WO2019008898A1

WO2019008898A1 - Resin film forming film and resin film forming composite sheet

Info

Publication number: WO2019008898A1
Application number: PCT/JP2018/018248
Authority: WO
Inventors: 啓示布施
Original assignee: リンテック株式会社
Priority date: 2017-07-06
Filing date: 2018-05-11
Publication date: 2019-01-10
Also published as: CN110831766A; KR20200026833A; SG11201913224TA; JPWO2019008898A1; MY194458A; TWI743361B; KR102507152B1; JP7044780B2; CN110831766B; TW201907491A; PH12020500005A1

Abstract

This resin film forming film satisfies the following conditions (i) and (ii): (i) when a first test specimen manufactured using a first laminated body which comprises a plurality of the resin film forming films laminated together and has a size of 50 mm × 50 mm and a thickness of 200 μm is immersed in pure water for two hours, the first test specimen has a water absorption of 0.55% or less; and (ii) when a second test specimen manufactured using a second laminated body in which the resin film forming film is attached to a silicon mirror wafer has been left in an environment of 23°C and 50% RH for 30 minutes, and when the second test specimen after the elapse of the time has been immersed in pure water for two hours, an adhesive force between the resin film forming films or a cured product thereof and the silicon mirror wafer measured before and after the immersion exhibits an adhesive force change rate of 60% or less.

Description

Resin film-forming film and resin film-forming composite sheet

The present invention relates to a resin film-forming film and a resin film-forming composite sheet.
Priority is claimed on Japanese Patent Application No. 2017-132980, filed July 6, 2017, the content of which is incorporated herein by reference.

In the process of manufacturing a semiconductor device, one 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 film (a semiconductor chip with a film for forming a resin film) provided with a film for forming a resin film for processing is handled. As said resin film, the hardened | cured material of the said film for resin film formation, etc. are mentioned, for example. In this case, after a film for resin film formation is attached to the surface (rear surface) opposite to the circuit surface of the semiconductor wafer, singulation of the semiconductor wafer into semiconductor chips and curing of the film for resin film formation are performed. By carrying out, a semiconductor chip with a resin film is produced.
On the other hand, as a semiconductor chip which becomes a use object of a film for resin film formation, what equipped with a bump which is an electrode on a circuit side, and a thing which is not equipped are mentioned.

Semiconductor chips that do not have bumps on the circuit surface are the most widely used, and on the back surface, usually, as a film for forming a resin film, the semiconductor chip is die-bonded to the circuit formation surface of the substrate. The film adhesive used is provided. That is, the film for resin film formation in this case is a film-like 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, a protective film is usually provided on the back surface as the resin film. That is, the resin film in this case is a protective film, and the film for resin film formation is a film for protective film formation.

The semiconductor chip with a resin film and the semiconductor chip with a film for resin film formation are manufactured using, for example, a composite sheet for resin film formation comprising a support sheet and comprising a resin film formation film on the support sheet. Be done. More specifically, it is as follows. That is, first, the composite sheet for resin film formation is attached to the back surface of the semiconductor wafer by the film for resin film formation in this 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 the cured product thereof into pieces into semiconductor chips. Next, the semiconductor chip is separated from the support sheet and picked up in a state where the back surface is provided with the resin film-forming film or the cured product after cutting. By the above, the semiconductor chip with a film for resin film formation or the semiconductor chip with a resin film is obtained. Although there are several methods for dicing, 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 types of composite sheets for resin film formation have been disclosed so far. For example, a film for thermosetting resin film formation which contains an inorganic filler in a specific range amount relative to the organic resin component, has a melt viscosity before thermal curing within the specific range, and is excellent in adhesion to an adherend There are disclosed a thermosetting type die bond film) and a composite sheet for forming a resin film (dicing die bond film) provided with this film (see Patent Documents 1 and 2).

On the other hand, conventionally, after carrying out blade dicing, when a semiconductor chip with a film for resin film formation or a semiconductor chip with a resin film is pulled apart from the support sheet and picked up, a film for resin film formation or a resin film to be picked up with the semiconductor chip The problem that part or all of the resin film remains on the support sheet, that is, a film-coated semiconductor chip with a film or a resin film-coated semiconductor chip can not be obtained normally, and pickup defects easily occur There was a problem of. Such a problem is remarkable in the case of a semiconductor chip with a film for forming a resin film having a small size or a semiconductor chip with a resin film in which the length of one side of the semiconductor chip is 4 mm or less.

On the other hand, are the film for thermosetting resin film formation disclosed by patent documents 1 and 2 and the composite sheet for resin film formation provided with this film can solve such a problem? Not sure.

Japanese Patent No. 4732472 Japanese Patent No. 5390209

The present invention is a resin film-forming film for forming a resin film-forming composite sheet together with a support sheet and for forming a resin film on the back surface of a semiconductor chip, wherein the resin film-forming film is used as a blade. When picking up a semiconductor chip with a film for resin film formation with a small size or a semiconductor chip with a resin film obtained after dicing, it is possible to suppress the remaining of the film or resin film for resin film formation on a support sheet. It is an object of the present invention to provide a resin film-forming film and a resin film-forming composite sheet provided with the film.

The present invention is a film for forming a resin film, wherein a first laminate having a size of 50 mm × 50 mm and a thickness of 200 μm, which is obtained by laminating a plurality of films for forming a resin film, is produced. When the film for film formation is energy ray curable, the first cured product obtained by energy ray curing of the first laminate is used as a first test piece, and the film for resin film formation is non-energy ray curable. In some cases, when the first test piece is immersed in pure water for 2 hours using the first laminate as a first test piece, the water absorption of the first test piece is 0.55% or less, And when the film for resin film formation sticks the 2nd laminated body which is stuck on a silicon mirror wafer, and the film for resin film formation is energy beam hardening property, the above-mentioned in the 2nd above-mentioned layered product Enel film for resin film formation The cured second laminate after Gie ray curing to form a second cured product is used as a second test piece, and the second test piece is allowed to stand for 30 minutes under an environment of a temperature of 23 ° C. and a relative humidity of 50%. The adhesion after the aging of the second cured product and the silicon mirror wafer when measured with time is measured, and the second test piece after aging is immersed in pure water for 2 hours, 2 When the adhesion after immersion between the cured product and the silicon mirror wafer is measured, the change in adhesion of the second test piece calculated from the adhesion after aging and the adhesion after immersion is 60% or less If the film for forming a resin film is non-energy ray curable, the second laminate is used as a second test piece, and the second test piece has a temperature of 23.degree. C. and a relative humidity of 50%. The resin film-forming film and the resin film when left to stand for 30 minutes under the environment of The adhesion after the aging with the silicon mirror wafer is measured, and when the second test piece after aging is immersed in pure water for 2 hours, it is between the resin film-forming film and the silicon mirror wafer. The film for resin film formation whose adhesive force change rate of the said 2nd test piece calculated from the adhesive force after immersion and adhesive force after immersion when measuring adhesive force after immersion is provided.

