculated from the adhesive strength after aging and the adhesive strength after immersion. When the rate is 60% or less, or when the resin film-forming film is non-energy ray curable, the second laminate is used as a second test piece, and the second test piece is heated to a temperature of 23. The adhesive force after aging between the resin film forming film and the silicon mirror wafer was measured when it was left standing for 30 minutes in an environment of ° C and relative humidity of 50%, and the first 2 When the adhesive strength after immersion between the resin film-forming film and the silicon mirror wafer was measured when the test piece was immersed in pure water for 2 hours, the adhesive strength after aging and the adhesive strength after immersion were measured. Provided is a resin film-forming film in which the calculated adhesive force change rate of the second test piece is 60% or less.

When a third laminate having a size of 15 mm × 150 mm and a thickness of 200 μm, which is formed by laminating a plurality of the resin film forming films, is prepared, and the resin film forming film is energy ray curable, The third cured product obtained by curing the third laminated body with energy rays is used as a third test piece. When the resin film forming film is non-energy ray curable, the third laminated body is As the test piece, when the third test piece was dipped in pure water for 2 hours, the tensile test according to JIS K 7127 was performed and the test speed was measured at 200 mm / min. The Young's modulus may be 15 MPa or more.
The resin film-forming film of the present invention contains a filler, and in the resin film-forming film, the ratio of the content of the filler to the total mass of the resin film-forming film is 25 to 75% by mass. May be
The present invention comprises a support sheet, a resin film-forming film provided on the support sheet, wherein the resin film-forming film is the resin film-forming film of the present invention described above. Providing composite sheets.

  The resin film forming film of the present invention can form a resin film forming composite sheet together with a support sheet, and can form a resin film on the back surface of a semiconductor chip. By using the resin film-forming film, blade dicing is performed to obtain a small resin film-forming film-equipped semiconductor chip or resin film-equipped semiconductor chip, and when these are picked up from the support sheet, to the support sheet. The resin film forming film or the resin film can be prevented from remaining.

It is sectional drawing which shows typically one Embodiment of the composite sheet for resin film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for resin film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for resin film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for resin film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for resin film formation of this invention.

◇ Resin film-forming film The resin film-forming film of the present invention has a water absorption rate of 0.55% or less in the following first test piece produced from the film, and in the following second test piece produced from the film. The rate of change in adhesive strength is 60% or less.
When the resin film forming film is non-energy ray curable, the first test piece is formed by laminating a plurality of the resin film forming films, and has a size of 50 mm × 50 mm and a thickness of 200 μm. It is one laminated body. When the resin film forming film is energy ray curable, the first test piece is a first cured product obtained by energy ray curing the first laminate.
When the resin film forming film is non-energy ray curable, the second test piece is a second laminated body obtained by sticking the resin film forming film to a silicon mirror wafer. Is energy ray curable, the second test piece is a cured second laminated body after the resin film forming film in the second laminated body is energy ray cured to form a second cured product. .
The water absorption of the first specimen (%) is calculated by the formula _{"(W B -W A) / W} A × 100 ". Here, W _A is the mass of the first specimen before soaking in pure water, W _B is the first test piece was immersed for 2 hours first test piece was measured W _A in pure water Is the mass of.
When the resin film forming film is non-energy ray curable, the adhesive force change rate (%) of the second test piece is calculated by the formula “(| P _B2- P _A2 |) / P _A2 × 100”. Here, P _A2 is the resin film-forming film and silicon in the second test piece when the second test piece is left standing for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. It is the adhesive force with the mirror wafer (adhesive force after lapse of time). In addition, P _B2 is between the resin film forming film in the second test piece after the immersion and the silicon mirror wafer when the second test piece after the aging is immersed in pure water for 2 hours. It is the adhesive strength (adhesive strength after immersion).
On the other hand, when the resin film forming film is energy ray curable, the adhesive force change rate (%) of the second test piece is calculated by the formula “(| P _B1 −P _A1 |) / P _A1 × 100”. . Here, P _A1 is the second cured product in the second test piece and the silicon mirror when the second test piece is left standing for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. It is the adhesive force with the wafer (adhesive force after aging). Further, P _B1 is the adhesion between the second cured product in the second test piece after the immersion and the silicon mirror wafer when the second test piece after the aging was immersed in pure water for 2 hours. Force (adhesion after immersion).
The water absorption rate and the adhesive force change rate described above will be described in more detail later.

  The resin film forming film of the present invention can be used for forming a resin film on the surface of the semiconductor chip opposite to the circuit surface (which may be referred to as "back surface" in this specification). .. The resin film-forming film of the present invention may be either curable or non-curable, as described later. In the present specification, unless otherwise specified, when the resin film forming film is curable, the cured product of the resin film forming film is regarded as a resin film, and the resin film forming film is In the case of being curable, it is considered that the resin film has been formed when the film for resin film formation is attached to the intended location.

When the semiconductor chip does not have bumps on the circuit surface, examples of the resin film forming film or resin film include a film adhesive used for die bonding the semiconductor chip to the circuit forming surface of the substrate. .
On the other hand, when the semiconductor chip has bumps on the circuit surface, such a semiconductor chip is flip-chip connected to the circuit formation surface of the substrate by the bumps, and the back surface of the semiconductor chip is exposed as it is. Becomes When used for such a semiconductor chip, the resin film forming film may be a protective film forming film, and the resin film may be a protective film for protecting the back surface.
That is, the resin film forming film of the present invention can be used for forming the film adhesive or the protective film.

The resin film-forming film of the present invention, when attached to the surface of the semiconductor wafer opposite to the circuit surface (may be referred to as “back surface” in the present specification in the same manner as the case of the semiconductor chip), The composite sheet for resin film formation can be used together with the support sheet.
As described above, the resin film forming film of the present invention satisfies both the conditions of the water absorption rate and the adhesive force change rate. By using such a resin film-forming film, after the blade dicing, when the semiconductor chip with the resin film-forming film or the semiconductor chip with the resin film having a small size is picked up from the supporting sheet, the resin film to the supporting sheet is formed. It is possible to suppress the formation film or the resin film from remaining. The reason why the resin film-forming film of the present invention exhibits such excellent pickup suitability is not clear, but it is presumed as follows.

  At the time of pickup, the resin film forming film and the resin film (cured product of the resin film forming film) are projected from the surface opposite to the side in contact with the semiconductor chip through the support sheet. The force is applied by the push-up means having the shape of. At this time, in the resin film forming film and the resin film, the portion to which a force is applied and the vicinity thereof have a strong force to be pressed against the semiconductor chip, and thus are difficult to peel off from the semiconductor chip. On the other hand, in the resin film forming film and the resin film, a portion apart from the portion to which the force is applied has a weaker force to be pressed against the semiconductor chip, so that the portion to which the force is applied and the vicinity thereof Is easily peeled off from the semiconductor chip. For example, when a force is applied to the vicinity of the center of the opposite surface of the resin film forming film or the resin film, the vicinity of the center of the resin film forming film or the resin film and its vicinity are peeled off from the semiconductor chip. It is difficult, but the peripheral portion and its vicinity separated from the vicinity of the center are more easily peeled from the semiconductor chip than the vicinity of the center and its vicinity. In the resin film forming film and the resin film, a portion to which a force is applied and its vicinity are relatively hard to be peeled off from the semiconductor chip as described above, but may be peeled off depending on conditions. ..

On the other hand, in the case of performing blade dicing, of the semiconductor wafer and the resin film forming film or the resin film, in order to suppress a temperature increase in the contact portion with the dicing blade, cooling water (" Dicing is performed while spraying cutting water). However, in the case of obtaining a semiconductor chip having a small size, the dicing time becomes long due to the large number of dicing points, and the resin film forming film and the resin film are exposed to cooling water for a long time. End up. In this case, the resin film forming film and the resin film become softer than before absorbing water due to water absorption and may be torn by the force applied at the time of pickup. When torn, the resin film forming film and the resin film, with the torn portion as a boundary, at least a portion apart from the portion to which force is applied may be easily peeled off from the semiconductor chip as described above, It is presumed that it remains on the support sheet. In addition, at the location where the resin film forming film or the resin film has been peeled off from the semiconductor chip, the cooling water (cutting water) used during dicing is not removed between the resin film forming film or the resin film and the semiconductor chip. Invades. Therefore, thereafter, in such a place, the resin film forming film or the resin film does not adhere to the semiconductor chip, while the resin film forming film or the resin film tends to adhere to the support sheet. . It is speculated that such an action makes it easier for the resin film-forming film or resin film after being torn to remain on the support sheet.
Such a problem is remarkable in the film for forming a resin film, but it is also remarkable in a resin film or a film having a low degree of curing such as one not completely cured. For example, in the cured product (energy-ray cured product) obtained by irradiating the resin film-forming film having both energy-ray curability and thermosetting property with energy beam as described later, the above-mentioned problems are recognized.

  On the other hand, when the resin film forming film of the present invention is used, both the water absorption rate and the adhesive force change rate are within a specific range, so that the problems as described above can be solved, and an excellent pickup It is speculated that aptitude will be obtained.

  In the above-mentioned "Japanese Patent No. 4732472" (Patent Document 1) and "Japanese Patent No. 5390209" (Patent Document 2), a thermosetting resin showing a moisture absorption in a specific range after thermosetting is described. A film-forming film (thermosetting die-bonding film) is disclosed, but a moisture absorption rate before thermosetting is not disclosed. This is because these thermosetting resin film forming films are intended to prevent cracks from occurring in the semiconductor package in the reflow process. That is, the subject of the invention disclosed in these patent documents is different from the subject of the present invention. Furthermore, the moisture absorption rate of the thermosetting resin film forming film disclosed in these patent documents is completely unrelated to the water absorption rate in the resin film forming film of the present invention, and the water absorption rate in the present invention. It does not remind me of anything.

  In the present specification, the term “semiconductor chip with resin film forming film” means “those having a resin film forming film on the back surface of the semiconductor chip”, and the term “semiconductor chip with resin film forming” means , "Having a resin film on the back surface of a semiconductor chip". The resin film in the semiconductor chip with a resin film may be a cured product obtained by completely curing the resin film forming film, or a cured product that is not completely cured (in other words, a cured product with a higher degree of curing). Thing).

In the present specification, the “energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, electron beams and the like. Ultraviolet rays can be emitted by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In addition, in the present specification, "energy ray-curable" means a property of being cured by irradiation with energy rays, and "non-energy ray-curable" is a property of not being cured by irradiation of energy rays. Means

The resin film forming film of the present invention may be curable or non-curable.
The curable resin film-forming film may be either thermosetting or energy ray curable, and may have both thermosetting and energy ray curable properties.
The resin film-forming film can be formed using a resin film-forming composition containing the constituent materials.
In addition, in this specification, "non-curable" means the property that it is not cured by any means such as heating or irradiation with energy rays.

  The film for forming a resin film of the present invention does not depend on the presence or absence of curability, and when it has curability, regardless of whether it is thermosetting or energy ray curable, a filler (described later) ( Those containing a filler such as D) are preferable. By using the filler, a resin film-forming film that satisfies both the conditions of the water absorption rate and the adhesive force change rate can be more easily manufactured.

  When the resin film forming film of the present invention contains a filler, in the resin film forming film, the ratio of the content of the filler to the total mass of the resin film forming film (in other words, the resin film forming The ratio of the content of the filler to the total content of the components other than the solvent in the composition for use is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass. Since the filler hardly absorbs water more remarkably than the other components, if the content ratio of the filler is equal to or more than the lower limit value, it becomes easier to set the water absorption rate to 0.55% or less. When the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the supporting sheet, the effect of suppressing the resin film forming film or the resin film remaining on the supporting sheet becomes higher. .. Moreover, the strength of the resin film forming film and the resin film is further improved when the content ratio of the filler is not more than the upper limit value. The filler will be described in detail later.

<< Water absorption of the first test piece >>
When the first test piece is immersed in pure water for 2 hours, the resin film-forming film has a water absorption rate of 0.55% or less. In the present specification, the unit “%” of water absorption rate means “mass%”. Hereinafter, the water absorption of the first test piece will be described in detail.

When the resin film forming film is non-energy ray curable, the first test piece has a size of 50 mm × 50 mm, which is formed by laminating a plurality of resin film forming films in the thickness direction thereof. The first laminated body has a thickness of 200 μm.
When the resin film forming film is energy ray curable, the first test piece is a first cured product obtained by irradiating the first laminate with energy rays to cure the first laminate with energy rays. .
When the resin film-forming film is thermosetting, the first laminate and the first cured product are irrespective of whether the resin film-forming film is energy ray curable or non-energy ray curable. It is preferable that neither is heat-cured.

All of the plurality of resin film forming films used for producing the first laminate have the same composition.
The plurality of resin film forming films may all have the same thickness, may have different thicknesses, or may have the same thickness, but preferably have the same thickness.

  The first laminated body is, for example, a plurality of resin film forming films of arbitrary size larger than 50 mm × 50 mm, laminated so as to have a total thickness of 200 μm, and pasted together to form a 50 mm × 50 mm size. It can be manufactured by punching (cutting). In addition, the first laminated body is formed by laminating a plurality of resin film forming films each having a size of 50 mm × 50 mm so that the positions of the peripheral portions thereof are the same so that the total thickness is 200 μm. It can also be made by pasting together.

When the resin film forming film is non-energy ray curable, the produced first laminate is used as it is as the first test piece.
When the oil film-forming film is energy ray-curable, the produced first laminate is further irradiated with energy rays to cure all the resin film-forming films in the first laminate with energy rays. Then, the obtained first cured product is used as a first test piece.

The irradiation conditions of the first laminated body (film for forming an oil film) with energy rays when producing the first cured product are not particularly limited as long as the first laminated body is sufficiently energy ray cured.
Usually, at the time of curing of the first laminate, the illuminance of the energy ray is preferably 120~280mW / cm ^2, light quantity of the energy ray is preferably 100~1000mJ / cm ^2.

In order to obtain the water absorption rate of the first test piece, first, the mass W _A of the first test piece before being immersed in pure water is measured. At this time, the mass W _A of the first test piece is preferably measured in a state where the manufactured first test piece does not show a clear change in mass due to moisture absorption or the like. By doing so, the water absorption rate described later can be obtained with higher accuracy.

First test piece was measured mass W _A is immersed for 2 hours in pure water. At this time, in order to prevent the first test piece from protruding and being exposed from the pure water (in other words, so that the entire first test piece is completely immersed in the pure water), the first test piece is exposed to a sufficient amount of pure water. 1 Submerge the test piece.

  The temperature of the pure water during the immersion of the first test piece is preferably 18 to 28 ° C. By doing so, the water absorption rate described later can be obtained with higher accuracy.

After soaking in pure water for 2 hours, the first test piece is immediately taken out from the pure water, and if necessary, for example, excess water droplets adhering to the surface of the first test piece are drained (removed). Then, the mass W _B of the first test piece after the immersion is measured.
Then, using the values of these _{W A} and _{W B,} the formula _{"(W B -W A) / W} A × 100 ", is calculated water absorption of the first specimen (%).

  In the present invention, the water absorption of the first test piece is 0.55% or less, preferably 0.53% or less, and may be 0.4% or less, for example. When the water absorption of the first test piece is less than or equal to the upper limit value, when a semiconductor chip with a resin film forming film or a semiconductor chip with a resin film having a small size is picked up from the support sheet, the resin film is formed on the support sheet. The effect of suppressing the remaining film or resin film for use becomes higher.