A third laminate having a size of 15 mm × 150 mm and a thickness of 200 μm, in which a plurality of the resin film-forming films are laminated, is prepared, and the resin film-forming film is energy beam curable. The third cured product obtained by energy beam curing the third laminate is used as a third test piece, and when the resin film-forming film is non-energy beam curable, the third laminate is As a test piece, when the third test piece is immersed in pure water for 2 hours, it is a tensile test based on JIS K 7127, and the test speed is measured as 200 mm / min. The Young's modulus may be 15 MPa or more.
The film for resin film formation of the present invention contains a filler, and in the film for resin film formation, the ratio of the content of the filler to the total mass of the film for resin film formation is 25 to 75% by mass. It may be
The present invention comprises a support sheet, and on the support sheet, a resin film-forming film, wherein the resin film-forming film is the resin film-forming film of the present invention described above. Provide a composite sheet.

The film for resin film formation of the present invention can constitute a composite sheet for resin film formation together with a support sheet, and can form a resin film on the back surface of a semiconductor chip. By using the film for forming a resin film, blade dicing is performed to obtain a semiconductor chip with a film for forming a resin film or a semiconductor chip with a resin film having a small size, and these are picked up from the support sheet to the support sheet. It is possible to suppress the remaining of the resin film-forming film or the resin film.

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.

フィルム Film for forming a resin film The film for forming a resin film of the present invention has a water absorption coefficient of 0.55% or less of the following first test piece produced from the film, and the following second test piece produced from the film The adhesive force change rate 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 1 laminated body. When the film for resin film formation is energy ray curable, the first test piece is a first cured product obtained by energy ray curing the first laminate.
When the film for resin film formation is non-energy ray curable, the second test piece is a second laminate formed by sticking the film for resin film formation on a silicon mirror wafer, and the film for resin film formation When it is energy ray curable, the second test piece is a cured second laminate after energy ray curing of the resin film-forming film in the second laminate to form a second cured product .
The water absorption rate (%) of the first test piece is calculated by the formula “(W _B −W _A ) / W _A × 100”. Here, W _A is the mass of the first test piece before immersion in pure water, and W _B is the first test piece after immersing the first test piece for which W _A was measured in pure water for 2 hours Mass of
When the film for resin film formation is non-energy ray curable, the adhesive strength change rate (%) of the second test piece is calculated by the formula “(| P _B2 −P _A2 |) / P _A2 × 100”. Here, PA ₂ is a film for forming a resin film and silicon in the second test piece when the second test piece is allowed to stand for 30 minutes under an environment of a temperature of 23 ° C. and a relative humidity of 50% for a lapse of time. Adhesive force with mirror wafer (adhesive force after aging). In addition, _PB2 is the time when the second test piece after this aging is immersed in pure water for 2 hours, between the resin film forming film and the silicon mirror wafer in the second test specimen after this immersion Adhesive force (adhesive force after immersion).
On the other hand, when the film for resin film formation 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 allowed to stand for 30 minutes under an environment of a temperature of 23 ° C. and a relative humidity of 50% for a while. Adhesive force with the wafer (adhesive force after aging). In addition, P _B1 is an adhesion between the second cured product in the second test piece after this immersion and the silicon mirror wafer when the second test piece after this aging is immersed in pure water for 2 hours. Force (adhesion after immersion).
The above-mentioned water absorption rate and adhesive force change rate will be described in more detail later.

The film for resin film formation of the present invention can be used to form a resin film on the surface of the semiconductor chip opposite to the circuit surface (sometimes referred to as "back surface" in this specification). . In addition, the film for resin film formation 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 not. If the resin film is curable, it is considered that the resin film is formed at the stage where the resin film-forming film is attached to the target location.

If the semiconductor chip does not have bumps on the circuit surface, examples of the resin film-forming film or resin film include a film-like adhesive used for die-bonding the semiconductor chip to the circuit-forming surface of the substrate. .
On the other hand, if the semiconductor chip has bumps on the circuit surface, such semiconductor chips are flip chip connected to the circuit formation surface of the substrate by bumps, and the back surface of the semiconductor chip is peeled off as it is. It becomes. The film for forming a resin film when used for such a semiconductor chip includes a film for forming a protective film, and the resin film includes a protective film for protecting the back surface.
That is, the film for resin film formation of this invention can be used for formation of the said film adhesive or protective film.

When the film for resin film formation of the present invention is attached to the surface of the semiconductor wafer opposite to the circuit surface (this specification may be referred to as “rear surface” as in the case of the semiconductor chip), It can be used in the state which comprised the composite sheet for resin film formation with a support sheet.
As described above, the resin film-forming film of the present invention satisfies the conditions of the water absorption rate and the adhesive strength change rate. By using such a film for resin film formation, when picking up a semiconductor chip with a film for resin film formation or a semiconductor chip with a resin film having a small size after blade dicing, the resin film to the support sheet Remaining of the film for formation or the resin film can be suppressed. Although the reason why the resin film-forming film of the present invention exhibits such excellent pickup aptitude is not clear, it is presumed as follows.

The film for resin film formation and the resin film (the cured product of the film for resin film formation) have a projection-like shape or the like from the surface opposite to the side in contact with the semiconductor chip at the time of pickup The force is applied by a pushing 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 are hard to be peeled off from the semiconductor chip because the force pressed against the semiconductor chip is strong. On the other hand, in the resin film-forming film and the resin film, since the force pressed against the semiconductor chip is weak at the place away from the place where the force is applied, the place where the force is applied and the vicinity thereof Also, it is easy to peel off the semiconductor chip. For example, when a force is applied near the center of the opposite surface of the resin film-forming film or resin film, the vicinity of the center and the vicinity of the resin film-forming film or resin film peel off from the semiconductor chip Although it is difficult, the peripheral edge far from the center and the vicinity thereof are more easily peeled from the semiconductor chip than the vicinity of the center and the vicinity thereof. As described above, among the resin film-forming film and the resin film, the portion to which a force is applied and the vicinity thereof are relatively difficult to be peeled off from the semiconductor chip as described above, but depending on the conditions, they may be peeled off. .

On the other hand, in the case of performing blade dicing, cooling water ("" in the contact points between the semiconductor wafer and the resin film-forming film or resin film) in order to suppress the temperature rise at the contact points with the dicing blade. Dicing while pouring (also called cutting water). However, in the case of obtaining a semiconductor chip having a small size, the dicing time becomes longer due to the large number of dicing points, and the time for which the resin film-forming film and the resin film are exposed to cooling water becomes long. I will. In this case, the resin film-forming film and the resin film become softer than before water absorption due to water absorption, and may be torn by the force applied at the time of pickup. In the case where the film for resin film formation and the resin film are separated, at least the place away from the place where the force is applied may be likely to be separated from the semiconductor chip as described above. It is presumed that it will remain on the support sheet. In addition, at the location where the resin film-forming film or resin film has been peeled off from the semiconductor chip, the cooling water (cutting water) used at dicing may be between the resin film-forming film or resin film and the semiconductor chip. Break into Therefore, after that, the film for resin film formation or the resin film does not adhere closely to the semiconductor chip at such a place, while the film or resin film for resin film formation easily maintains the state of adhesion to the support sheet . It is inferred that such an action makes the resin film-forming film or resin film after being torn be easily left on the support sheet.
Such a problem is remarkable in the film for resin film formation, but it is remarkable even in the case of a resin film, even a resin film having a low degree of curing, such as one not completely cured. For example, the above-mentioned problems are recognized in a cured product (energy beam cured product) by energy beam irradiation of a film for forming a resin film having both energy beam curing properties and thermosetting properties as described later.

On the other hand, when the resin film-forming film of the present invention is used, the above-mentioned problems can be solved by both the water absorption coefficient and the adhesive power change ratio being within the specific range, and an excellent pickup It is presumed that aptitude can be obtained.

In the above-mentioned "Japanese Patent No. 4732472" (Patent Document 1) and "Japanese Patent No. 5390209 Specification" (Patent Document 2), a thermosetting resin which shows a moisture absorption in a specific range after thermosetting. Although a film for film formation (a thermosetting type die-bonding film) is disclosed, the moisture absorption rate before the thermosetting is not disclosed. This is because these films for thermosetting resin film formation are intended to prevent the generation of cracks in the semiconductor package in the reflow process. That is, the subject of the invention currently disclosed by these patent documents differs from the subject of this invention. Furthermore, the moisture absorption rate of the film for thermosetting resin film formation disclosed in these patent documents is completely unrelated to the water absorption rate in the film for resin film formation of the present invention, and the water absorption rate in the present invention It does not recall anything.

In the present specification, "a semiconductor chip with a film for resin film formation" means "a semiconductor chip with a film for resin film formation on the back surface", and "a semiconductor chip with a resin film". , “Having a resin film on the back surface of the semiconductor chip”. The resin film in the semiconductor chip with a resin film may be a cured product in which the resin film-forming film is completely cured, or a cured product which is not completely cured (in other words, a curing in which the curing degree is further increased) Object).

In the present specification, the term "energy beam" means an electromagnetic wave or charged particle beam having energy quantum, and examples thereof include ultraviolet light, radiation, electron beam and the like. The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet light source. The electron beam can irradiate what was generated by the electron beam accelerator or the like.
Furthermore, in the present specification, "energy ray curing property" means a property to be cured by irradiation with energy rays, and "non energy ray curing property" is a property to be not cured even by irradiating 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 film for resin film formation can be formed using the composition for resin film formation containing the constituent material.
In addition, in this specification, "non-hardenable" means the property which is not hardened | cured by any means, such as heating and irradiation of an energy ray.

The film for forming a resin film of the present invention has a hardenability which does not depend on the presence or absence of curability, and in the case where the film has curability, the filler described later regardless of which one of thermosetting and energy ray curable. Those containing fillers such as D) are preferred. By using the filler, it is possible to more easily manufacture a resin film-forming film which satisfies the conditions of the water absorption rate and the adhesive force change rate.

When the film for resin film formation of the present invention contains a filler, in the film for resin film formation, the ratio of the content of the filler to the total mass of the film for resin film formation (in other words, the resin film formation) The ratio of the content of the filler to the total content of 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 is significantly less likely to absorb water than the other components, it is easier to set the water absorption to 0.55% or less when the ratio of the content of the filler is the lower limit value or more. And when picking up a semiconductor chip with a film for resin film formation with a small size or a semiconductor chip with a resin film from a support sheet, the effect which controls residual of a film for resin film formation or a resin film to a support sheet becomes higher. . Moreover, the intensity | strength of the film for resin film formation and the resin film improves more because the ratio of content of a filler is below the said upper limit. The filler will be described in detail later.

<< Water absorption of first test piece >>
In the resin film-forming film, when the first test piece is immersed in pure water for 2 hours, the water absorption of the first test piece is 0.55% or less. In addition, in this specification, all unit "%" of a moisture absorption means "mass%". Below, the water absorption of a 1st test piece is demonstrated in detail.

When the resin film-forming film is non-energy ray curable, the first test piece is 50 mm × 50 mm in size, in which a plurality of resin film-forming films are laminated in their thickness direction. It is a first laminate having 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 film for resin film formation is a thermosetting, regardless of whether the film for resin film formation is energy ray curing or non-energy ray curing, the first laminate and the first cured product are It is preferable that none of them is thermally cured.

The plurality of resin film-forming films used for producing the first laminate all have the same composition.
The thicknesses of the plurality of resin film-forming films may be all the same, all may be different, or only some may be the same, but preferably all are the same.

In the first laminate, for example, a plurality of resin film-forming films of any size larger than 50 mm × 50 mm are laminated and bonded so that the total thickness is 200 μm, and the size of 50 mm × 50 mm It can be produced by punching out (cutting). In the first laminate, for example, a plurality of resin film-forming films with a size of 50 mm × 50 mm are laminated with their peripheral edge portions aligned so that the total thickness is 200 μm. It can also be produced by pasting together.

When the film for resin film formation is non-energy ray curable, the produced 1st laminated body is used as a 1st test piece as it is.
When the oil film-forming film is energy ray curable, the prepared first laminate is further irradiated with energy rays to cure all resin film forming films in the first laminate. The obtained first cured product is used as a first test piece.

The irradiation conditions of the energy beam to the first laminate (film for forming a fat film) when producing the first cured product are not particularly limited as long as the first laminate is sufficiently energy beam cured.
In general, the illuminance of energy rays during curing of the first laminate is preferably 120 to 280 mW / cm ² , and the light amount of energy rays is preferably 100 to 1000 mJ / cm ² .