  In the present invention, the lower limit of the water absorption rate of the first test piece is not particularly limited and may be 0%, for example. It can be said that the lower the water absorption rate of the first test piece, the more difficult the physical properties of the first test piece (in other words, the resin film-forming film or the resin film) are, even if the first test piece is exposed to water for a long time. From the viewpoint of facilitating the production of the resin film forming film, the water absorption of the first test piece is preferably 0.01% or more, more preferably 0.05% or more.

  In the present invention, the water absorption rate of the first test piece can be appropriately adjusted so as to fall within a numerical range determined by arbitrarily combining any of the above lower limit values and any of the above upper limit values. For example, the water absorption of the first test piece is preferably 0 to 0.55%, more preferably 0 to 0.53%, and may be 0 to 0.4%. However, these are examples of the water absorption of the first test piece.

<< Adhesive force change rate of second test piece >>
In the resin film-forming film, the water absorption rate of the first test piece satisfies the above-mentioned conditions, and the adhesive force change rate of the second test piece is 60% or less. The adhesive force change rate of the second test piece will be described in detail below. This rate of change in adhesive strength indicates the degree of change in adhesive strength before and after the second test piece was immersed in pure water under specific conditions.

When the resin film forming film is non-energy ray curable, the second test piece is a second laminated body in which the resin film forming film is attached to a silicon mirror wafer.
When the resin film forming film is energy ray curable, the second test piece means that the resin film forming film in the second laminate is irradiated with energy rays to cure the resin film forming film with energy rays. It is the cured second laminated body (that is, the cured body of the second laminated body) after the second cured body is obtained.
When the resin film-forming film is thermosetting, the second laminate and the second cured product are irrespective of whether the resin film-forming film is energy ray curable or non-energy ray curable. It is preferable that neither is heat-cured.

  The second laminated body can be produced by attaching one surface of the resin film forming film to the mirror surface of the silicon mirror wafer.

The size of the silicon mirror wafer used for producing the second laminated body may be equal to or larger than the size of the resin film forming film, and can be appropriately adjusted so that the adhesive force described later can be accurately measured. .
The thickness of the silicon mirror wafer is preferably 350 to 760 μm. By doing so, the adhesive force described later can be measured with higher accuracy.

The size of the resin film forming film used for producing the second laminate is not particularly limited.
However, it is preferable that the width of the resin film forming film, which is the object of measuring the adhesive force with the silicon mirror wafer (in other words, is peeled from the silicon mirror wafer), is 25 mm. The length of the resin film forming film which is the measurement target is not particularly limited as long as the adhesive force can be measured with high accuracy, but it is preferably 150 to 250 mm. The size of the resin film-forming film that is the object of measurement of the adhesive strength after aging (adhesion before immersion described below) and the size of the film of resin film formation that is the object of measurement of the adhesive strength after immersion are the same. .

  At the time of producing the second laminate, it is preferable that the resin film forming film is heated to, for example, 35 to 45 ° C. and attached to the silicon mirror wafer. By doing so, a more stable second laminated body can be obtained.

When the resin film forming film is non-energy ray curable, the produced second laminate is used as it is as the second test piece.
When the film for forming an oil film is energy ray-curable, the resin film forming film in the produced second laminate is further treated with energy from the side of the film opposite to the side having the silicon mirror wafer. The cured second laminated body (that is, the cured product of the resin film forming film after the resin film forming film in the second laminated body is subjected to energy ray curing to be a second cured product by irradiating a ray. The provided silicon mirror wafer) is used as the second test piece.

The irradiation condition of the energy film to the oil film forming film when the second cured product (the cured second laminated body) is produced is particularly limited as long as the oil film forming film is sufficiently energy ray cured. Not done.
Usually, the illuminance and the amount of light of the energy ray during the production of the second cured product can be the same as the illuminance and the amount of energy of the energy ray during the curing of the first laminated body described above.

When the film for resin film formation is energy ray curable When the film for oil film formation is energy ray curable, in order to obtain the adhesive force change rate of the second test piece, first, the second test The piece is allowed to stand for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Next, in the second test piece after the passage of time, in the environment of 23 ° C., the adhesive force after the passage between the second cured product and the silicon mirror wafer (referred to as “adhesion force before immersion” in this specification). _Yes ) P _A1 is measured. At this time, it is preferable to measure the adhesive force P _A1 after aging in a state where the manufactured second test piece does not show a clear change in characteristics. By doing so, the rate of change in adhesive force, which will be described later, can be obtained with higher accuracy.

  On the other hand, when the adhesive strength after immersion is measured, the second test piece after aging of the measurement object is immersed in pure water for 2 hours. At this time, in order to prevent the second test piece from protruding and being exposed from the pure water (in other words, so that the entire second test piece is completely immersed in the pure water), the second test piece is exposed to a sufficient amount of pure water. 2 Sink the test piece.

  The temperature of pure water during immersion of the second test piece can be the same as the temperature of pure water during immersion of the first test piece. By doing so, the rate of change in adhesive force, which will be described later, can be obtained with higher accuracy.

After soaking in pure water for 2 hours, the second test piece is immediately taken out of the pure water, and if necessary, for example, excess water droplets adhering to the surface of the second test piece are drained (removed). Then, in the second test piece after the immersion, the post-immersion adhesive force P _B1 between the second cured product and the silicon mirror wafer is measured in an environment of 23 ° C. At this time, it is preferable to measure the adhesive force P _B1 after immersion in a state where the second test piece after immersion does not show a clear change in characteristics. By doing so, the rate of change in adhesive force, which will be described later, can be obtained with higher accuracy.

Then, using the values of P _A1 and P _B1 , the adhesive force change rate (%) of the second test piece is calculated by the formula “(| P _B1 −P _A1 |) / P _A1 × 100”.

The adhesive force after aging (adhesive force before immersion) P _A1 and the adhesive force after immersion P _B1 may be prepared by preparing a plurality of the same second test pieces, and may be separately measured in these second test pieces, or one piece. The same second test piece may be sequentially measured.
In one identical second test piece, when the adhesive force P _A1 after aging and the adhesive force P _B1 after immersion are sequentially measured, for example, in one identical second test piece, at different positions from each other, The adhesive force P _A1 after aging and the adhesive force P _B1 after immersion may be measured separately.

In the present invention, the adhesive force P _A1 after aging and the adhesive force P _B1 after immersion are both peeling forces measured when the operation of peeling the second cured product from the silicon mirror wafer is performed. At the time of measuring the adhesive force P _A1 after aging and the adhesive force P _B1 after immersion, for example, interface fracture may occur between the second cured product and the silicon mirror wafer, or the second cured product may be aggregated in the second cured product. Destruction may occur.

At the time of measuring the adhesive force P _A1 after the lapse of time, a pure speed of 300 mm / min was applied so that the angle formed by the two peeled surfaces generated when the second cured product was peeled off in the second test piece was 180 °. The so-called 180 ° peeling is performed to peel off the second cured product before the immersion in water. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the adhesive force P _A1 after aging.
For example, in the case where the interface breakdown occurs between the second cured product and the silicon mirror wafer, the above-mentioned “angle formed by the two separated surfaces” means “to the second cured product silicon mirror wafer”. Angle formed by the surface of the adhesive tape attached to the second cured product of the silicon mirror wafer. If cohesive failure has occurred in the second cured product, the above-mentioned “angle formed by the two peeled surfaces” is the “angle formed by the two cohesive failure surfaces in the second cured product”.

At this time, the second cured product may be peeled off using a strong adhesive tape. That is, at the time of measuring the adhesive force P _A1 after aging, a strong adhesive tape is attached to the second cured product before immersion in pure water, which is the object of measurement. Then, by using the strong adhesive tape as an object to which a peeling force is directly applied, the peeling speed is 300 mm / min and the stage before immersion in pure water is set so that the angle formed by the peeling surface becomes 180 °. In the second test piece, the second cured product and the laminate of the strong adhesive tape are peeled off and 180 ° peeling is performed. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the adhesive force P _A1 after aging.

  When the strong adhesive tape is used, the strong adhesive tape is attached to the resin film forming film before the resin film forming film is cured, and then the resin film forming film is cured to obtain a second cured product. Alternatively, the strong adhesive tape is not attached to the resin film forming film, but the resin film forming film is cured to form a second cured product, and the strong adhesive tape is attached to the second cured product. May be.

The post-immersion adhesive force P _B1 can also be measured by the same method as the case of the post-aging adhesive force P _A1 .
That is, at the time of measuring the adhesive strength P _B1 after immersion, the two surfaces produced when the second test piece after the lapse of time described above is immersed in pure water for 2 hours and then the second cured product is peeled off from the second test piece The second cured product is peeled off at a peeling speed of 300 mm / min so that the angle formed by the peeling surface of 180 ° is 180 °, so-called 180 ° peeling is performed. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the post-immersion adhesive force P _B1 .
Here, the “angle formed by the two peeled surfaces” is the same as in the case of measuring the above-described adhesive force P _A1 after aging.

A strong adhesive tape may be used when measuring the adhesive force P _B1 after immersion. That is, a strong adhesive tape is attached to the second cured product before immersion in pure water, which is the object of measurement of the adhesive force P _B1 after immersion. Then, the second test piece to which the strong adhesive tape is attached is dipped in pure water for 2 hours, and then the object to which the peeling force is directly applied is the strong adhesive tape, whereby the angle formed by the peeling surface is 180 °. The peeling rate is 300 mm / min and the second test piece is peeled off the laminate of the second cured product and the strong adhesive tape by 180 ° peeling. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the post-immersion adhesive force P _B1 .

Even when measuring the adhesive force P _B1 after immersion, as in the case of measuring the adhesive force after aging (adhesion force before immersion) P _A1 , before the resin film forming film is cured, the strong adhesive tape is used for forming the resin film. It may be attached to a film and then the resin film forming film may be cured to obtain a second cured product. Alternatively, the resin film forming film may be cured without attaching the strong adhesive tape to the resin film forming film. As a second cured product, the strong adhesive tape may be attached to the second cured product.

The size of the strong adhesive tape is the same as the size of the second cured product that is the object of measurement of the adhesive force P _A1 after aging and the adhesive force P _B1 after immersion (in other words, peeling from the silicon mirror wafer). Is preferred.

When the strong adhesive tape smaller than the size of the resin film forming film used for producing the second laminate is used, the resin film forming film is formed along the outer periphery of the strong adhesive tape in the second laminate. It is preferable to measure the adhesive force P _A1 after lapse of time and the adhesive force P _B1 after immersion after forming the notches. By doing so, the adhesive force P _A1 after aging can be more easily measured. Further, when measuring after immersion adhesive strength P _B1, not only after immersion adhesive strength P _B1 can be more easily measured, it can more accurately reflect the effect of immersion in pure water of the second cured product, after dipping adhesion P _B1 can be measured with higher accuracy.

-When the resin film-forming film is non-energy ray-curable When the resin film-forming film is non-energy ray-curable, the second laminate is used as it is as the second test piece (in other words, a silicon mirror). A method similar to that in the case where the resin film forming film is energy ray curable, except that the object of measuring the adhesive force between the wafer and the wafer is not the second cured product but the resin film forming film. Then, the adhesive force change rate (%) of the second test piece can be obtained.
More specifically, it is as follows.

When the film for forming an oil film is non-energy ray curable, in order to obtain the adhesive force change rate of the second test piece, first, the second test piece is placed in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Allow to stand for 30 minutes underneath for aging. Then, in the second test piece after the passage of time, the post-aging adhesive force (adhesion before immersion) P _A2 between the resin film forming film and the silicon mirror wafer is measured in an environment of 23 ° C. At this time, it is preferable to measure the adhesive force P _A2 after aging in a state where the second test piece after fabrication does not show a clear change in characteristics. By doing so, the rate of change in adhesive force, which will be described later, can be obtained with higher accuracy.

  On the other hand, when the adhesive strength after immersion is measured, the second test piece after aging of the measurement object is immersed in pure water for 2 hours. At this time, the second test piece can be immersed in pure water in the same manner as in the case where the oil film-forming film is energy ray curable.

After soaking in pure water for 2 hours, the second test piece is immediately taken out of the pure water, and if necessary, for example, excess water droplets adhering to the surface of the second test piece are drained (removed). Then, in the second test piece after the immersion, the post-immersion adhesive force P _B2 between the resin film forming film and the silicon mirror wafer is measured in an environment of 23 ° C. At this time, it is preferable to measure the adhesive force P _B2 after immersion in a state where the second test piece after immersion does not show a clear change in characteristics. By doing so, the rate of change in adhesive force, which will be described later, can be obtained with higher accuracy.

Then, using these values of P _A2 and P _B2 , the adhesive force change rate (%) of the second test piece is calculated by the formula “(| P _B2 −P _A2 |) / P _A2 × 100”.

The adhesive strength after aging (adhesive strength before immersion) P _A2 and the adhesive strength after immersion P _B2 may be prepared by preparing a plurality of the same second test pieces, and may be separately measured in these second test pieces, or one piece. The same second test piece may be sequentially measured.
When sequentially measuring the adhesive force P _A2 after aging and the adhesive force P _B2 after immersion in one and the same second test piece, for example, in one and the same second test piece, at mutually different locations, The adhesive force P _A2 after aging and the adhesive force P _B2 after immersion may be measured separately.

In the present invention, both the adhesive force P _A2 after aging and the adhesive force P _B2 after immersion are peeling forces measured when an operation of peeling the resin film forming film from the silicon mirror wafer is performed. When measuring the adhesive force P _A2 after aging and the adhesive force P _B2 after immersion, for example, interface breakdown may occur between the resin film forming film and the silicon mirror wafer, or in the resin film forming film. May cause cohesive failure.

At the time of measuring the adhesive force P _A2 after the lapse of time, at a peeling speed of 300 mm / min, the angle formed by the two peeling surfaces generated when the resin film-forming film was peeled off in the second test piece was 180 °, The so-called 180 ° peeling is performed in which the resin film forming film is peeled off before the immersion in pure water. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the adhesive force P _A2 after aging.
For example, when the interface destruction occurs between the resin film forming film and the silicon mirror wafer, the above-mentioned “angle formed by the two peeled surfaces” means “the silicon mirror of the resin film forming film”. The angle between the surface attached to the wafer and the surface attached to the resin film forming film of the silicon mirror wafer ”. If cohesive failure occurs in the resin film-forming film, the above-mentioned “angle formed by the two peeling surfaces” is the “angle formed by the two cohesive failure surfaces in the resin film-forming film”. is there.

At this time, the resin film forming film may be peeled off using a strong adhesive tape. That is, at the time of measuring the adhesive force P _A2 after aging, a strong adhesive tape is attached to the resin film forming film before immersion in pure water, which is the object of measurement. Then, by using the strong adhesive tape as an object to which a peeling force is directly applied, the peeling speed is 300 mm / min and the stage before immersion in pure water is set so that the angle formed by the peeling surface becomes 180 °. In the second test piece, the laminate of the resin film forming film and the strong adhesive tape is peeled off and 180 ° peeling is performed. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the adhesive force P _A2 after aging.

The post-immersion adhesive force P _B2 can also be measured by the same method as in the case of the post-immersion adhesive force P _A2 .
That is, when the adhesive strength P _B2 after immersion is measured, it occurs when the second test piece after the above-mentioned aging is immersed in pure water for 2 hours and then the resin film forming film is peeled off from the second test piece. The so-called 180 ° peeling is performed, in which the resin film forming film is peeled off at a peeling speed of 300 mm / min so that the angle formed by the peeled surface is 180 °. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the post-immersion adhesive force P _B2 .
Here, the “angle formed by the two peeled surfaces” is the same as in the case of measuring the above-mentioned adhesive force P _A2 after aging.