In order to determine 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, it is preferable to measure the mass W _A of the first test piece in a state where the first test piece after preparation does not show a clear mass change due to moisture absorption or the like. By doing this, the water absorption rate described later can be determined with higher accuracy.

The first test piece whose mass W _A has been measured is immersed in pure water for 2 hours. At this time, the first test piece is not exposed in the pure water so as to be exposed (in other words, so that the whole first test piece is completely immersed in the pure water) 1 Sink the test piece.

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

After immersing in pure water for 2 hours, the first test piece is promptly taken out of the pure water, and if necessary, excess water droplets adhering to the surface of the first test piece are drained (removed), for example. Then, the mass W _B of the first test piece after this immersion is measured.
Then, using the values of these W _A and W _B , the water absorption (%) of the first test piece is calculated by the formula “(W _B −W _A ) / W _A × 100”.

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

In the present invention, the lower limit value of the water absorption rate of the first test piece is not particularly limited, and may be, for example, 0%. It can be said that the physical properties of the first test piece (in other words, the film for forming a resin film or a resin film) are less likely to change in physical properties as the water absorption rate of the first test piece is lower. The water absorption rate of the first test piece is preferably 0.01% or more, and more preferably 0.05% or more from the viewpoint of facilitating the production of the resin film-forming film.

In the present invention, the water absorption rate of the first test piece can be appropriately adjusted to be a numerical value range determined by arbitrarily combining any of the lower limit values described above and any upper limit value. For example, the water absorption rate of the first test piece is preferably 0 to 0.55%, more preferably 0 to 0.53%, and may be 0 to 0.4% or the like. However, these are examples of the water absorption of a 1st 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-described condition, and the adhesive strength change rate of the second test piece is 60% or less. Below, the adhesive force change rate of a 2nd test piece is demonstrated in detail. The rate of change in adhesion indicates the degree of change in adhesion before and after the second test piece is immersed in pure water under specific conditions.

When the film for resin film formation is non-energy ray curable, the second test piece is a second laminate in which the film for resin film formation is attached to a silicon mirror wafer.
When the film for resin film formation is energy ray curable, the second test piece irradiates the film for resin film formation in the second laminate with an energy ray to cure the film for resin film energy ray curing It is a cured 2nd laminated body (namely, hardened | cured material of 2nd laminated body) after making it be 2nd hardened | cured material.
When the resin film-forming film is a thermosetting resin, the second laminate and the second cured product are the same regardless of whether the resin film-forming film is energy ray curable or non-energy ray curable. It is preferable that none of them is thermally cured.

The second laminate can be produced by sticking one surface of a resin film-forming film to the mirror surface of a silicon mirror wafer.

The size of the silicon mirror wafer used for producing the second laminate 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 measured accurately. .
The thickness of the silicon mirror wafer is preferably 350 to 760 μm. By doing this, it is possible to measure the adhesive force described later 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 film for resin film formation which is a measuring object of the adhesive force with a silicon mirror wafer (in other words, it peels from a silicon mirror wafer) is 25 mm. The length of the resin film-forming film to be measured is not particularly limited as long as the adhesive strength can be measured with high accuracy, but it is preferably 150 to 250 mm. The size of the film for resin film formation, which is a measurement target of the adhesion after the aging (adhesion before immersion described later), and the size of the film for formation of a resin film, which is measurement of adhesion after the immersion, are the same. .

At the time of production of the second laminate, it is preferable to heat the resin film-forming film at, for example, 35 to 45 ° C. and attach it to a silicon mirror wafer. By doing so, a more stable second laminate can be obtained.

When the film for resin film formation is non-energy ray curable, the produced second laminate is used as it is as a second test piece.
When the oil film-forming film is energy ray curable, the resin film-forming film in the produced second laminate is further subjected to energy from the side opposite to the side provided with the silicon mirror wafer of this film. The cured second laminate (i.e., the cured product of the resin film-forming film) after irradiation of the wire and energy beam curing of the resin film-forming film in the second laminate to obtain a second cured product The provided silicon mirror wafer is used as a second test piece.

The irradiation conditions of the energy ray to the film for oil film formation when producing the second cured product (the cured second laminate) are particularly limited as long as the oil film-forming film is sufficiently energy ray cured. I will not.
In general, the illuminance and the light amount of the energy ray at the time of preparation of the second cured product can be the same as the illuminance and the light amount of the energy ray at the time of curing of the first laminate 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 pieces are allowed to stand for 30 minutes in an environment of temperature 23 ° C. and relative humidity 50% for aging. Then, in the second test piece after this aging, the adhesion after aging between the second cured product and the silicon mirror wafer under an environment of 23 ° C. (herein referred to as “adhesion before immersion”) There is also a measure) _PA1 . At this time, the second test piece after fabricated, while not shown a clear characteristic change, it is preferable to measure the time after adhesion P _A1. By doing this, it is possible to obtain the rate of change in adhesive force described later with higher accuracy.

On the other hand, when measuring the adhesion after immersion, the second test piece after aging of the measuring object is immersed in pure water for 2 hours. At this time, in order to prevent the second test piece from being exposed out of the pure water (in other words, so that the entire second test piece is completely immersed in pure water), 2 Sink the test piece.

The temperature of pure water during immersion of the second test piece may be the same as the temperature of pure water during immersion of the first test piece described above. By doing this, it is possible to obtain the rate of change in adhesive force described later with higher accuracy.

After immersing in pure water for 2 hours, the second test piece is promptly 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) and, in the second specimen after the immersion, in an environment of 23 ° C., to measure the dip after adhesion P _B1 between the second cured silicon mirror wafer. At this time, the second test piece after immersion in a state do not show a definite change in characteristics, it is preferable to measure the dip after adhesion P _B1. By doing this, it is possible to obtain the rate of change in adhesive force described later with higher accuracy.

Then, using the values of these _{P A1} and _{P B1,} the formula by _{_{"(| | P B1 -P A1)}} / P A1 × 100 ", is calculated adhesion rate of change of the second specimen (%).

After aging adhesive force (before immersion adhesive strength) P _A1 and after immersion adhesion P _B1 is the same second specimen plurality prepared, may be measured separately in these second test pieces, one The same second test piece may be measured sequentially.
In one second specimen of the same, when successively measured with time after adhesion P _A1 and after immersion adhesion P _B1, for example, in one and the same second specimen, at different locations, with time after adhesion P _A1 and after immersion adhesion P _B1 may be measured separately.

In the present invention, any time after adhesive strength P _A1 and after immersion adhesion P _B1 is a peel force measured when performing the operation for peeling off the second cured silicon mirror wafer. During the measurement of time after the adhesive strength P _A1 and after immersion adhesion P _B1, for example, interfacial failure may have occurred between the second cured product and the silicon mirror wafer, agglomeration in a second cured product Destruction may have occurred.

When measured with time after adhesion P _A1, such that dihedral angle formed with the release surface of the produced when peeled off second cured product in the second specimen becomes 180 °, at a peel rate of 300 mm / min, pure At a stage before immersion in water, the second cured product is peeled off, so-called 180 ° peeling is performed. The peel strength at this time is (mN / 25 mm) was measured, this value may be a time after the adhesive strength _{P A1.}
For example, in the case where interface fracture occurs between the second cured product and the silicon mirror wafer, the above-mentioned "angle formed by the peeling surface of the two surfaces" means "to the silicon mirror wafer of the second cured product". And the attached surface of the silicon mirror wafer to the second cured product. If cohesive failure occurs in the second cured product, the above-mentioned "angle formed by the peeling surface of the two surfaces" is "angle formed by the cohesive failure surface of the second cured product".

At this time, the second cured product may be peeled off using a strong adhesive tape. That is, when measured with time after adhesion P _A1, the measurement object, the second cured before immersion in pure water, keep sticking a strong adhesive tape. Then, by setting the object to which the peeling force is directly applied as the strong adhesive tape, the peeling speed is 300 mm / min so that the angle formed by the peeling surface is 180 °, at a stage before immersion in pure water In the second test piece, the 180 ° peel is performed to peel off the laminate of the second cured product and the strong adhesive tape. The peel strength at this time is (mN / 25 mm) was measured, it is also possible to this value with time after adhesion _{P A1.}

When the strong adhesive tape is used, the strong adhesive tape is attached to the resin film-forming film before curing the resin film-forming film, and then the resin film-forming film is cured to obtain a second cured product. Alternatively, without attaching the strong adhesive tape to the resin film-forming film, 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

After immersion adhesive strength P _B1 can also be measured in the case of time after adhesion P _A1 and the same method.
That is, when measuring after immersion adhesive strength P _B1, after immersion for 2 hours in pure water a second test piece after the above aging, two surfaces occurs when the second cured product was peeled off in the second test piece The second cured product is peeled at a peeling speed of 300 mm / min, so-called 180 ° peeling is performed so that the angle formed by the peeling surface is 180 °. And the peeling force (mN / 25 mm) at this time can be measured, and this value can be made into post-immersion adhesive power _PB1 .
Here, the "angle formed peeling two face" is similar to the case of the measurement of time after the adhesive strength P _A1 above.

Further, when measuring after immersion adhesive strength P _B1 may use a strong adhesive tape. That is, the measurement target after immersion adhesive strength P _B1, the second cured before immersion in pure water, keep sticking a strong adhesive tape. Then, the second test piece to which the strong adhesive tape is attached is immersed in pure water for 2 hours, and then the object to which the peeling force is directly applied is the strong adhesive tape, and the angle of the peeling surface is 180 ° In the second test piece, the 180 ° peeling is performed to peel off the laminate of the second cured product and the strong pressure-sensitive adhesive tape at a peeling speed of 300 mm / min. And the peeling force (mN / 25 mm) at this time can be measured, and this value can be made into post-immersion adhesive power _PB1 .

Even when measuring after immersion adhesive strength P _B1, after aging adhesive strength in the same manner as in the measurement of (before immersion adhesive strength) P _A1, prior to curing of the resin film for forming a film, for the resin film forming the strong adhesive tape The film for resin film formation may be cured to be a second cured product by sticking to a film, and then the film for resin film formation may be cured without sticking the strong adhesive tape to the film for resin film formation. The second adhesive may be a second cured product, and the strong adhesive tape may be attached to the second cured product.

That the size of the strong adhesive tape is measured with time after adhesion P _A1 and after immersion adhesive strength P _B1 (in other words, is peeled from the silicon mirror wafer) and the magnitude of the second cured product are the same Is preferred.

When using the said strong adhesive tape smaller than the size of the film for resin film formation used for preparation of the 2nd laminated body, in the 2nd laminated body, the film for resin film formation along the outer periphery of the said strong adhesive tape cut after forming, it is preferred to measure the time after adhesion P _A1 and after immersion adhesion P _B1. By doing so, the adhesive power _PA1 can be more easily measured after the passage of time. Further, when measuring after immersion adhesive strength P _B1, not only after immersion adhesive strength P _B1 it can be more easily measured, 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 film for resin film formation is non-energy ray curable If the film for resin film formation is non-energy ray curable, the second laminate is used as it is as a second test piece (in other words, a silicon mirror The same method as in the case where the above-mentioned resin film-forming film is energy ray curable except that the target of measurement of the adhesive force with the wafer is not the second cured product but the film for resin film formation). 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 strength change rate of the second test piece, first, the second test piece is subjected to an environment at a temperature of 23.degree. C. and a relative humidity of 50%. Let stand for 30 minutes and let it age. Then, in a second test piece after the aging under 23 ° C. environment after aging adhesion between the resin film for forming a film and the silicon mirror wafer (before immersion adhesive strength) is measured P _A2. At this time, the second test piece after fabricated, while not shown a clear characteristic change, it is preferable to measure the time after adhesion P _A2. By doing this, it is possible to obtain the rate of change in adhesive force described later with higher accuracy.

On the other hand, when measuring the adhesion after immersion, the second test piece after aging of the measuring object is immersed in pure water for 2 hours. The immersion of the second test piece in the pure water at this time can be performed in the same manner as in the case where the above-mentioned oil film-forming film is energy ray curable.

After immersing in pure water for 2 hours, the second test piece is promptly 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) and, in the second specimen after the immersion, under 23 ° C. environment to measure the dip after adhesion P _B2 between the resin film for forming a film and the silicon mirror wafer. At this time, the second test piece after immersion in a state do not show a definite change in characteristics, it is preferable to measure the dip after adhesion P _B2. By doing this, it is possible to obtain the rate of change in adhesive force described later with higher accuracy.

Then, using the values of these _{P A2} and _{P B2,} wherein the _{_{"(| | P B2 -P A2)}} / P A2 × 100 ", is calculated adhesion rate of change of the second specimen (%).

After aging adhesive force (before immersion adhesive strength) P _A2 and after immersion adhesion P _B2 is the same second specimen plurality prepared, may be measured separately in these second test pieces, one The same second test piece may be measured sequentially.
In one and the same second specimen, if sequential measuring the time after adhesion P _A2 and after immersion adhesion P _B2, for example, in one and the same second specimen, at different locations, After aging, the adhesive power _PA2 and the post-immersion adhesive power _PB2 may be separately measured.