A strong adhesive tape may be used when measuring the adhesive force P _B2 after immersion. That is, the strong adhesive tape is attached to the resin film forming film before immersion in pure water, which is the object of measurement of the adhesive force P _B2 after immersion. Then, the second test piece to which the strong adhesive tape is attached is dipped in pure water for 2 hours, and then the object to which the peeling force is directly applied is the strong adhesive tape, whereby the angle formed by the peeling surface is 180 °. In such a manner, the second test piece is subjected to 180 ° peeling at a peeling speed of 300 mm / min to peel off the laminate of the resin film forming film and the strong adhesive tape. Then, the peeling force (mN / 25 mm) at this time can be measured, and this value can be used as the post-immersion adhesive force P _B2 .

The size of the strong adhesive tape is the same as the size of the resin film forming film which is the object of measurement of the adhesive force P _A2 after aging and the adhesive force P _B2 after immersion (in other words, it is peeled from the silicon mirror wafer). It is preferable.

When using the strong adhesive tape smaller than the size of the resin film forming film used for producing the second laminated body, in the second laminated body (second test piece), along the outer periphery of the strong adhesive tape. It is preferable to measure the adhesive force P _A2 after aging and the adhesive force P _B2 after immersion after forming a notch in the resin film forming film. By doing so, the adhesive strength P _A2 after aging can be more easily measured. Further, when measuring after immersion adhesive strength P _B2 is not only more easily measured after immersion adhesive strength P _B2, it can more accurately reflect the effect of immersion in pure water of the resin film for forming a film, after dipping adhesive The force P _B2 can be measured with higher accuracy.

  In the present invention, the rate of change in adhesive strength of the second test piece is 60% or less, preferably 50% or less, more preferably 45% or less, and particularly preferably 40% or less. When the rate of change in adhesive strength of the second test piece is less than or equal to the upper limit value, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the support sheet, the resin to the support sheet is The effect of suppressing the remaining film forming film or the resin film becomes higher.

  In the present invention, the lower limit of the rate of change in adhesive strength of the second test piece is not particularly limited and may be 0%, for example. It can be said that the lower the adhesive force change rate of the second test piece, the more difficult the adhesive strength of the second test piece (in other words, the resin film forming film or the resin film) is to change, even if the second test piece is exposed to water for a long time. From the viewpoint of facilitating the production of the resin film forming film, the rate of change in adhesive strength of the second test piece is preferably 3% or more, more preferably 5% or more.

  In the present invention, the adhesive force change rate of the second test piece can be appropriately adjusted so as to fall within a numerical range determined by arbitrarily combining any of the above lower limit values and any of the above upper limit values. .. For example, the adhesive force change rate of the second test piece is preferably 0 to 60%, more preferably 0 to 50%, further preferably 0 to 45%, and 0 to 40%. It is particularly preferable that However, these are examples of the adhesive force change rate of the second test piece.

<<Young's modulus of the third test piece after immersion >>
The resin film-forming film was measured by a tensile test according to JIS K 7127 at a test speed of 200 mm / min when the third test piece was immersed in pure water for 2 hours. The Young's modulus of the test piece is preferably 15 MPa or more.

When the resin film-forming film is non-energy ray curable, the third test piece is a plurality of resin film-forming films laminated in the thickness direction thereof, and has a size of 15 mm × 150 mm, It is a third laminated body having a thickness of 200 μm.
When the resin film forming film is energy ray curable, the third test piece is a third cured product obtained by irradiating the third laminate with energy rays to cure the third laminate with energy rays. .
When the resin film-forming film is thermosetting, the third laminate and the third cured product are irrespective of whether the resin film-forming film is energy ray curable or non-energy ray curable. It is preferable that neither is heat-cured.

  When the Young's modulus of the third test piece after immersion is equal to or more than the lower limit value, when a semiconductor chip with a resin film-forming film or a semiconductor chip with a resin film having a small size is picked up from the support sheet, The effect of suppressing the remaining of the resin film forming film or the resin film is further enhanced.

All of the plurality of resin film forming films used for producing the third laminate have the same composition.
The plurality of resin film forming films may all have the same thickness, may have different thicknesses, or may have the same thickness, but preferably have the same thickness.

  The third laminate has a size of 15 mm × 150 mm, for example, by laminating a plurality of resin film forming films having an arbitrary size larger than 15 mm × 150 mm so as to have a total thickness of 200 μm, and adhering the films. It can be manufactured by punching (cutting). In addition, the third laminated body is formed by laminating a plurality of resin film forming films having a size of 15 mm × 150 mm, for example, so that the positions of the peripheral portions are the same so that the total thickness is 200 μm. It can also be made by pasting together.

When the resin film forming film is non-energy ray curable, the produced third laminate is used as it is as the third test piece.
When the resin film forming film is energy ray curable, the produced third laminated body is further irradiated with energy rays to cure all the resin film forming films in the third laminated body with the energy ray. Then, the obtained third cured product is used as a third test piece.

Irradiation conditions of the energy ray to the third laminate (film for forming an oil film) at the time of producing the third cured product are not particularly limited as long as the third laminate is sufficiently energy ray-cured.
Usually, the illuminance and the amount of light of the energy rays during the production of the third cured product can be the same as the illuminance and the amount of light of the energy rays during the curing of the above-mentioned first laminated body.

  When a semiconductor chip with a resin film forming film or a semiconductor chip with a resin film having a small size is picked up from the supporting sheet, the effect of suppressing the remaining of the resin film forming film or the resin film on the supporting sheet becomes higher. The Young's modulus of the third test piece after the immersion is more preferably 17 MPa or more, and particularly preferably 19 MPa or more.

  In the present invention, the upper limit value of the Young's modulus of the third test piece after immersion is not particularly limited. Usually, the Young's modulus is preferably 350 MPa or less, more preferably 300 MPa or less, and particularly preferably 250 MPa or less. The resin film-forming film having the Young's modulus of not more than the upper limit value is easier to manufacture.

  In the present invention, the Young's modulus of the third test piece after immersion is appropriately set so as to fall within a numerical range determined by arbitrarily combining any of the above lower limit values and any of the above upper limit values. Can be adjusted. For example, the Young's modulus is preferably 15 to 350 MPa, more preferably 17 to 300 MPa, and particularly preferably 19 to 250 MPa. However, these are examples of the Young's modulus.

<<Young's modulus of the third test piece before immersion >>
In the present invention, the Young's modulus of the third test piece before being dipped in pure water measured by a tensile test according to JIS K 7127 at a test speed of 200 mm / min is 20 to 200 MPa. It is more preferably 30 to 190 MPa, particularly preferably 40 to 180 MPa. When the Young's modulus of the third test piece before immersion is in such a range, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the support sheet, The effect of suppressing the remaining of the resin film forming film or the resin film is further enhanced.

<< Elongation at break of third test piece after immersion >>
The resin film-forming film was measured by a tensile test according to JIS K 7127 at a test speed of 200 mm / min when the third test piece was immersed in pure water for 2 hours. The breaking elongation of the test piece is preferably 15 to 410%, more preferably 20 to 390%. When the breaking elongation of the third test piece after immersion is in such a range, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the supporting sheet, The effect of suppressing the remaining of the resin film forming film or the resin film is further enhanced.
The breaking elongation of the third test piece is obtained from the elongation of the third test piece when the third test piece breaks during the measurement of the Young's modulus of the third test piece described above. This is the same both before and after the third test piece is immersed in pure water.

  In the present specification, "the breaking elongation is X%" (X is a positive number) means that the test piece is pulled, and the test piece has the original length in the pulling direction (in other words, the pulling When the length of the test piece is increased by X%, that is, when the total length in the tensile direction of the test piece is [1 + X / 100] times the length before being pulled, the test is performed. It means that the piece breaks.

<< Elongation at break of third test piece before immersion >>
In the present invention, the breaking elongation of the third test piece before immersion in pure water measured by a tensile test according to JIS K 7127 at a test speed of 200 mm / min is 20 to 550%. It is preferable and it is more preferable that it is 25 to 500%. When the breaking elongation of the third test piece before immersion is in such a range, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the supporting sheet, The effect of suppressing the remaining of the resin film forming film or the resin film is further enhanced.

<< Breaking stress of the third test piece after immersion >>
The resin film-forming film was measured by a tensile test according to JIS K 7127 at a test speed of 200 mm / min when the third test piece was immersed in pure water for 2 hours. It is preferable that the breaking stress of the test piece is 0.8 to 7 MPa, and more preferably 0.8 to 5.5 MPa. When the breaking stress of the third test piece after immersion is in such a range, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the supporting sheet, The effect of suppressing the remaining of the resin film forming film or the resin film becomes higher.
The rupture stress of the third test piece is obtained from the force applied to the third test piece when the third test piece broke when the Young's modulus of the third test piece was measured. This is the same both before and after the third test piece is immersed in pure water.

<< Breaking stress of the third test piece before immersion >>
In the present invention, the breaking stress of the third test piece before immersion in pure water measured by a tensile test according to JIS K 7127 at a test speed of 200 mm / min is 1.1 to 8 MPa. It is preferable, and it is more preferable that it is 1.1 to 6.5 MPa. When the breaking stress of the third test piece before immersion is in such a range, when the semiconductor chip with the resin film forming film or the semiconductor chip with the resin film having a small size is picked up from the supporting sheet, The effect of suppressing the resin film forming film or the resin film from remaining becomes higher.

○ Thermosetting Resin Film Forming Film Preferred examples of the thermosetting resin film forming film include those containing the polymer component (A) and the thermosetting component (B). ), A thermosetting component (B) and a filler (D) are more preferable. The polymer component (A) is a component that can be regarded as formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction by using heat as a reaction trigger. In the present invention, the polymerization reaction also includes a polycondensation reaction.

  The thermosetting resin film forming film may be composed of one layer (single layer) or plural layers of two or more layers. When the thermosetting resin film forming film comprises a plurality of layers, these plurality of layers may be the same or different from each other.

The thickness of the thermosetting resin film-forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the thermosetting resin film-forming film is equal to or more than the lower limit value, the thickness uniformity becomes higher. In addition, when the thickness of the thermosetting resin film forming film is equal to or less than the upper limit value, the amount of cutting waste of the oil film forming film or the resin film generated during blade dicing of the semiconductor wafer is suppressed.
Here, the "thickness of the thermosetting resin film forming film" means the total thickness of the thermosetting resin film forming film, for example, the thermosetting resin film forming film consisting of a plurality of layers. The thickness means the total thickness of all layers constituting the thermosetting resin film forming film.

After the thermosetting resin film-forming film is attached to the back surface of the semiconductor wafer, the curing conditions for thermosetting are not particularly limited as long as the degree of curing is such that the cured product sufficiently exhibits its function. It may be appropriately selected depending on the type of the curable resin film forming film.
For example, the heating temperature during thermosetting of the thermosetting resin film-forming film is preferably 100 to 200 ° C, more preferably 110 to 180 ° C, and particularly preferably 120 to 170 ° C. .. The heating time for curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.

<< Thermosetting Resin Film Forming Composition >>
The thermosetting resin film-forming film can be formed by using the thermosetting resin film-forming composition containing the constituent material. For example, by applying the composition for forming a thermosetting resin film to the formation target surface of the film for forming a thermosetting resin film, and drying it as necessary, to form a thermosetting resin film at the target site. A film can be formed.

  The coating of the composition for forming a thermosetting resin film 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, Examples thereof include a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

  The conditions for drying the thermosetting resin film-forming composition are not particularly limited, but when the thermosetting resin film-forming composition contains the solvent described below, it is preferable to heat-dry. The thermosetting resin film-forming composition containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes. However, in the present invention, it is preferable to dry the composition for forming a thermosetting resin film so that the formed film for forming a thermosetting resin film is not thermoset.

<Thermosetting resin film forming composition (III-1)>
As a preferable thermosetting resin film forming composition, for example, a thermosetting resin film forming composition (III- containing a polymer component (A), a thermosetting component (B) and a filler (D). 1) (in this specification, it may be abbreviated as "composition (III-1)") and the like.

[Polymer component (A)]
The polymer component (A) is a component for imparting film forming properties and flexibility to the thermosetting resin film forming film.
The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting resin film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

  Examples of the polymer component (A) include acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, and thermosetting polyimide, and acrylic resin is preferable. ..

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 15,000,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit, the shape stability (temporal stability during storage) of the thermosetting resin film-forming film is improved. Further, when the weight average molecular weight of the acrylic resin is not more than the upper limit value, the thermosetting resin film forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting resin film formation Generation of voids and the like between the film and the film for use is further suppressed.
In addition, in this specification, a weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

  The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., more preferably −30 to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit, for example, the adhesive force between the cured product of the resin film forming film and the support sheet is suppressed, and the releasability of the support sheet is appropriately improved. Further, when the Tg of the acrylic resin is not more than the upper limit value, the adhesive force between the thermosetting resin film forming film and the adherend of the cured product thereof is improved.

  The acrylic resin is selected from, for example, one or more polymers of (meth) acrylic acid ester; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-methylolacrylamide. Examples thereof include copolymers of two or more kinds of monomers.

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

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

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

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

  The acrylic resin may have a functional group capable of binding 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 functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described below, or may be directly bonded to another compound without the crosslinking agent (F). .. When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the resin film-forming composite sheet tends to be improved.

  In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply abbreviated as “thermoplastic resin”) is used alone without using an acrylic resin. Or may be used in combination with an acrylic resin. By using the thermoplastic resin, the releasability of the resin film from the support sheet is improved, and the thermosetting resin film forming film easily follows the uneven surface of the adherend, and the adherend and thermosetting Occurrence of voids and the like may be further suppressed between the film for forming a flexible resin film.

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

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

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

  The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting resin film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio 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 forming film, the thermosetting resin film formation The ratio of the content of the polymer component (A) to the total mass of the film for use is preferably 3 to 85 mass% regardless of the type of the polymer component (A), and is 3 to 80 mass%. It is more preferable that the amount is 3 to 65% by mass, 3 to 50% by mass, 3 to 35% by mass, and 3 to 20% by mass.

  The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains components 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).

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing the thermosetting resin film forming film.
The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting resin film may be only one kind, or two or more kinds, and when two or more kinds are contained, The combination and the ratio can be arbitrarily selected.

  Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, with epoxy thermosetting resins being preferred.

(Epoxy thermosetting resin)
The epoxy thermosetting resin comprises an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting resin film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

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

  An epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (B1). An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor chip with a resin film obtained by using the composite sheet for forming a resin film is improved.

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

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but from the viewpoint of the curability of the thermosetting resin film forming film and the strength and heat resistance of the resin film after curing, it is preferably 300 to 30,000. The range of 300 to 10,000 is more preferable, and the range of 300 to 3000 is particularly preferable.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 150 to 950 g / eq.

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

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anhydrate, and the like, and a phenolic hydroxyl group, an amino group, or an acid group is anhydrate. It is preferably a group, and more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenol-based 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. .
Among the thermal curing agents (B2), examples of the amine 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 obtained by substituting a part of a hydroxyl group of a phenol resin with a group having an unsaturated hydrocarbon group, an aromatic ring of a phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

  When a phenolic curing agent is used as the thermosetting agent (B2), it is preferable that the thermosetting agent (B2) has a high softening point or glass transition temperature from the viewpoint that the releasability of the resin film from the support sheet is improved. ..

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

  As the thermosetting agent (B2), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

  In the composition (III-1) and the film for forming a thermosetting resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (B1). It is preferably 1 part by mass, more preferably 1-200 parts by mass, and for example, any one of 1-100 parts by mass, 1-50 parts by mass, 1-25 parts by mass, and 1-10 parts by mass. It may be. When the content of the thermosetting agent (B2) is equal to or more than the lower limit value, the thermosetting resin film-forming film is more easily cured. Further, when the content of the thermosetting agent (B2) is not more than the upper limit value, the moisture absorption rate of the thermosetting resin film-forming film is reduced, and the composite sheet for resin film-forming was obtained. Improves package reliability.

  In the composition (III-1) and the thermosetting resin film-forming film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is The content of the polymer component (A) is preferably 5 to 600 parts by mass, for example, 50 to 600 parts by mass, 100 to 600 parts by mass, 200 to 600 parts by mass, and 300 to 600 parts by mass. Any of parts by mass, 400 to 600 parts by mass, and 500 to 600 parts by mass may be used. When the content of the thermosetting component (B) is in such a range, for example, the adhesive force between the cured product of the resin film forming film and the support sheet is suppressed, and the peelability of the support sheet is improved. To do.

[Filler (D)]
When the thermosetting resin film-forming film contains the filler (D), it becomes easier to adjust the water absorption rate and the adhesive force change rate within the target ranges. Further, the thermosetting resin film forming film and the cured product (resin film) thereof contain the filler (D), whereby the thermal expansion coefficient can be adjusted more easily. Then, by optimizing the coefficient of thermal expansion with respect to the thermosetting resin film forming film or the object to be formed with the resin film, a resin film-forming semiconductor chip obtained by using the resin film forming composite sheet Reliability is further improved. In addition, the thermosetting resin film-forming film can reduce the moisture absorption rate of the resin film and improve the heat dissipation by containing the filler (D).

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

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

  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, for the thermosetting resin film forming film in the thermosetting resin film forming film). The ratio of the content of the filler (D) with respect to the total mass of the film) is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass. Since the filler (D) is significantly less likely to absorb water than the other components, if the ratio is equal to or more than the lower limit value, it becomes easier to set the water absorption rate to 0.55% or less. Then, when a small-sized resin film-coated semiconductor chip is picked up from the support sheet, the effect of suppressing the resin film remaining on the support sheet becomes higher. Further, when the ratio is equal to or less than the upper limit value, the strength of the resin film forming film and the resin film which is a cured product thereof is further improved.

[Curing accelerator (C)]
The composition (III-1) and the thermosetting resin film-forming film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like imidazoles (one or more hydrogen atoms other than hydrogen atoms Substituted with a group of), organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Examples thereof include tetraphenylboron salts such as tetraphenylborate.

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

  When the curing accelerator (C) is used, in the composition (III-1) and the film for forming a thermosetting resin film, the content of the curing accelerator (C) is 100 parts by weight of the thermosetting component (B). It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass with respect to parts by mass. When the content of the curing accelerator (C) is at least the lower limit value, the effect of using the curing accelerator (C) can be obtained more significantly. When the content of the curing accelerator (C) is not more than the upper limit value, for example, the highly polar curing accelerator (C) is contained in the thermosetting resin film forming film under high temperature and high humidity conditions. In the above, the effect of suppressing the segregation by moving to the adhesion interface side with the adherend becomes higher. As a result, the reliability of the semiconductor chip with a resin film obtained by using the composite sheet for forming a resin film is further improved.

[Coupling agent (E)]
The composition (III-1) and the thermosetting resin film-forming film may contain a coupling agent (E). By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, it is possible to improve the adhesiveness and adhesiveness of the thermosetting resin film-forming film to an adherend. it can. Further, by using the coupling agent (E), the cured product (resin film) of the thermosetting resin film forming film has improved water resistance without impairing heat resistance.

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

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

  When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the thermosetting resin film-forming film is the polymer component (A) and the thermosetting component. It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass based on 100 parts by mass of the total content of (B). Is particularly preferable. When the content of the coupling agent (E) is at least the lower limit value, the dispersibility of the filler (D) in the resin is improved, and the thermosetting resin film-forming film is adhered to the adherend. The effect of using the coupling agent (E), such as improved properties, can be more remarkably obtained. Moreover, when the content of the coupling agent (E) is not more than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (F)]
As the polymer component (A), those having a functional group such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group or an isocyanate group, which can be bonded to other compounds, such as the above acrylic resin. When used, the composition (III-1) and the thermosetting resin film-forming film may contain a crosslinking agent (F). The cross-linking agent (F) is a component for bonding the functional group in the polymer component (A) to another compound for cross-linking. By thus cross-linking, the thermosetting resin film-forming film is formed. The initial adhesive strength and cohesive strength of can be adjusted.

  As the cross-linking agent (F), for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group), etc. Is mentioned.

  As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compound etc." Abbreviated); trimers such as the aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds and polyol compounds Etc. The "adduct" is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil or the like. It means a reaction product of a compound containing a molecular active hydrogen. Examples of the adduct include a trimethylolpropane xylylene diisocyanate adduct as described below. Further, the “terminal isocyanate urethane prepolymer” is as described above.

  As the organic polyvalent isocyanate compound, more specifically, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4. , 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol A compound in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of hydroxyl groups of polyol such as propane; lysine diisocyanate and the like can be mentioned.

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

  When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a reaction between the cross-linking agent (F) and the polymer component (A) produces a thermosetting resin film-forming film. A crosslinked structure can be easily introduced.

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

  When the crosslinking agent (F) is used, in the composition (III-1), the content of the crosslinking agent (F) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (A). It is preferably 0.1 part by mass, more preferably 0.1-10 parts by mass, and particularly preferably 0.5-5 parts by mass. When the content of the cross-linking agent (F) is at least the lower limit value, the effect of using the cross-linking agent (F) can be more remarkably obtained. Further, when the content of the crosslinking agent (F) is not more than the upper limit value, excessive use of the crosslinking agent (F) is suppressed.

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

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

  Examples of the acrylate-based compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and the like (meth) acrylate containing a chain aliphatic skeleton; Cycloaliphatic skeleton-containing (meth) acrylate such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; oligoester (meth) acrylate; urethane (meth) acrylate oligomer An epoxy-modified (meth) acrylate; a polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; an itaconic acid oligomer and the like.

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

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

  The energy ray-curable resin (G) contained in the composition (III-1) and the thermosetting resin film-forming film may be only one kind, two or more kinds, or two or more kinds, The combination and ratio of can be arbitrarily selected.

  When the energy ray-curable resin (G) is used, in the composition (III-1), the content of the energy ray-curable resin (G) is 1 to the total mass of the composition (III-1). 95 mass% is preferable, 1-90 mass% is more preferable, 1-85 mass% is especially preferable, for example, 1-70 mass%, 1-55 mass%, 1-40 It may be any of mass%, 1 to 25 mass%, 1 to 10 mass% and the like.

[Photopolymerization initiator (H)]
When the composition (III-1) and the thermosetting resin film-forming film contain the energy ray-curable resin (G), in order to efficiently proceed the polymerization reaction of the energy ray-curable resin (G), The polymerization initiator (H) may be contained.

Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal. Benzoin compounds such as; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2, Acylphosphine oxide compounds such as 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; 1-hydroxycyclohexyl Α-ketol compounds such as phenyl 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; 4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
Examples of the photopolymerization initiator also include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines.

  The photopolymerization initiator (H) contained in the composition (III-1) and the thermosetting resin film-forming film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, those The combination and the ratio can be arbitrarily selected.

  When the photopolymerization initiator (H) is used, in the composition (III-1), the content of the photopolymerization initiator (H) is 100 parts by mass of the energy ray-curable resin (G). It is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

[Colorant (I)]
The composition (III-1) and the thermosetting resin film-forming film may contain a colorant (I).
Examples of the colorant (I) include known pigments such as inorganic pigments, organic pigments and organic dyes.

  Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squarylium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, phthalocyanines. Dye, naphthalocyanine dye, naphtholactam dye, azo dye, condensed azo dye, indigo dye, perinone dye, perylene dye, dioxazine dye, quinacridone dye, isoindolinone dye, quinophthalone dye , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, dioxazine dyes, naphthol dyes, azomethine dyes Examples thereof include dyes, benzimidazolone dyes, pyranthrone dyes and slene 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 ( Examples thereof include indium tin oxide) dyes and ATO (antimony tin oxide) dyes.

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

  When the colorant (I) is used, the content of the colorant (I) in the thermosetting resin film forming film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting resin film forming film and adjusting the light transmittance of the resin film, the visibility of printing when laser printing is performed on the resin film Can be adjusted. Further, by adjusting the content of the colorant (I) in the thermosetting resin film forming film, it is possible to improve the designability of the resin film and make it difficult to see the grinding marks on the back surface of the semiconductor wafer. Considering this point, 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-forming film, The ratio of the content of the colorant (I) to the total mass of the thermosetting resin film-forming film) is preferably 0.1 to 10% by mass, and 0.1 to 7.5% by mass. Is more preferable, and 0.1 to 5 mass% is particularly preferable. When the ratio of the content of the colorant (I) is at least the lower limit value, the effect of using the colorant (I) can be more remarkably obtained. Moreover, when the ratio of the content of the colorant (I) is not more than the upper limit value, an excessive decrease in the light transmittance of the thermosetting resin film-forming film is suppressed.

[General-purpose additive (J)]
The composition (III-1) and the thermosetting resin film-forming film may contain a general-purpose additive (J) as long as the effects of the present invention are not impaired.
The general-purpose additive (J) may be a known one and can be arbitrarily selected according to the purpose and is not particularly limited, but preferable examples include, for example, a plasticizer, an antistatic agent, an antioxidant, a gettering agent and the like. Is mentioned.

The general-purpose additive (J) contained in the composition (III-1) and the thermosetting resin film-forming film may be only one kind, or may be two or more kinds and, in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.
The content of the general-purpose additive (J) in the composition (III-1) and the thermosetting resin film forming film is not particularly limited and may be appropriately selected depending on the purpose.

[solvent]
The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the composition (III-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.

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

  The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected depending on the type of components other than the solvent, for example.

The preferred composition (III-1) includes, for example, a polymer component (A), a thermosetting component (B) and a filler (D), and the content of these components is Those included in any of the preferred numerical ranges described in 1 above.
As an embodiment of such a preferable composition (III-1), for example, in the composition (III-1), the content of the polymer component (A) relative to the total content of all components other than the solvent is The proportion is 3 to 85% by mass, and the content of the thermosetting component (B) is 5 to 600 parts by mass with respect to 100 parts by mass of the content of the polymer component (A), and The content ratio of the filler (D) to the total content of all components other than the solvent is 25 to 75% by mass.
In addition, as an embodiment of such a preferable composition (III-1), for example, in the composition (III-1), the content of the polymer component (A) relative to the total content of all components other than the solvent is included. The amount ratio is 3 to 35% by mass, and the content of the thermosetting component (B) is 300 to 600 parts by mass with respect to 100 parts by mass of the content of the polymer component (A). Moreover, the ratio of the content of the filler (D) to the total content of all components other than the solvent is 28 to 72% by mass.

More preferable composition (III-1) is, for example, polymer component (A), thermosetting component (B), curing accelerator (C), filler (D), coupling agent (E). , A cross-linking agent (F), an energy ray-curable resin (G) and a photopolymerization initiator (H), and the content of each of these components falls within any of the preferred numerical ranges described above. There are things.
As one embodiment of such a more preferable composition (III-1), for example, in the composition (III-1), the content of the polymer component (A) with respect to the total content of all components other than the solvent. Is 3 to 35% by mass, and the content of the thermosetting component (B) is 300 to 600 parts by mass with respect to 100 parts by mass of the content of the polymer component (A), And the ratio of the content of the filler (D) to the total content of all components other than the solvent is 28 to 72% by mass, and the content of the curing accelerator (C) is a thermosetting component. The content of the coupling agent (E) is 0.01 to 10 parts by mass with respect to the content of 100 parts by mass of (B), and the content of the coupling agent (E) is the polymer component (A) and the thermosetting component (B). Is 0.03 to 20 parts by mass with respect to 100 parts by mass of the total content, and the content of the crosslinking agent (F) is 0 with respect to 100 parts by mass of the content of the polymer component (A). 0.01 to 20 parts by mass, and the content of the photopolymerization initiator (H) is 2 to 5 parts by mass with respect to 100 parts by mass of the energy ray-curable resin (G), and The ratio of the content of the energy ray-curable resin (G) to the total mass of the composition (III-1) is 1 to 10% by mass.

<< Production Method of Thermosetting Resin Film-Forming Composition >>
The composition for forming a thermosetting resin film such as the composition (III-1) can be obtained by blending each component for constituting the composition.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any of the compounding ingredients other than the solvent and diluting this compounding ingredient in advance, or by diluting any of the compounding ingredients other than the solvent in advance. Alternatively, the solvent may be used as a mixture with these ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; It may be selected appropriately.
The temperature and time at the time of adding and mixing 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.

Film for forming energy ray-curable resin film Examples of the film for forming energy ray-curable resin film include those containing the energy ray-curable component (a). What is contained is preferable.
In the energy ray-curable resin film forming film, the energy ray-curable component (a) is preferably uncured, preferably has tackiness, and more preferably uncured and tacky. Here, "energy ray" and "energy ray curability" are as described above.

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

The thickness of the energy ray-curable resin film-forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the energy ray-curable resin film forming film is equal to or more than the lower limit value, the thickness uniformity becomes higher. Further, the thickness of the energy ray-curable resin film forming film is equal to or less than the upper limit value, thereby suppressing the amount of cutting waste of the oil film forming film or the resin film generated during blade dicing of the semiconductor wafer. .
Here, the "thickness of the film for forming an energy ray-curable resin film" means the thickness of the entire film for forming an energy ray-curable resin film, for example, the formation of an energy ray-curable resin film composed of a plurality of layers. The thickness of the film for use means the total thickness of all layers constituting the film for forming an energy ray-curable resin film.

After the energy ray-curable resin film-forming film is attached to the back surface of the semiconductor wafer, the curing conditions for curing are not particularly limited as long as the cured product has a degree of curing sufficient to exert its function. It may be appropriately selected depending on the type of the film for forming the linear curable resin film.
For example, the illuminance of energy rays during curing of the energy ray-curable resin film-forming film is preferably 120 to 280 mW / cm ² . And, the light amount of the energy ray at the time of curing is preferably 100 to 1000 mJ / cm ² .

<< Energy ray curable resin film forming composition >>
The energy ray-curable resin film forming film can be formed by using the energy ray-curable resin film forming composition containing the constituent material. For example, the composition for forming an energy ray-curable resin film is applied to the surface on which the film for forming an energy ray-curable resin film is formed, and dried if necessary, so that the energy ray-curable resin is applied to a target site. A film forming film can be formed.

  The energy ray-curable resin film-forming composition can be applied, for example, by the same method as in the case of applying the thermosetting resin film-forming composition described above.

  The conditions for drying the energy ray-curable resin film-forming composition are not particularly limited, but when the energy ray-curable resin film-forming composition contains the solvent described below, it is preferable to heat-dry. Then, the energy ray-curable resin film-forming composition containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes. However, in the present invention, it is preferable to dry the composition for forming an energy ray-curable resin film so that the formed film for forming an energy ray-curable resin film is not thermally cured.