In the present invention, any time after adhesive strength P _A2 and after immersion adhesion P _B2 is the peel force is measured when performing the operation of peeling from the silicon mirror wafer pulling a resin film for forming a film. During the measurement of time after the adhesive strength P _A2 and after immersion adhesion P _B2, for example, interfacial failure may also be caused between the resin film for forming a film and the silicon mirror wafer, a resin film for forming a film of Cohesive failure may occur.

After the measurement of adhesive strength P _A2 over time, so that angle formed the release surface of the two surfaces occurs when peeled resin film forming film in the second test piece is 180 °, at a peel rate of 300 mm / min, At a stage before immersion in pure water, the film for resin film formation is peeled off, so-called 180 ° peeling is performed. The peel strength at this time is (mN / 25 mm) was measured, this value may be a time after the adhesive strength _{P A2.}
For example, in the case where interfacial failure occurs between the resin film-forming film and the silicon mirror wafer, the above-mentioned "angle between two peeling surfaces" means "silicon mirror of resin film-forming film". This is the angle between the bonding surface to the wafer and the bonding surface of the silicon mirror wafer to the resin film-forming film. If cohesive failure occurs in the film for resin film formation, the above-mentioned "angle between two peeling surfaces" means "angle between two cohesive failure surfaces of the film for resin film". is there.

At this time, the resin film-forming film may be peeled off using a strong adhesive tape. That is, when measured with time after adhesion P _A2, the measurement object, the resin film for forming a film before immersion in pure water, keep sticking a strong adhesive tape. Then, by setting the object to which the peeling force is directly applied as the strong adhesive tape, the peeling speed is 300 mm / min so that the angle formed by the peeling surface is 180 °, at a stage before immersion in pure water In the second test piece, the laminate of the film for resin film formation and the strong pressure-sensitive adhesive tape is peeled off at 180 °. The peel strength at this time is (mN / 25 mm) was measured, it is also possible to this value with time after adhesion _{P A2.}

The post-dipping adhesive power _PB2 can also be measured after aging in the same manner as in the case of the adhesive power _PA2 .
That is, when measuring after immersion adhesive strength P _B2 is generated when the second test piece after the above aging was immersed for 2 hours in pure water, the peel the resin film for forming a film in the second test piece 2 The film for resin film formation is peeled off at a peeling speed of 300 mm / min so that the angle formed by the peeling surface of the surface is 180 °, so-called 180 ° peeling is performed. And the peeling force (mN / 25 mm) at this time can be measured, and this value can be made into post-dipping adhesive power _PB2 .
Here, the "angle formed peeling two face" is similar to the case of the measurement of time after the adhesive strength P _A2 above.

Further, when measuring after immersion adhesive strength P _B2 may use a strong adhesive tape. That is, the measurement target after immersion adhesive strength P _B2, before immersion in pure water with respect to the resin film for forming a film in advance by attaching a strong adhesive tape. Then, the second test piece to which the strong adhesive tape is attached is immersed 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 the second test piece, the laminate of the film for resin film formation and the strong pressure-sensitive adhesive tape is peeled off at 180 ° at a peeling speed of 300 mm / min. The peel strength at this time is (mN / 25 mm) was measured, it is also possible to this value after immersion adhesive strength _{P B2.}

The size of the strong adhesive tape is measured with time after adhesion P _A2 and after immersion adhesive strength P _B2 (in other words, is peeled from the silicon mirror wafer) and the size of the resin film for forming a film are the same Is preferred.

When using the said strong adhesive tape smaller than the size of the film for resin film formation used for preparation of the 2nd laminated body, in the 2nd laminated body (2nd test piece), along the outer periphery of the said strong adhesive tape , after forming a notch for the resin film forming a film, it is preferable to measure the time after adhesion P _A2 and after immersion adhesion P _B2. By doing so, the adhesive power _PA2 can be more easily measured after the passage of time. 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 adhesive strength change rate 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 picking up a semiconductor chip with a film for forming a resin film or a semiconductor chip with a resin film having a small size from the support sheet by the adhesive force change rate of the second test piece being equal to or less than the upper limit value, the resin to the support sheet The effect of suppressing the remaining of the film for film formation or the resin film is further enhanced.

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

In the present invention, the adhesive force change rate of the second test piece can be appropriately adjusted so as to be a numerical range determined by arbitrarily combining any of the lower limit values described above and any upper limit value. . For example, the adhesive strength change rate of the second test piece is preferably 0 to 60%, more preferably 0 to 50%, still more preferably 0 to 45%, and 0 to 40%. Being particularly preferred. However, these are examples of the adhesive force change rate of a 2nd test piece.

<<Young's modulus of the third test piece after immersion >>
The film for resin film formation is a tensile test based on JIS K 7127 when the third test piece is immersed in pure water for 2 hours, and the third film after immersion is measured at a test speed of 200 mm / min. That whose Young's modulus of a test piece becomes 15 or more MPa is preferred.

When the resin film-forming film is non-energy ray curable, the third test piece is a laminate of a plurality of resin film-forming films in the thickness direction, and the size is 15 mm × 150 mm, It is a third laminate with 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 an energy beam and energy ray curing the third laminate. .
When the resin film-forming film is a thermosetting resin, the third laminate and the third cured product are the same regardless of whether the resin film-forming film is energy ray curable or non-energy ray curable. It is preferable that none of them is thermally cured.

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

The plurality of resin film-forming films used for producing the third laminate all have the same composition.
The thicknesses of the plurality of resin film-forming films may be all the same, all may be different, or only some may be the same, but preferably all are the same.

In the third laminate, for example, a plurality of resin film-forming films of any size larger than 15 mm × 150 mm are laminated and bonded such that the total thickness is 200 μm, and the size of 15 mm × 150 mm It can be produced by punching out (cutting). In the third laminate, for example, a plurality of resin film-forming films each having a size of 15 mm × 150 mm are laminated with their peripheral edge portions aligned so that the total thickness is 200 μm. It can also be produced by pasting together.

When the film for resin film formation is non-energy ray curable, the produced 3rd laminated body is used as a 3rd test piece as it is.
If the resin film-forming film is energy ray curable, the prepared third laminate is further irradiated with energy rays to cure all resin film-forming films in the third laminate. The resulting third cured product is used as a third test piece.