<Energy ray curable resin film forming composition (IV-1)>
As a preferable composition for forming an energy ray-curable resin film, for example, a composition for forming an energy ray-curable resin film (IV-1) containing the energy ray-curable component (a) and a filler (this specification) In the above, it may be simply abbreviated as "composition (IV-1)") and the like.

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and imparts film-forming properties, flexibility, and the like to the energy-ray-curable resin film-forming film, and hard resin after curing. It is also a component for forming a film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000, and an energy ray-curable group having a molecular weight of 100 to 80,000. The compound (a2) may be mentioned. At least a part of the polymer (a1) may be crosslinked with a crosslinking agent, or may not be crosslinked.

(Polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and An acrylic resin (a1-1) obtained by reacting a group that reacts with a functional group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond is mentioned. ..

Examples of the functional group capable of reacting with the group of another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (wherein one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). And a epoxy group. However, the functional group is preferably a group other than a carboxy group in terms of preventing corrosion of circuits such as a semiconductor wafer and a semiconductor chip.
Among these, the functional group is preferably a hydroxyl group.

.Acrylic polymer having functional group (a11)
Examples of the functional group-containing acrylic polymer (a11) include those obtained by copolymerizing the functional group-containing acrylic monomer and the functional group-free acrylic monomer. In addition to the monomer, a monomer (non-acrylic monomer) other than the acrylic monomer may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method can be adopted as a polymerization method.

  Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

  Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-adhesives such as vinyl alcohol and allyl alcohol. Examples thereof include saturated alcohols (unsaturated alcohols having no (meth) acryloyl skeleton).

  Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid, maleic acid, citracone An ethylenically unsaturated dicarboxylic acid such as an acid (dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; and a (meth) acrylic acid carboxyalkyl ester such as 2-carboxyethyl methacrylate. Be done.

  The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer.

  The functional group-containing acrylic monomer constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof are arbitrarily set. You can choose.

  Examples of the acrylic monomer having no functional group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth ) Hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), and other alkyl groups constituting the alkyl ester have a carbon number of 1 Examples thereof include (meth) acrylic acid alkyl ester having a chain structure of -18.

  Examples of the acrylic monomer having no functional group include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as phenyl (meth) acrylic acid; non-crosslinkable (meth) acrylamide and Derivatives thereof; (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like are also included. ..

  The acrylic monomer having no functional group, which constitutes the acrylic polymer (a11), may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof are arbitrary. You can choose to.

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene.
The non-acrylic monomer constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

  In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is 0.1 to 50 mass. %, More preferably 1 to 40% by mass, particularly preferably 3 to 30% by mass. When the ratio is within such a range, the energy in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) is increased. The content of the linear curable group can easily adjust the degree of curing of the resin film within a preferable range.

  The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof are arbitrarily set. You can choose.

  In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (that is, the total amount of the films in the energy ray-curable resin film forming film). The ratio of the content of the acrylic resin (a1-1) to the mass) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass. Is particularly preferable.

・ Energy ray curable compound (a12)
The energy ray-curable compound (a12) is one or two kinds selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferable, and those having an isocyanate group as the above group are more preferable. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

  The energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably 1 to 3 energy-curable groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl). Ethyl isocyanate;
An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

  The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or may be two or more types, and in the case of two or more types, their combination and ratio are arbitrary. You can choose to.

  In the acrylic resin (a1-1), the content of the energy ray-curable group derived from the energy ray-curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). Is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the resin film after curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 15,000,000.
Here, the “weight average molecular weight” is as described above.

  When at least a part of the polymer (a1) is cross-linked with a cross-linking agent, the polymer (a1) has been described as constituting the acrylic polymer (a11). A monomer that does not correspond to any of the monomers and has a group that reacts with a crosslinking agent may be polymerized to be crosslinked at a group that reacts with the crosslinking agent, or the energy ray-curable compound ( The group which is derived from a12) and which reacts with the functional group may be crosslinked.

  The polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray-curable resin film may be only one kind, or two or more kinds, and in the case of two or more kinds, those The combination and the ratio can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include groups containing an energy ray-curable double bond, and preferred examples include (meta ) Examples thereof include an acryloyl group and a vinyl group.

  The compound (a2) is not particularly limited as long as it satisfies the above conditions, but has a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and an energy ray-curable group. Examples thereof include phenolic resins.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include a polyfunctional monomer or oligomer, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4. -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate, 1 , 10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, etc. A bifunctional (meth) acrylate of:
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as (meth) acrylates;
Examples thereof include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

  Among the compounds (a2), the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group are described, for example, in paragraph 0043 of “JP 2013-194102 A”. Any thing can be used. Such a resin corresponds to a resin constituting a thermosetting component described later, but is treated as the compound (a2) in the present invention.

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

  The compound (a2) contained in the composition (IV-1) and the film for forming an energy ray-curable resin film may be only one kind, or may be two or more kinds and, in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

[Polymer (b) having no energy ray-curable group]
When the composition (IV-1) and the energy ray-curable resin film-forming film contain the compound (a2) as the energy ray-curable component (a), the polymer further has no energy ray-curable group. It is preferable to also contain (b).
At least a part of the polymer (b) may be crosslinked with a crosslinking agent, or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins and the like.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as “acrylic polymer (b-1)”).

  The acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one type of acrylic monomer or a copolymer of two or more types of acrylic monomer. Alternatively, it may be a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

  Examples of the acrylic monomer forming the acrylic polymer (b-1) include (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, Examples thereof include a hydroxyl group-containing (meth) acrylic acid ester and a substituted amino group-containing (meth) acrylic acid ester. Here, the “substituted amino group” is as described above.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-methacrylate. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth) The alkyl group constituting the alkyl ester, such as hexadecyl acrylate (palmethyl acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate) has 1 to 1 carbon atoms. Examples thereof include (meth) acrylic acid alkyl ester having a chain structure of 18.

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

Examples of the glycidyl group-containing (meth) acrylic acid ester include glycidyl (meth) acrylate.
Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Examples thereof include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate.

  Examples of the non-acrylic monomer that constitutes the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

Examples of the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked with a crosslinking agent, include those in which the reactive functional group in the polymer (b) has reacted with the crosslinking agent. Can be mentioned.
The reactive functional group may be appropriately selected according to the type of the cross-linking agent and is not particularly limited. For example, when the cross-linking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group and an amino group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and among these, a carboxy group having high reactivity with an epoxy group is preferable. . However, the reactive functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip.

  Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer, which are mentioned as the monomers constituting the acrylic polymer (b-1), have the reactive functional group. You can use it. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester, and in addition to this, the above-mentioned acryl Examples thereof include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the above-mentioned reactive functional group in the system monomer or the non-acrylic monomer.

  In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the structural units constituting the polymer is 1 to 20. It is preferably mass%, and more preferably 2 to 10 mass%. When the ratio is within such a range, the degree of crosslinking in the polymer (b) becomes a more preferable range.

  The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to 2,000,000 from the viewpoint that the film-forming property of the composition (IV-1) becomes better. It is more preferably 100,000 to 15,000,000. Here, the "weight average molecular weight" is as described above.

  The polymer (b) containing no energy ray-curable group contained in the composition (IV-1) and the energy ray-curable resin film-forming film may be only one type, or may be two or more types. When there are more than one species, their combination and ratio can be arbitrarily selected.

  Examples of the composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2). And when the composition (IV-1) contains the compound (a2), it is preferable that the composition (IV-1) further contains a polymer (b) having no energy ray-curable group. In this case, the composition (IV) further contains (a1). It is also preferable to contain. Moreover, the composition (IV-1) may contain neither the compound (a2) but the polymer (a1) and the polymer (b) having no energy ray-curable group. ..

  When the composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group, in the composition (IV-1), The content of the compound (a2) is preferably 10 to 400 parts by mass based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. More preferably 30 to 350 parts by mass.

  In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (that is, In the energy ray-curable resin film forming film, the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total mass of the film) is %, Preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray-curability of the energy ray-curable resin film forming film becomes better.

[Filling material]
The energy ray-curable resin film forming film containing the filler has the same effect as the thermosetting resin film forming film containing the filler (D).

  The filler contained in the composition (IV-1) and the energy ray-curable resin film forming film includes the composition (III-1) and the filler (D) contained in the thermosetting resin film forming film. The same can be mentioned.

  The filler contained in the composition (IV-1) and the film for forming an energy ray-curable resin film may be only one type, or may be two or more types, and in the case of two or more types, their combination and ratio are It can be arbitrarily selected.

  In the composition (IV-1), the ratio of the content of the filler to the total content of all components other than the solvent (that is, the filler relative to the total mass of the film in the energy ray-curable resin film forming film). The content ratio) is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass. Since the filler is more difficult to absorb water than the other components, the water absorption rate of 0.55% or less can be easily achieved by setting the ratio to the lower limit or more. Then, when a small-sized resin film-coated semiconductor chip is picked up from the support sheet, the effect of suppressing the resin film remaining on the support sheet becomes higher. Further, when the ratio is equal to or less than the upper limit value, the strength of the resin film forming film and the resin film which is a cured product thereof is further improved.

  The composition (IV-1) comprises a thermosetting component, a coupling agent, a cross-linking agent, a photopolymerization initiator, a colorant, and a general-purpose additive in addition to the energy ray-curable component and the filler, depending on the purpose. You may contain 1 type (s) or 2 or more types selected from the group consisting of.

  As the thermosetting component, the coupling agent, the cross-linking agent, the photopolymerization initiator, the colorant, and the general-purpose additive in the composition (IV-1), the thermosetting component (in the composition (III-1) ( The same as the B), the coupling agent (E), the cross-linking agent (F), the photopolymerization initiator (H), the colorant (I) and the general-purpose additive (J) can be mentioned.

For example, the energy ray-curable resin film-forming film formed by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component has an adhesive force to an adherend by heating. And the strength of the resin film formed from this energy ray-curable resin film forming film is also improved.
The energy ray-curable resin film-forming film formed by using the composition (IV-1) containing the energy ray-curable component and the colorant is the thermosetting resin film-forming film described above. The same effect as when the film for use contains the colorant (I) is exhibited.

  In the composition (IV-1), the thermosetting component, the coupling agent, the cross-linking agent, the photopolymerization initiator, the colorant and the general-purpose additive may be used alone or in combination of two kinds. The above may be used in combination, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.

  The content of the thermosetting component, the coupling agent, the cross-linking agent, the photopolymerization initiator, the colorant, and the general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the purpose and is not particularly limited. ..

It is preferable that the composition (IV-1) further contains a solvent because the handling property thereof is improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (IV-1) may be only one kind or two or more kinds.

<< Method for producing composition for forming energy ray-curable resin film >>
The composition for forming an energy ray-curable resin film such as the composition (IV-1) can be obtained by blending each component for constituting the same.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any of the compounding ingredients other than the solvent and diluting this compounding ingredient in advance, or by diluting any of the compounding ingredients other than the solvent in advance. Alternatively, the solvent may be used as a mixture with these ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; It may be selected appropriately.
The temperature and time at the time of adding and mixing 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.

○ Non-curable resin film forming film The non-curable resin film forming film does not show changes in characteristics due to curing, but in the present invention, it is adhered to a desired position such as the back surface of a semiconductor wafer. At the stage, it is considered that a resin film has been formed.

  Examples of the non-curable resin film forming film include those containing a thermoplastic resin, and those containing a thermoplastic resin and a filler are preferable.

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

The thickness of the non-curable resin film forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the non-curable resin film forming film is equal to or more than the lower limit value, the uniformity of the thickness becomes higher. In addition, when the thickness of the non-curable resin film forming film is equal to or less than the upper limit value, the amount of cutting scraps of the oil film forming film or the resin film generated during blade dicing of the semiconductor wafer is suppressed.
Here, the "thickness of the non-curable resin film forming film" means the total thickness of the non-curable resin film forming film, for example, the non-curing resin film forming film consisting of a plurality of layers. The thickness means the total thickness of all layers constituting the non-curable resin film forming film.

<< Non-curable resin film forming composition >>
The non-curable resin film forming film can be formed using the non-curable resin film forming composition containing the constituent material. For example, by applying the composition for forming a non-curable resin film on the surface to be formed of the film for forming a non-curable resin film, and drying it if necessary, to form the non-curable resin film on the target site. A film can be formed.

  The coating of the non-curable resin film forming composition can be performed, for example, by the same method as in the case of coating the thermosetting resin film forming composition described above.

  The conditions for drying the non-curable resin film-forming composition are not particularly limited, but when the non-curable resin film-forming composition contains the solvent described below, it is preferable to heat-dry. Then, the non-curable resin film-forming composition containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.

<Non-curable resin film forming composition (V-1)>
As a preferable non-curable resin film-forming composition, for example, a non-curable resin film-forming composition (V-1) containing the thermoplastic resin and the filler (in the present specification, simply "composition (V-1) "may be abbreviated) and the like.

[Thermoplastic resin]
The thermoplastic resin is not particularly limited.
More specifically, as the thermoplastic resin, for example, curability of acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc., which are mentioned as the components contained in the above composition (III-1). The same as the resin which is not included.

  The thermoplastic resin contained in the composition (V-1) and the non-curable resin film-forming film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof. Can be arbitrarily selected.

  In the composition (V-1), the ratio of the content of the thermoplastic resin to the total content of components other than the solvent (that is, the amount of the heat relative to the total mass of the film in the non-curable resin film forming film) The ratio of the content of the plastic resin) is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass.

[Filling material]
The non-curable resin film forming film containing the filler has the same effect as the thermosetting resin film forming film containing the filler (D).

  The filler contained in the composition (V-1) and the non-curable resin film forming film is the same as the filler (D) contained in the composition (III-1) and the thermosetting resin film forming film. There are things.

  The filler contained in the composition (V-1) and the non-curable resin film forming film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are arbitrary. You can choose to.

  In the composition (V-1), the ratio of the content of the filler to the total content of all components other than the solvent (that is, in the non-curable resin film-forming film, with respect to the total mass of the film, the content of the filler is The ratio (content ratio) is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass. Since the filler is more difficult to absorb water than the other components, the water absorption rate of 0.55% or less can be easily achieved by setting the ratio to the lower limit or more. Then, when a small-sized resin film-coated semiconductor chip is picked up from the support sheet, the effect of suppressing the resin film remaining on the support sheet becomes higher. Further, when the ratio is not more than the upper limit value, the strength of the resin film forming film (resin film) is further improved.

The composition (V-1) may contain other components in addition to the thermoplastic resin and the filler depending on the purpose.
The other components are not particularly limited and can be arbitrarily selected according to the purpose.
For example, the non-curable resin film-forming film formed by using the composition (V-1) containing the thermoplastic resin and the colorant is the thermosetting resin film-forming film described above. The same effect as when the colorant (I) is contained is exhibited.

  In the composition (V-1), the other components may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio are It can be arbitrarily selected.

  The content of the other component in the composition (V-1) may be appropriately adjusted according to the purpose and is not particularly limited.

It is preferable that the composition (V-1) further contains a solvent because the handling property thereof is improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the above composition (III-1).
The solvent contained in the composition (V-1) may be only one kind or two or more kinds.

<< Method for producing non-curable resin film-forming composition >>
The composition for forming a non-curable resin film such as the composition (V-1) can be obtained by blending the respective components constituting the composition.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any of the compounding ingredients other than the solvent and diluting this compounding ingredient in advance, or by diluting any of the compounding ingredients other than the solvent in advance. Alternatively, the solvent may be used as a mixture with these ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; It may be selected appropriately.
The temperature and time at the time of adding and mixing 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.

◇ Resin film forming composite sheet The resin film forming composite sheet of the present invention comprises a support sheet, and a resin film forming film on the support sheet, wherein the resin film forming film is the above-mentioned book. It is the resin film forming film of the invention.

INDUSTRIAL APPLICABILITY The resin film-forming composite sheet of the present invention is suitable for being attached to the back surface of a semiconductor wafer and used when individualizing (dividing) the semiconductor wafer into small-sized semiconductor chips by blade dicing. The resin film forming film in the resin film forming composite sheet can be used for forming a resin film on the back surface of a semiconductor wafer or a semiconductor chip, and the support sheet can be used as a dicing sheet. Obtained by blade dicing, a semiconductor chip with a resin film forming film or a semiconductor chip with a resin film having a small size is excellent in suitability for picking up from a supporting sheet, and at the time of picking up, a film or resin film for forming a resin film on the supporting sheet. Is suppressed.
Hereinafter, the constitution of the composite sheet for resin film formation of the present invention other than the film for resin film formation will be described in detail.

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

  Preferred support sheets include, for example, a base material and an adhesive layer laminated on the base material; a base material, an intermediate layer laminated on the base material, and an adhesive layer on the intermediate layer. Examples include those in which an agent layer is laminated; those including only a base material and the like.

  Examples of the composite sheet for forming a resin film of the present invention will be described below for each type of such support sheet with reference to the drawings. In the drawings used in the following description, in order to facilitate understanding of the features of the present invention, for the sake of convenience, there may be a case where an essential part is enlarged and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

FIG. 1 is a cross-sectional view schematically showing one embodiment of the resin film forming composite sheet of the present invention.
The composite sheet 101 for forming a resin film shown here includes a pressure-sensitive adhesive layer 12 on a base material 11 and a resin film-forming film 13 on the pressure-sensitive adhesive layer 12. The support sheet 1 is a laminate of a base material 11 and an adhesive layer 12, and in other words, the resin film forming composite sheet 101 has a resin film forming film 13 laminated on one surface 1a of the support sheet 1. It has a different configuration. Further, the resin film forming composite sheet 101 further includes a release film 15 on the resin film forming film 13.

  In the resin film forming composite sheet 101, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the resin film forming film 13 is laminated on the entire one surface 12a of the pressure-sensitive adhesive layer 12. The jig adhesive layer 16 is laminated on a part of the one surface 13a of the film forming film 13, that is, in the region near the peripheral portion, and the jig adhesive on the surface 13a of the resin film forming film 13 is laminated. The release film 15 is laminated on the surface on which the layer 16 is not laminated and on the surface 16 a (upper surface and side surface) of the jig adhesive layer 16.

  In the resin film forming composite sheet 101, the resin film forming film 13 satisfies both the conditions of the water absorption rate and the adhesive force change rate described above.

  The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which a layer containing an adhesive component is laminated on both surfaces of a sheet as a core material. It may have a structure.

In the resin film forming composite sheet 101 shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is attached to the front surface 13a of the resin film forming film 13 in a state where the release film 15 is removed. A jig such as a ring frame is attached to the upper surface of the surface 16a of the adhesive layer 16 for use.
In the adhesive layer 16 for a jig, the boundary between the upper surface and the side surface may not be clearly distinguished.

  FIG. 2 is a cross-sectional view schematically showing another embodiment of the resin film-forming composite sheet of the present invention. 2 and subsequent figures, the same components as those shown in the already-described figures are designated by the same reference numerals as those in the already-illustrated figures, and detailed description thereof will be omitted.

  The resin film forming composite sheet 102 shown here is the same as the resin film forming composite sheet 101 shown in FIG. 1 except that the jig adhesive layer 16 is not provided. That is, in the resin film forming composite sheet 102, the adhesive layer 12 is laminated on one surface 11 a of the base material 11, and the resin film forming film 13 is laminated on the entire one surface 12 a of the adhesive layer 12. The release film 15 is laminated on the entire one surface 13a of the resin film forming film 13.

  The resin film forming composite sheet 102 shown in FIG. 2 is a semiconductor wafer (not shown) in a partial region on the center side of the surface 13a of the resin film forming film 13 with the release film 15 removed. The back surface is attached, and a jig such as a ring frame is attached to the region near the peripheral edge of the resin film forming film 13 for use.

FIG. 3 is a sectional view schematically showing still another embodiment of the resin film-forming composite sheet of the present invention.
The resin film-forming composite sheet 103 shown here is the same as the resin film-forming composite sheet 101 shown in FIG. 1 except that the adhesive layer 12 is not provided. That is, in the resin film forming composite sheet 103, the support sheet 1 is composed of only the base material 11. Then, the resin film forming film 13 is laminated on one surface 11a of the base material 11 (in other words, one surface 1a of the support sheet 1), and a part of the surface 13a of the resin film forming film 13, that is, the peripheral edge. The jig adhesive layer 16 is laminated in the region near the portion, and the surface of the resin film forming film 13 on which the jig adhesive layer 16 is not laminated and the jig adhesive layer 16 The release film 15 is laminated on the surface 16a (top surface and side surface) of the.

  Similar to the resin film forming composite sheet 101 shown in FIG. 1, the resin film forming composite sheet 103 shown in FIG. 3 has a semiconductor wafer on the surface 13 a of the resin film forming film 13 with the release film 15 removed. A back surface (not shown) is attached, and a jig such as a ring frame is attached on the upper surface of the surface 16a of the jig adhesive layer 16 for use.

FIG. 4 is a sectional view schematically showing still another embodiment of the resin film-forming composite sheet of the present invention.
The resin film-forming composite sheet 104 shown here is the same as the resin film-forming composite sheet 103 shown in FIG. 3 except that the jig adhesive layer 16 is not provided. That is, in the resin film forming composite sheet 104, the resin film forming film 13 is laminated on one surface 11 a of the base material 11, and the release film 15 is laminated on the entire one surface 13 a of the resin film forming film 13. Has been done.

  Similar to the resin film forming composite sheet 102 shown in FIG. 2, the resin film forming composite sheet 104 shown in FIG. 4 is one of the surfaces 13a of the resin film forming film 13 with the release film 15 removed. The back surface of a semiconductor wafer (not shown) is attached to a partial area on the center side, and a jig such as a ring frame is attached to an area in the vicinity of the peripheral edge of the resin film forming film 13 for use. ..

FIG. 5 is a sectional view schematically showing still another embodiment of the resin film-forming composite sheet of the present invention.
The resin film forming composite sheet 105 shown here is the same as the resin film forming composite sheet 102 shown in FIG. 2 except that the shape of the resin film forming film is different. That is, the resin film forming composite sheet 105 includes the adhesive layer 12 on the base material 11 and the resin film forming film 23 on the adhesive layer 12. The support sheet 1 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and in other words, the resin film forming composite sheet 105 has the resin film forming film 23 laminated on one surface 1 a of the support sheet 1. It has a different configuration. Further, the resin film forming composite sheet 105 further includes a release film 15 on the resin film forming film 23.

  In the resin film forming composite sheet 105, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and a part of the one surface 12a of the pressure-sensitive adhesive layer 12, that is, the width direction of the support sheet 1 (see FIG. The resin film forming film 23 is laminated in the central region in the left-right direction in FIG. Then, on the surface 12a of the pressure-sensitive adhesive layer 12 on which the resin film forming film 23 is not laminated and on one surface 23a (top surface and side surface) of the resin film forming film 23, the release film 15 is formed. It is stacked.

  When the resin film forming composite sheet 105 is viewed from above and seen in a plan view, the resin film forming film 23 has a smaller surface area than the adhesive layer 12, and has, for example, a circular shape or the like.

  In the resin film forming composite sheet 105, the resin film forming film 23 satisfies both the conditions of the water absorption rate and the adhesive force change rate described above.

  In the resin film forming composite sheet 105 shown in FIG. 5, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the resin film forming film 23 in a state where the release film 15 is removed. A jig such as a ring frame is attached to the surface of the surface 12a of the surface 12a on which the resin film forming film 23 is not laminated and is used.

  In addition, in the composite sheet 105 for resin film formation shown in FIG. 5, among the surfaces 12 a of the pressure-sensitive adhesive layer 12, the surface on which the resin film formation film 23 is not laminated is similar to that shown in FIGS. 1 and 3. An adhesive layer for a jig may be laminated on (not shown). The resin film forming composite sheet 105 including such a jig adhesive layer is formed on the surface of the jig adhesive layer on the surface of the jig adhesive layer in the same manner as the resin film forming composite sheet shown in FIGS. 1 and 3. A jig such as is attached and used.

  The composite sheet for forming a resin film of the present invention may have any shape of the support sheet and the film for forming a resin film, and may have an adhesive layer for a jig.

  The composite sheet for forming a resin film of the present invention is not limited to those shown in FIGS. 1 to 5, and within a range not impairing the effects of the present invention, a part of the configuration shown in FIGS. It may be deleted or may have other configurations added to those described above.

For example, in the resin film forming composite sheet shown in FIGS. 3 and 4, an intermediate layer may be provided between the base material 11 and the resin film forming film 13. Any intermediate layer can be selected according to the purpose.
Further, in the resin film forming composite sheet shown in FIGS. 1, 2 and 5, an intermediate layer may be provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a resin film of the present invention, the support sheet may be formed by laminating the base material, the intermediate layer, and the adhesive layer in this order. Here, the intermediate layer is the same as the intermediate layer that may be provided in the composite sheet for resin film formation shown in FIGS. 3 and 4.
Moreover, in the composite sheet for resin film formation shown in FIGS. 1 to 5, layers other than the intermediate layer may be provided at arbitrary positions.
Further, in the resin sheet-forming composite sheet of the present invention, a gap may be partially formed between the release film and the layer in direct contact with the release film.
Moreover, in the composite sheet for forming a resin film of the present invention, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

-Substrate The substrate is in the form of a sheet or a film, and examples of its constituent material include various resins.
Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene and norbornene resin. Polyolefin: Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer and other ethylene-based copolymers (ethylene as a monomer Polyvinyl chloride, vinyl chloride resin such as vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Polyesters such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all constituent units have an aromatic cyclic group; Polymers; poly (meth) acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; polyether ketone and the like.
Examples of the resin also include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin obtained by crosslinking one or two or more of the resins exemplified above; a modification of an ionomer or the like using one or two or more of the resins exemplified above Resins are also included.

  The resin constituting the base material may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

  The substrate may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers may be the same or different from each other. The combination of layers is not particularly limited.

The thickness of the substrate is preferably 50 to 300 μm, more preferably 60 to 140 μm. When the thickness of the base material is in such a range, the flexibility of the resin film-forming composite sheet and the sticking property to the semiconductor wafer or the semiconductor chip are further improved.
Here, the “thickness of the base material” means the total thickness of the base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all layers constituting the base material. means.

  It is preferable that the base material has a high thickness accuracy, that is, the base material in which the thickness variation is suppressed regardless of the site. Among the above-mentioned constituent materials, examples of materials that can be used to form such a highly accurate base material include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.

  The base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst and a softening agent (plasticizer) in addition to the main constituent materials such as the resin. May be.

The base material may be transparent or opaque, may be colored depending on the purpose, and may have another layer deposited thereon.
When the resin film forming film is energy ray curable, the substrate is preferably one that transmits energy rays.

  The substrate is roughened by sandblasting, solvent treatment or the like in order to improve the adhesiveness with a layer provided thereon (for example, an adhesive layer, an intermediate layer or a film for forming a resin film); corona discharge treatment The surface may be subjected to an electron beam irradiation treatment, a plasma treatment, an ozone / ultraviolet irradiation treatment, a flame treatment, a chromic acid treatment, an oxidation treatment such as a hot air treatment, or the like. Further, the base material may have a surface treated with a primer.

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

O Adhesive Layer The adhesive layer is in the form of a sheet or a film and contains an adhesive.
Examples of the pressure-sensitive adhesive include pressure-sensitive adhesive resins such as acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, polyvinyl ethers, polycarbonates, ester-based resins, etc., and acrylic-based resins are preferred. ..

  In the present invention, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, and for example, not only the resin itself having adhesiveness, Also included are resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness in the presence of a trigger such as heat or water.

  The pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same or different from each other. The combination of a plurality of layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the total thickness of the pressure-sensitive adhesive layer, for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

The pressure-sensitive adhesive layer may be transparent or opaque, and may be colored depending on the purpose.
When the film for resin film formation is energy ray curable, the adhesive layer preferably transmits energy rays.

  The 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. That is, the pressure-sensitive adhesive layer may be either energy ray curable or non-energy ray curable. The energy ray-curable pressure-sensitive adhesive layer can easily adjust physical properties before and after curing.

<< adhesive composition >>
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive composition can be formed on a target site by applying the pressure-sensitive adhesive composition to the surface on which the pressure-sensitive adhesive layer is to be formed, and drying it as necessary. A more specific method of forming the pressure-sensitive adhesive layer will be described later in detail together with a method of forming other layers.

  The pressure-sensitive adhesive composition can be applied, for example, by the same method as in the case of applying the thermosetting resin film-forming composition described above.

  When the pressure-sensitive adhesive layer is provided on the base material, for example, the pressure-sensitive adhesive composition may be applied on the base material and dried as necessary to laminate the pressure-sensitive adhesive layer on the base material. When the pressure-sensitive adhesive layer is provided on the base material, for example, the pressure-sensitive adhesive composition is applied onto the release film and dried if necessary to form the pressure-sensitive adhesive layer on the release film. Alternatively, the exposed surface of the pressure-sensitive adhesive layer may be attached to one surface of the substrate to laminate the pressure-sensitive adhesive layer on the substrate. In this case, the release film may be removed at any timing in the manufacturing process of the resin film forming composite sheet.

  The drying conditions for the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains the solvent described below, it is preferable to heat-dry it. The pressure-sensitive adhesive composition containing the solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.

  When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable pressure-sensitive adhesive A pressure-sensitive adhesive composition (I-1) containing a resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; non-energy. Energy ray-curable pressure-sensitive adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, referred to as “adhesive resin (I-2a)”). A pressure-sensitive adhesive composition (I-2) containing (may be abbreviated); a pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound, and the like. Is mentioned.

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

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from an alkyl (meth) acrylate ester.
The acrylic resin may have only one type of structural unit, or may have two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred.
As the (meth) acrylic acid alkyl ester, more specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, ( Hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, icosyl (meth) acrylate, etc. Is mentioned.

  From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms. From the viewpoint that the adhesive force of the pressure-sensitive adhesive layer is further improved, the alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Further, the (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms is preferably an acrylic acid alkyl ester.

The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer, in addition to the structural unit derived from the (meth) acrylic acid alkyl ester.
As the functional group-containing monomer, for example, the functional group becomes a starting point of crosslinking by reacting with a crosslinking agent described later, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later. Examples of the acrylic polymer include those capable of introducing an unsaturated group into the side chain.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

  Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-adhesives such as vinyl alcohol and allyl alcohol. Examples thereof include saturated alcohols (unsaturated alcohols having no (meth) acryloyl skeleton).

  Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid, maleic acid, citracone An ethylenically unsaturated dicarboxylic acid such as an acid (dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; and a (meth) acrylic acid carboxyalkyl ester such as 2-carboxyethyl methacrylate. Be done.

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

  The functional group-containing monomer that constitutes the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

  In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, based on the total amount of the structural unit. It is particularly preferably 3 to 30% by mass.