The irradiation conditions of the energy beam to the third laminate (film for forming a fat film) when producing the third cured product are not particularly limited as long as the third laminate is sufficiently energy beam cured.
In general, the illuminance and the light amount of the energy ray at the time of preparation of the third cured product may be the same as the illuminance and the light amount of the energy ray at the time of curing of the first laminate.

When picking up a small semiconductor chip with a film for resin film formation or a semiconductor chip with a resin film from the support sheet, the effect of suppressing the film or resin film for resin film formation on the support sheet is enhanced. The Young's modulus of the third test piece after 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 film for resin film formation in which the Young's modulus is equal to or less than the upper limit is easier to manufacture.

In the present invention, the Young's modulus of the third test piece after immersion is appropriately selected so that it is determined by arbitrarily combining any of the lower limit values described above and any upper limit value. It 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 immersion in pure water measured at a test speed of 200 mm / min in a tensile test in accordance with JIS K 7127 is 20 to 200 MPa. The pressure is preferably 30 to 190 MPa, more 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 a film for forming a resin film or the 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.

<< Elongation at break of third test piece after immersion >>
The film for resin film formation is a tensile test based on JIS K 7127 when the third test piece is immersed in pure water for 2 hours, and the third film after immersion is measured at a test speed of 200 mm / min. The elongation at break of the test piece is preferably 15 to 410%, and 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 a film for forming a resin film or the 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.
The breaking elongation of the third test piece is determined from the elongation of the third test piece when the third test piece breaks when measuring the Young's modulus of the third test piece described above. This is the same both before and after immersing the third test piece in pure water.

In this specification, “the elongation at break is X%” (X is a positive number) means that the test piece is pulled, and the test piece has its original length in the tensile direction (in other words, it is pulled Test when extended by X% of the length when not being taken, that is, when the overall length in the tensile direction of the test piece becomes [1 + X / 100] times the length before pulling 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 at a test speed of 200 mm / min in a tensile test based on JIS K 7127, is 20 to 550%. Is preferable, and 25 to 500% is more preferable. By setting the breaking elongation of the third test piece before immersion to such a range, when picking up a semiconductor chip with a film for forming a resin film or a semiconductor chip with a resin film having a small size from the support sheet, The effect of suppressing the remaining of the resin film-forming film or the resin film is further enhanced.

<< Stress at break of the third test piece after immersion >>
The film for resin film formation is a tensile test based on JIS K 7127 when the third test piece is immersed in pure water for 2 hours, and the third film after immersion is measured at a test speed of 200 mm / min. The breaking stress of the test piece is preferably 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 falls within such a range, when picking up a semiconductor chip with a film for forming a resin film or a semiconductor chip with a resin film having a small size from the support sheet, The effect of suppressing the remaining of the resin film-forming film or the resin film is further enhanced.
The breaking stress of the third test piece is determined from the force applied to the third test piece when the third test piece breaks when measuring the Young's modulus of the third test piece described above. This is the same both before and after immersing the third test piece in pure water.

<< Stress at break of the third specimen before immersion >>
In the present invention, the breaking stress of the third test piece before immersion in pure water measured at a test speed of 200 mm / min in a tensile test based on JIS K 7127 is 1.1 to 8 MPa. Is preferable, and 1.1 to 6.5 MPa is more preferable. When the breaking stress of the third test piece before immersion is within such a range, when picking up a semiconductor chip with a film for forming a resin film or a semiconductor chip with a resin film having a small size from the support sheet, The effect of suppressing the remaining of the resin film-forming film or the resin film is further enhanced.

○ Film for thermosetting resin film formation As a film for thermosetting resin film formation, a thing containing a polymer component (A) and a thermosetting component (B) is mentioned, for example, A polymer component (A) is mentioned. And the thermosetting component (B) and the filler (D) are more preferable. The polymer component (A) is a component that can be considered to be formed by the polymerization reaction of the polymerizable compound. The thermosetting component (B) is a component that can undergo curing (polymerization) reaction using heat as a reaction trigger. In the present invention, the polymerization reaction also includes a polycondensation reaction.

The film for thermosetting resin film formation may consist of one layer (single layer), or may consist of two or more layers. When the film for thermosetting resin film formation consists of multiple layers, these multiple layers may mutually be same or different.

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. By the thickness of the film for thermosetting resin film formation being more than the said lower limit, the uniformity of thickness becomes higher. Moreover, when the thickness of the film for thermosetting resin film formation is below the said upper limit, the generation amount of the cuttings of the film for resin film formation or resin film which generate | occur | produces at the time of blade dicing of a semiconductor wafer is suppressed.
Here, "the thickness of the film for thermosetting resin film formation" means the thickness of the whole film for thermosetting resin film formation, for example, the film for thermosetting resin film formation which consists of multiple layers. The thickness means the total thickness of all the 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 heat curing are not particularly limited as long as the cured product has a degree of cure sufficient to exhibit its function. It may be appropriately selected according to the type of the curable resin film-forming film.
For example, the heating temperature at the time of thermosetting of the film for thermosetting resin film formation is preferably 100 to 200 ° C., more preferably 110 to 180 ° C., and particularly preferably 120 to 170 ° C. . The heating time at the time of curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.

<< Composition for forming thermosetting resin film >>
The film for thermosetting resin film formation can be formed using the composition for thermosetting resin film formation containing the constituent material. For example, the composition for thermosetting resin film formation is applied to the formation target surface of the film for thermosetting resin film formation, and it is made to dry at the target site by making it dry if needed. It can form a film.

Coating of the composition for thermosetting resin film formation 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 include methods using various coaters such as a knife coater, a screen coater, a Mayer bar coater, and a kiss coater.

Although the drying conditions of the composition for thermosetting resin film formation are not specifically limited, When the composition for thermosetting resin film formation contains the solvent mentioned later, it is preferable to heat-dry. Then, the composition for forming a thermosetting resin film 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 thermosetting resin film formation so that the film for thermosetting resin film formation to be formed is not thermally cured.

<Composition for forming a thermosetting resin film (III-1)>
As a preferable composition for thermosetting resin film formation, for example, a composition for thermosetting resin film formation containing a polymer component (A), a thermosetting component (B) and a filler (D) (III- 1) (In the present specification, it may simply be abbreviated as “composition (III-1)”) and the like.

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

Examples of the polymer component (A) include acrylic resins, polyesters, urethane resins, acrylic urethane resins, silicone resins, rubber resins, phenoxy resins, thermosetting polyimides and the like, with acrylic resins being preferred. .