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

  The other monomer constituting the acrylic polymer may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The acrylic polymer can be used as the non-energy ray curable adhesive resin (I-1a).
On the other hand, the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) to obtain the above-mentioned energy ray-curable tackiness. It can be used as a resin (I-2a).

  The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof are arbitrary. You can choose.

  In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 5 to 99% by mass. , 10 to 95 mass% is more preferable, and 15 to 90 mass% is particularly preferable.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4 -Poly (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Examples thereof include (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the above-exemplified monomers.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that it has a relatively large molecular weight and does not easily lower the storage elastic modulus of the pressure-sensitive adhesive layer.

  The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..

  In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound with respect to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass, It is more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

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

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

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

  In the pressure-sensitive adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a), It is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

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

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and other benzoin compounds; acetophenone, 2-hydroxy Acetophenone compounds such as 2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxides and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo Azo compounds such as bisisobutyronitrile; 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 and the like.
Moreover, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine, or the like can be used.

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

  In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound, and 0 It is more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not correspond to any of the above components, as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agents, antioxidants, softening agents (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers. Known additives such as a reaction retarder, a crosslinking accelerator (catalyst), and the like can be mentioned.
The reaction retarder is, for example, an undesired crosslinking reaction in the adhesive composition (I-1) during storage due to the action of a catalyst mixed in the adhesive composition (I-1). It suppresses the progress. Examples of the reaction retarder include those that form a chelate complex by chelating with respect to a catalyst, and more specifically, those that have two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

  As the other additive contained in the pressure-sensitive adhesive composition (I-1), only one kind may be used, or two or more kinds may be used, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

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

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

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

  As the solvent, for example, the solvent used in the production of the adhesive resin (I-1a) may be directly used in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a). However, the solvent of the same or different kind as that used in the production of the adhesive resin (I-1a) may be added separately during the production of the adhesive composition (I-1).

  The solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or may be two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

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

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

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

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

  The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof are arbitrary. You can choose.

  In the pressure-sensitive adhesive composition (I-2), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-2) is preferably 5 to 99% by mass. , 10 to 95 mass% is more preferable, and 10 to 90 mass% is particularly preferable.

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

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same crosslinking agents as in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

  In the pressure-sensitive adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a), It is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

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

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

  In the pressure-sensitive adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a). , 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not correspond to any of the above components, as long as the effects of the present invention are not impaired.
Examples of the other additives in the pressure-sensitive adhesive composition (I-2) include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
As the other additive contained in the pressure-sensitive adhesive composition (I-2), only one kind may be used, or two or more kinds may be used, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.

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

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

<Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound.

  In the pressure-sensitive adhesive composition (I-3), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-3) is preferably 5 to 99% by mass. , 10 to 95 mass% is more preferable, and 15 to 90 mass% is particularly preferable.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. The same thing as the energy ray-curable compound contained in the thing (I-1) is mentioned.
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected. ..

  In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is preferably 0.03 to 200 parts by mass, more preferably 0.05 to 100 parts by mass.

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

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

  In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 100 parts by mass with respect to the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound. It is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not correspond to any of the above components, as long as the effects of the present invention are not impaired.
Examples of the other additives include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
As the other additive contained in the pressure-sensitive adhesive composition (I-3), only one kind may be used, or two or more kinds may be used, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

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

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

<Adhesive composition other than the adhesive compositions (I-1) to (I-3)>
Up to this point, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described. General pressure-sensitive adhesive compositions other than these three kinds of pressure-sensitive adhesive compositions (herein, referred to as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)"). However, it can be used similarly.

Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions, in addition to the energy-ray curable pressure-sensitive adhesive composition.
Examples of the non-energy ray curable pressure sensitive adhesive composition include non-energy ray curable materials such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates and ester resins. A pressure-sensitive adhesive composition (I-4) containing an adhesive resin (I-1a) is preferable, and one containing an acrylic resin is preferable.

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

<Adhesive composition (I-4)>
Preferred examples of the adhesive composition (I-4) include those containing the adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same as the adhesive resin (I-1a) in the adhesive composition (I-1).
The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily set. You can choose.

  In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-4) is preferably 5 to 99% by mass. , 10 to 95 mass% is more preferable, and 15 to 90 mass% is particularly preferable.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition ( I-4) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same as the crosslinking agent in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

  In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a), It is more preferably 0.1 to 47 parts by mass, and particularly preferably 0.3 to 44 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not correspond to any of the above components, as long as the effects of the present invention are not impaired.
Examples of the other additives include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
As the other additive contained in the pressure-sensitive adhesive composition (I-4), only one kind may be used, or two or more kinds may be used, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

  The content of other additives in the pressure-sensitive adhesive composition (I-4) is not particularly limited and may be appropriately selected depending on the type.

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.
The content of the solvent in the pressure-sensitive adhesive composition (I-4) is not particularly limited and may be appropriately adjusted.

  In the resin film-forming composite sheet of the present invention, when the resin film-forming film described later is energy ray curable, the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because if the pressure-sensitive adhesive layer is energy ray-curable, it may not be possible to prevent the pressure-sensitive adhesive layer from being simultaneously cured when the resin film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the resin film-forming film, the cured product of the resin film-forming film and the pressure-sensitive adhesive layer may stick to the interface between them so that they cannot be peeled off. In that case, it becomes difficult to peel the cured product of the resin film forming film, that is, the semiconductor chip having the resin film on the back surface (that is, the semiconductor chip with the resin film) from the support sheet having the cured product of the adhesive layer. , It becomes impossible to normally pick up the semiconductor chip with the resin film. By making the pressure-sensitive adhesive layer non-energy ray curable in the support sheet of the present invention, such a problem can be reliably avoided and the semiconductor chip with a resin film can be more easily picked up.

  Here, the effect when the pressure-sensitive adhesive layer is non-energy ray curable has been described, but even if the layer that is in direct contact with the resin film forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer, If the layer is non-energy ray curable, the same effect is obtained.

<< Production Method of Adhesive Composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive composition (I-4). It is obtained by blending the above-mentioned pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition, such as components other than the above-mentioned pressure-sensitive adhesive.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any of the compounding ingredients other than the solvent and diluting this compounding ingredient in advance, or by diluting any of the compounding ingredients other than the solvent in advance. Alternatively, the solvent may be used as a mixture with these ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; It may be selected appropriately.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◇ Method for producing composite sheet for resin film formation The composite sheet for resin film formation of the present invention can be produced by sequentially laminating the above-mentioned layers in a corresponding positional relationship. The method of forming each layer is as described above.
For example, when the pressure-sensitive adhesive layer is laminated on the base material when manufacturing the support sheet, the above-mentioned pressure-sensitive adhesive composition may be applied onto the base material and dried as necessary.

  On the other hand, for example, in the case of further laminating a resin film forming film on a pressure-sensitive adhesive layer already laminated on a substrate, a resin film forming composition is applied onto the pressure-sensitive adhesive layer to form a resin film. It is possible to directly form the forming film. For layers other than the resin film forming film, this layer can be laminated on the pressure-sensitive adhesive layer by the same method using the composition for forming this layer. As described above, when using any of the compositions to form a continuous two-layer laminated structure, the composition is applied onto the layer formed from the composition to newly form a new layer. Can be formed. However, of these two layers, the layer to be laminated later is formed beforehand by using the composition on another release film, and the side of the formed layer which is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the exposed surface on the opposite side to the exposed surface of the remaining layer that has already been formed. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as needed after the laminated structure is formed.

  For example, a resin film-forming composite sheet in which a pressure-sensitive adhesive layer is laminated on a substrate, and a resin film-forming film is laminated on the pressure-sensitive adhesive layer (in other words, a support sheet is a laminate of the substrate and the pressure-sensitive adhesive layer). In the case of producing a resin film-forming composite sheet) which is a product, a pressure-sensitive adhesive composition is applied onto a base material and dried if necessary to form a pressure-sensitive adhesive layer on the base material. Then, separately, the resin film forming composition is applied onto the release film and dried as necessary to form the resin film forming film on the release film. Then, the exposed surface of the resin film forming film is bonded to the exposed surface of the pressure-sensitive adhesive layer already laminated on the base material, and the resin film forming film is laminated on the pressure-sensitive adhesive layer to form a resin film. A composite sheet is obtained.

When laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, apply the pressure-sensitive adhesive composition on the release film. The adhesive layer is formed on the release film by drying it if necessary, and the exposed surface of this layer is attached to one surface of the substrate to form the adhesive layer on the substrate. You may laminate.
In any method, the release film may be removed at any timing after forming the target laminated structure.

◇ Method of Using Composite Sheet for Forming Resin Film The composite sheet for forming a resin film of the present invention can be used, for example, by the following method.
That is, first, the resin film forming composite sheet is attached to the back surface of the semiconductor wafer by the resin film forming film.

  Next, when the resin film-forming film is energy ray-curable, the resin film-forming film is energy ray-cured to form a resin film by irradiation with energy rays, or is left as it is without being energy ray-cured. If the resin film forming film is non-energy ray curable, the resin film forming film is left as it is. Then, the semiconductor wafer is divided together with the resin film forming film or the resin film by blade dicing to obtain semiconductor chips. At this time, it is preferable to adjust the size of the semiconductor chip to be small. More specifically, the length of one side of the semiconductor chip is preferably 4 mm or less, and may be, for example, 3.5 mm or less, 3 mm or less, 2.5 mm or less, or the like.

  Then, the semiconductor chip is picked up by separating it from the support sheet with the resin film forming film or the resin film being stuck to the back surface (that is, as the semiconductor chip with the resin film forming film or the resin film forming semiconductor chip). To do. At this time, by using the resin film forming film of the present invention, even if the semiconductor chip with a resin film forming film or a semiconductor chip with a resin film having a small size, when picking them up from the support sheet, It is possible to suppress the resin film forming film or the resin film from remaining on the support sheet.

In addition, when the resin film forming film is thermosetting (for example, when the resin film forming film is thermosetting rather than energy ray curable, or both energy ray curable and thermosetting characteristics) In the above case), it is preferable that the resin film forming film or the non-thermoset resin film attached to the semiconductor chip is not thermoset until the end of pickup. That is, the film for forming a thermosetting resin film of the present invention is preferably thermoset after the semiconductor chip is picked up.
When blade dicing is performed without curing the energy ray curable resin film forming film with energy rays, the resin film formed on the back surface of the semiconductor chip is formed at any stage after blade dicing. The film for use may be cured with energy rays to form a resin film, or may not be cured with energy rays.

After that, the target semiconductor device may be manufactured by a method similar to the conventional method depending on the application of the resin film.
For example, when a resin film forming film or a resin film is used as a film adhesive, the semiconductor chip is die-bonded to the circuit surface of the substrate with the film adhesive, and if necessary, the semiconductor chip is further provided with a semiconductor chip. One or more are laminated, wire bonding is performed, and then the whole is sealed with a resin to obtain a semiconductor package. Then, an intended semiconductor device is manufactured using this semiconductor package.
For example, when the resin film forming film is used as the protective film forming film (in other words, the resin film is used as the protective film), the semiconductor chip with the protective film is flip-chip connected to the circuit surface of the substrate and then the semiconductor package is formed. To do. Then, a desired semiconductor device may be manufactured using this semiconductor package. In this case, the resin film (protective film) may be formed by curing the resin film forming film at any timing before and after blade dicing.

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

<Raw material for producing the resin film forming composition>
The raw materials used for producing the resin film-forming composition are shown below.
[Polymer component (A)]
(A) -1: Copolymerized with 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). An acrylic resin (weight average molecular weight 800,000, glass transition temperature -28 ° C).
[Thermosetting component (B)]
・ Epoxy resin (B1)
(B1) -1: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles ("BPA328" manufactured by Nippon Kayaku Co., epoxy equivalent 235 g / eq).
(B1) -2: Dicyclopentadiene type epoxy resin (“XD-1000-L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 248 g / eq).
(B1) -3: Dicyclopentadiene type epoxy resin ("Epiclone HP-7200HH" manufactured by DIC, epoxy equivalent 255-260 g / eq).
・ Thermosetting agent (B2)
(B2) -1: Dicyandiamide (heat activated latent epoxy resin curing agent, "ADEKA HARDNER EH-3636AS" manufactured by ADEKA, active hydrogen amount 21 g / eq)
[Curing accelerator (C)]
(C) -1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ" manufactured by Shikoku Chemicals Co., Ltd.)
[Filler (D)]
(D) -1: Spherical silica (Admatex "SC2050")
[Coupling agent (E)]
(E) -1: Silicate compound to which γ-glycidoxypropyltrimethoxysilane is added (“MKC silicate MSEP2” manufactured by Mitsubishi Chemical Corporation)
[Crosslinking agent (F)]
(F) -1: Tolylene diisocyanate trimer adduct of trimethylolpropane ("BHS8515" manufactured by Toyochem Co., Ltd.)
[Energy ray curable resin (G)]
(G) -1: tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., an ultraviolet curable resin)
[Photopolymerization initiator (H)]
Photopolymerization initiator (H) -1: 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184" manufactured by BASF Japan Ltd.)

<Production of composite sheet for resin film formation>
[Example 1]
(Production of Thermosetting Resin Film Forming Composition (III-1))
As shown in Table 1, polymer component (A) -1 (9.56 parts by mass), epoxy resin (B1) -1 (12.75 parts by mass), epoxy resin (B1) -2 (12.75 parts by mass). Parts), epoxy resin (B1) -3 (25.50 parts by mass), thermosetting agent (B2) -1 (1.08 parts by mass), curing accelerator (C) -1 (1.08 parts by mass), Filler (D) -1 (30.00 parts by mass), coupling agent (E) -1 (0.38 parts by mass), crosslinking agent (F) -1 (0.32 parts by mass), energy ray curability. Resin (G) -1 (6.37 parts by mass) and photopolymerization initiator (H) -1 (0.20 parts by mass) were mixed together, and methyl ethyl ketone was added thereto so that the solid content concentration became 55% by mass. Diluted to obtain a thermosetting resin film forming composition (III-1). In addition, the compounding amounts of components other than methyl ethyl ketone shown here are all solid contents.

(Manufacture of resin film forming film)
The composition (III) obtained above was applied to the release-treated surface of a release film (“SP-PET381031” manufactured by Lintec Co., Ltd., thickness: 38 μm) obtained by subjecting one side of a polyethylene terephthalate (PET) film to a release treatment by silicone treatment. -1) was applied and dried at 100 ° C. for 1 minute to form a resin film forming film having a thickness of 20 μm.
Further, on the exposed surface of the resin film-forming film (the surface on the side opposite to the side provided with the release film), one side of a polyethylene terephthalate (PET) film is separately subjected to a release treatment by silicone treatment. The release-treated surfaces of a film (“SP-PET502150” manufactured by Lintec Co., Ltd., thickness 50 μm) were attached to each other to prepare a laminated film in which the release films were laminated on both sides of the resin film forming film.

(Manufacture of composite sheet for resin film formation)
The resin film-forming film was exposed by removing the release film that was later attached from the laminated film obtained above.
An ethylene-methacrylic acid copolymer (EMAA) film (thickness 40 μm) and a polypropylene (PP) film (thickness 50 μm) are laminated to form a two-layer structure film (total thickness of two layers: 90 μm). The base material (support sheet) and the resin film-forming film are laminated by bonding the newly exposed surface of the resin film-forming film to the surface of the polypropylene film side used as the base material. A composite sheet for forming a resin film was obtained.

<Evaluation of resin film forming film>
(Water absorption rate of the first test piece)
The plurality of resin film-forming films obtained above were laminated and adhered to each other to produce a laminate having a total thickness of 200 μm. Next, this laminated body was punched (cut) into a size of 50 mm × 50 mm to prepare a first laminated body having a size of 50 mm × 50 mm and a thickness of 200 μm. Then, by using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Co., Ltd.), the first laminate is irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ² , The first laminate was ultraviolet-cured to prepare a first cured product that was not thermally cured. Using this first cured as a first specimen, and immediately measuring the mass W _A. Then, the first test piece was immersed in pure water at 23 ° C. for 2 hours, taken out from the pure water, and excess water droplets adhering to the surface were removed. Then, the mass of the first test piece after the immersion the W _B was measured. Then, by the equation _{"(W B -W A) / W} A × 100 " was calculated water absorption of the first specimen (%). When dipping the first test piece in pure water, a sufficient amount of pure water was used so that the entire first test piece was completely immersed in pure water. The results are shown in Table 1.

(Adhesion change rate of the second test piece)
The resin film-forming film obtained above was heated to 40 ° C. and attached to the entire surface of a 6-inch silicon mirror wafer (thickness: 350 μm). Then, the resin film forming film protruding from the silicon mirror wafer was cut and removed. Further, a strong adhesive tape having a width of 25 mm, a length of 200 mm, and a thickness of 70 μm is attached to a plurality of locations on the exposed surface of the resin film forming film (in other words, the surface opposite to the side having the silicon mirror wafer). Then, a notch was formed in the resin film forming film along the outer periphery of the strong adhesive tape. As described above, the second laminated body was produced. Then, using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Co., Ltd.), ultraviolet rays were applied to the resin film forming film in the second laminate under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ^2. The resin film-forming film was UV-cured by irradiating with to obtain a second non-heat-cured product. A second laminated body (cured second laminated body) provided with this second cured product was used as a second test piece, and immediately this second test piece was subjected to an environment of a temperature of 23 ° C. and a relative humidity of 50% for 30 minutes. It was left to stand and aged. Then, immediately after the passage of time, the adhesive strength of the second cured product and the silicon mirror wafer (dip Pre-adhesion strength) P _A1 was measured. Then, the second test piece after this aging was immersed in pure water at 23 ° C. for 2 hours. Next, this second test piece was taken out of pure water, excess water droplets adhering to the surface were removed, and immediately after this immersion, another strong adhesive tape was attached to the second test piece. In the place, the adhesive force P _B1 after immersion between the second cured product and the silicon mirror wafer was measured in an environment of 23 ° C. Then, the adhesive force change rate (%) of the second test piece was calculated by the formula “(| P _B1 −P _A1 |) / P _A1 × 100”. In this way, the adhesive force before immersion and the adhesive force after immersion were continuously measured at different points in the same second test piece. Further, when the second test piece was immersed in pure water, a sufficient amount of pure water was used so that the entire second test piece was completely immersed in pure water.

  In addition, at the time of measuring the adhesive force before immersion and the adhesive force after immersion, using a universal tensile tester “Autograph” manufactured by Shimadzu Corporation, both of the two peeled surfaces generated when the second cured product was peeled off were measured. So-called 180 ° peeling was performed at a peeling speed of 300 mm / min so that the laminated body of the second cured product and the strong adhesive tape was peeled off so that the angle to be made was 180 °. Then, the peeling force (mN / 25 mm) at this time was measured and used as the adhesive force before immersion and the adhesive force after immersion. The results are shown in Table 1.

(Young's modulus, breaking elongation and breaking stress of the third test piece)
A plurality of resin film-forming films obtained above were laminated to produce a laminate having a total thickness of 200 μm. Next, this laminated body was punched (cut) into a size of 15 mm × 150 mm to produce a third laminated body having a size of 15 mm × 150 mm and a thickness of 200 μm. Then, using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Co., Ltd.), the third laminated body is irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ² , The third laminate was UV-cured to produce a non-thermoset third cured product. Using this third cured product as a third test piece, a tensile test was performed on the third test piece in an environment of 23 ° C. at a test speed of 200 mm / min in accordance with JIS K 7127, and Young's modulus ( Young's modulus before immersion (MPa) was measured.
Separately, the same third test piece was immersed in pure water at 23 ° C. for 2 hours. Then, the third test piece after the immersion was immediately subjected to a tensile test in the same manner in an environment of 23 ° C. to measure the Young's modulus (Young's modulus after immersion) (MPa). When dipping the third test piece in pure water, a sufficient amount of pure water was used so that the entire third test piece was completely immersed in pure water. The results are shown in Table 1.

  In addition, when measuring the Young's modulus before soaking and the Young's modulus after soaking of the third test piece, from the elongation of the third test piece when the third test piece ruptures, the elongation at break before immersion of the third test piece ( %) And the elongation at break after immersion (%), respectively, and from the force applied to the third test piece when the third test piece broke, the breaking stress before immersion (MPa) and the breaking stress after immersion (MPa) ) Respectively. The results are shown in Table 1.

<Evaluation of composite sheet for resin film formation>
(Suitability for picking up semiconductor chip with resin film (manufacturability for semiconductor chip with resin film))
A back grinding tape (“ADWILL E-8180HR” manufactured by Lintec Co., Ltd.) was attached to an 8-inch silicon mirror wafer using a tape laminator (“RAD3510” manufactured by Lintec Co., Ltd.). Then, using a grinder (“DGP8760” manufactured by Disco Corporation), the surface of the 8-inch silicon mirror wafer opposite to the side to which the back grinding tape was attached was ground to a thickness of 350 μm. . Then, this silicon mirror wafer was left for 72 hours after grinding. Then, using a wafer mounter (“RAD2700” manufactured by Lintec Co., Ltd.), the composite sheet for resin film formation obtained above is heated to 40 ° C. on the ground surface of the silicon mirror wafer after being left to stand, and the resin film is formed. The film for forming was applied at an application speed of 20 mm / sec. Then, after removing the back grind tape, using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Co., Ltd.), under the conditions of an illuminance of 230 mW / cm ² and a light amount of 120 mJ / cm ² , this resin film formation By irradiating the resin film-forming film in the composite sheet with ultraviolet rays, the resin film-forming film was UV-cured to prepare a resin film that was not thermally cured. Then, using a dicing device (“DFD6361” manufactured by Disco Co., Ltd.), the silicon mirror wafer together with the resin film is diced while applying cooling water at a flow rate of 1.0 L / min. Separated into chips.

  A work in which a large number of silicon chips with a resin film after dicing were fixed to a support sheet was immersed in pure water at 23 ° C. for 2 hours. Then, using a pickup / die bonding apparatus (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.), the operation of picking up the resin film-attached silicon chip by separating it from the support sheet (the base material) in the work after the immersion is performed 100 times. I went there. At this time, the pickup was of a type in which one resin film-coated silicon chip was pushed up by one pin, the bumping speed was 20 mm / s, and the bumping amount was 200 μm. Then, using an optical microscope ("VHX-100" manufactured by Keyence Corporation), the surface of the supporting sheet after the operation, which was provided with the resin film-attached silicon chip, was observed to confirm the presence or absence of the resin film. .. Then, on the surface of the support sheet, out of 100 places where the resin film-attached silicon chip was provided, the number of places where the resin film remained, the number of times that the pickup was not normally performed, that is, the pickup suitability. The number of defectives was specified. It is judged that the silicon chip with the resin film could not be normally picked up on the surface of the support sheet where the resin film remains. The results are shown in Table 1. Among the evaluation result columns in Table 1, the “number of defects in pick-up suitability” column shows the evaluation result of this item.

<Production and Evaluation of Resin Film Forming Film and Resin Film Forming Composite Sheet>
[Examples 2-3, Comparative Examples 1-2]
A resin film-forming film was formed in the same manner as in Example 1 except that the content of each component of the thermosetting resin film-forming composition (resin film-forming film) was changed as shown in Table 1. And a composite sheet for resin film formation was manufactured and evaluated. The results are shown in Table 1.
In addition, description of "-" in the column of the contained component in Table 1 means that the thermosetting resin film forming composition does not contain the component.

  As is clear from the above results, in Examples 1 to 3, the number of defects in picking suitability of the silicon chip with the resin film was suppressed to 4 or less.

In Examples 1 to 3, the water absorption rate of the first test piece was 0.24 to 0.50%, and the adhesive force change rate of the second test piece was 16.5 to 38.4%. At the time of measuring the adhesive force before immersion (adhesive force after lapse of time) P _A1 between the second cured product and the silicon mirror wafer and when measuring the adhesive force P _B1 after immersion, the peeled portion of the second test piece was visually observed. As a result of observation, in Examples 1 to 3, cohesive failure occurred in the second cured product of the second test piece both before and after immersion.
That is, the energy ray-cured products of the resin film forming films of Examples 1 to 3 have a low water absorption rate, a change in adhesive strength before and after immersion (water absorption) is suppressed, and even after immersion, the aptitude for pickup is high. Was excellent.

  Moreover, in Examples 1 to 3, the Young's modulus of the third test piece after immersion was 20.7 to 104.5 MPa, and the energy ray cured products of the resin film forming films of Examples 1 to 3 were intended for pickup. It was difficult for cutting to occur at the outside, and had more preferable characteristics. Further, in Examples 1 to 3, the breaking elongation after immersion of the third test piece was 25 to 384%, and the breaking stress after immersion of the third test piece was 0.9 to 4.6 MPa.

  On the other hand, in Comparative Example 1, the number of defects in the pick-up suitability of the resin film-coated silicon chip was 56, which was clearly inferior to the pick-up suitability.

In Comparative Example 1, the water absorption rate of the first test piece was 0.96%, which was a high level.
On the other hand, as in the case of Examples 1 to 3, the peeling point of the second test piece was visually observed at the time of measuring the adhesive force before immersion (adhesive force after aging) P _A1 and when measuring the adhesive force P _B1 after immersion. As a result of the observation, after the immersion, the interfacial destruction occurred between the second cured product and the silicon mirror wafer, but before the immersion, the interfacial destruction occurred between the second cured product and the strong adhesive tape. Therefore, the second cured product and the silicon mirror wafer remained in close contact with each other. That is, in Comparative Example 1, the peeling force before immersion did not represent the adhesive force between the second cured product and the silicon mirror wafer, and the measured peeling force was 23584 (mN / 25 mm). From the above, it was only confirmed that the adhesive force between the second cured product and the silicon mirror wafer was greater than 23584 (mN / 25 mm), and the adhesive force change rate of the second test piece was greater than 66.0%. It was However, it was confirmed that the rate of change in adhesive strength was at a high level.
That is, the energy ray-cured product of the resin film-forming film of Comparative Example 1 had a high water absorption rate, and the change in the adhesive force before and after immersion (water absorption) was not suppressed, and after the immersion, the aptitude was good. However, it did not have desirable characteristics.

  Further, in Comparative Example 1, the Young's modulus after immersion of the third test piece was 1.0 MPa, and the energy ray cured product of the resin film forming film of Comparative Example 1 was cut at an unintended place during pickup. It was easy to obtain, and also in this respect, it did not have preferable characteristics.

  In Comparative Example 2 as well, the number of defective pickup suitability of the semiconductor chip with the resin film was 45, which was clearly inferior to the pickup suitability.

In Comparative Example 2, the water absorption rate of the first test piece was 0.62%, which was a high level.
On the other hand, in Comparative Example 2 as well, as in Comparative Example 1, after the immersion, the interfacial destruction occurred between the second cured product and the silicon mirror wafer, but before the immersion, the second cured product. The interfacial destruction occurred between the adhesive tape and the strong adhesive tape, and the second cured product and the silicon mirror wafer remained in close contact with each other. That is, also in Comparative Example 2, the peeling force before immersion did not represent the adhesive force between the second cured product and the silicon mirror wafer, and the measured peeling force was 25877 (mN / 25 mm). From the above, it is only confirmed that the adhesive force between the second cured product and the silicon mirror wafer is larger than 25877 (mN / 25 mm), and the adhesive force change rate of the second test piece is larger than 69.0%. It was However, it was confirmed that the rate of change in adhesive strength was at a high level.
That is, the energy ray cured product of the resin film-forming film of Comparative Example 2 also had a high water absorption rate, and the change in the adhesive strength before and after immersion (water absorption) was not suppressed, and the pick-up aptitude after immersion was good. However, it did not have desirable characteristics.

  In Comparative Example 2, the Young's modulus after immersion of the third test piece was 5.1 MPa, and the energy ray cured product of the resin film-forming film of Comparative Example 2 was also cut at an unintended portion during pickup. It was easy to obtain, and also in this respect, it did not have preferable characteristics.

  The present invention can be used for manufacturing a semiconductor device.

  101, 102, 103, 104, 105 ... Composite sheet for resin film formation, 1 ... Support sheet, 11 ... Base material, 12 ... Adhesive layer, 13, 23 ... Resin film formation Film for

Claims (4)

A film for forming a resin film,
A first laminate having a size of 50 mm × 50 mm and a thickness of 200 μm, which is formed by laminating a plurality of the resin film forming films,
When the resin film forming film is energy ray curable, the first cured product obtained by curing the first laminate with energy ray is used as a first test piece, and the resin film forming film is non-energy ray curable. When the first test piece is immersed in pure water for 2 hours, the water absorption rate of the first test piece is 0.55% or less. Yes, and
A second laminated body is produced in which the resin film forming film is attached to a silicon mirror wafer,
When the resin film forming film is energy ray curable, the cured second laminated body after the resin film forming film in the second laminated body is energy ray cured to form a second cured product Between the second cured product and the silicon mirror wafer when the second test piece is allowed to stand for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The adhesive strength after aging was measured, and the adhesive strength after immersion between the second cured product and the silicon mirror wafer was measured when the second test piece after aging was immersed in pure water for 2 hours. At this time, the adhesive force change rate of the second test piece calculated from the adhesive force after aging and the adhesive force after immersion is 60% or less, or
When the resin film forming film is non-energy ray curable, the second laminate is used as a second test piece, and the second test piece is used for 30 minutes under an environment of a temperature of 23 ° C. and a relative humidity of 50%. The adhesive strength after aging between the resin film forming film and the silicon mirror wafer was measured when the film was left standing and aged, and the second test piece after aging was immersed in pure water for 2 hours. When the adhesive strength after immersion between the film for resin film formation and the silicon mirror wafer was measured, the adhesive strength change of the second test piece calculated from the adhesive strength after aging and the adhesive strength after immersion. A film for forming a resin film having a rate of 60% or less.   When a third laminated body having a size of 15 mm × 150 mm and a thickness of 200 μm, which is formed by laminating a plurality of the resin film forming films, is prepared, and the resin film forming film is energy ray curable, The third cured product obtained by curing the third laminated body with energy rays is used as a third test piece. When the resin film forming film is non-energy ray curable, the third laminated body is As a test piece, when the third test piece was immersed in pure water for 2 hours, a tensile test based on JIS K 7127 was performed and the test speed was measured at 200 mm / min. The film for forming a resin film according to claim 1, having a Young's modulus of 15 MPa or more. The resin film-forming film contains a filler,
The film for resin film formation according to claim 1 or 2, wherein in the film for resin film formation, the ratio of the content of the filler with respect to the total mass of the film for resin film formation is 25 to 75% by mass. .. A support sheet, on the support sheet, comprising a resin film forming film,
A composite sheet for resin film formation, wherein the resin film formation film is the resin film formation film according to any one of claims 1 to 3.

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