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 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the lower limit value, the shape stability (the temporal stability during storage) of the film for forming a thermosetting resin film is improved. In addition, when the weight average molecular weight of the acrylic resin is not more than the upper limit value, the film for thermosetting resin film formation easily follows the uneven surface of the adherend, and the adherend and the thermosetting resin film are formed. The generation of voids and the like between the film and the film is further suppressed.
In addition, in this specification, a weight average molecular weight is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method unless there is particular notice.

The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. When the Tg of the acrylic resin is not less than the lower limit value, for example, the adhesion 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. Moreover, the adhesive force with the to-be-adhered body of the film for thermosetting resin film formation and its hardened | cured material improves because Tg of acrylic resin is below the said upper limit.

The acrylic resin is selected, for example, from one or more polymers of (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide, etc. The copolymer etc. of 2 or more types of monomers are mentioned.

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

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (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 , (Meth) acrylic acid undecyl, (meth) acrylic acid dodecyl ((meth) acrylic acid Uryl), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester such as heptadecyl acrylate or octadecyl (meth) acrylate (stearyl (meth) acrylate) has a chain structure of 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxy alkyl esters such as (meth) acrylic acid dicyclopentenyl oxyethyl ester;
(Meth) acrylic imides;
Glycidyl group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth ) Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, "substituted amino group" means a group obtained 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-methylol acrylamide, etc. in addition to the (meth) acrylic acid ester. May be copolymerized.

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

The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound through a crosslinking agent (F) described later, or may be directly bonded to another compound without the crosslinking agent (F) . There is a tendency for the reliability of the package obtained using the composite sheet for resin film formation to improve because acrylic resin couple | bonds with the other compound by the said functional group.

In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) may be used alone without using an acrylic resin. It may be used in combination with an acrylic resin. By using the thermoplastic resin, the removability of the resin film from the support sheet can be improved, or the film for thermosetting resin film formation can easily follow the uneven surface of the adherend, and the adherend and the thermosetting resin The occurrence of voids and the like may be further suppressed between the resin film-forming film.

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

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

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

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

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all the components other than the solvent (that is, the formation of a thermosetting resin film in a film for thermosetting resin film formation) The proportion of the content of the polymer component (A) with respect to the total mass of the film for use is preferably 3 to 85% by mass, regardless of the type of the polymer component (A), and 3 to 80% by mass It is more preferable that, for example, it is 3 to 65% by mass, 3 to 50% by mass, 3 to 35% by mass, 3 to 20% by mass or the like.

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) And polymer component (A) and thermosetting component (B).

[Thermosetting component (B)]
A thermosetting component (B) is a component for hardening the film for thermosetting resin film formation.
The thermosetting component (B) contained in the composition (III-1) and the thermosetting resin film-forming film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.

As a thermosetting component (B), an epoxy-type thermosetting resin, a thermosetting polyimide, polyurethane, unsaturated polyester, a silicone resin etc. are mentioned, for example, An epoxy-type thermosetting resin is preferable.

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

・ Epoxy resin (B1)
As an epoxy resin (B1), a well-known thing is mentioned, For example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, an ortho cresol novolak epoxy resin, a dicyclopentadiene type epoxy resin, The bifunctional or more epoxy compound such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. may be mentioned.

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

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

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30000 from the viewpoint of the curability of the film for thermosetting resin film formation and the strength and heat resistance of the resin film after curing. Preferably, it is 300 to 10,000, and more preferably 300 to 3,000.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 150 to 950 g / eq.

An epoxy resin (B1) may be used individually by 1 type, and 2 or more types may be used together, and when using 2 or more types together, the combination and ratio of those can be selected arbitrarily.

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

Among the heat curing agents (B2), as a phenol type curing agent having a phenolic hydroxyl group, for example, polyfunctional phenol resin, biphenol, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin and the like can be mentioned. .
Among the thermosetting agents (B2), examples of amine-based curing agents 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 hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group, an aromatic ring of a phenol resin, The compound etc. which a group which has a saturated hydrocarbon group directly couple | bonds are mentioned.
The said unsaturated hydrocarbon group in a thermosetting agent (B2) is a thing similar to the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.

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

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

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

In the composition (III-1) and the thermosetting resin film-forming 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). Part is preferable, and 1 to 200 parts by mass is more preferable, for example, 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, and 1 to 10 parts by mass etc. It may be. When the content of the thermosetting agent (B2) is equal to or more than the lower limit value, curing of the film for thermosetting resin film formation is more easily progressed. Moreover, the moisture absorption of the film for thermosetting resin film formation was reduced by the said content of a thermosetting agent (B2) being below the said upper limit, and it was obtained using the composite sheet for resin film formation. Package reliability is further improved.

In the composition (III-1) and the film for thermosetting resin film formation, 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 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, 300 to 600, based on 100 parts by mass of the polymer component (A). It may be any one of parts by mass, 400 to 600 parts by mass, 500 to 600 parts by mass, and the like. 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 releasability of the support sheet is improved. Do.

[Filler (D)]
By containing the filler (D), the film for thermosetting resin film formation can be more easily adjusted to the target range of the water absorption coefficient and the adhesive force change ratio. Moreover, the film for thermosetting resin film formation and its hardened | cured material (resin film) contain a filler (D), and adjustment of a thermal expansion coefficient becomes easier. Then, the thermal expansion coefficient is optimized with respect to a thermosetting resin film-forming film or an object to be formed with a resin film, whereby a semiconductor chip with a resin film obtained using the resin film-forming composite sheet Reliability is further improved. Moreover, the film for thermosetting resin film formation can also reduce the moisture absorption rate of a resin film, or can improve heat dissipation by containing a 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, bengala, silicon carbide, boron nitride, etc .; spherical beads of these inorganic fillers; surface modification of these inorganic fillers Articles: 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 film for thermosetting resin film formation may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.

In the composition (III-1), the ratio of the content of the filler (D) to the total content of all the components other than the solvent (that is, for forming a thermosetting resin film in a film for forming a thermosetting resin film) The ratio of the content of the filler (D) 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) hardly absorbs water significantly more than the other components, when the ratio is at least the lower limit value, it is easier to make the water absorption coefficient 0.55% or less. And when picking up a semiconductor chip with a resin film with a small size from a support sheet, the effect which controls residual of a resin film on a support sheet becomes high. Moreover, the intensity | strength of the film for resin film formation and the resin film which is its hardened | cured material improves more because the said ratio is below the said upper limit.

[Hardening 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 and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are not hydrogen atoms Imidazoles substituted with the following groups: organic phosphines such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine (phosphines in which one or more hydrogen atoms are substituted with an organic group); tetraphenyl phosphonium tetraphenyl borate Tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.

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

When the curing accelerator (C) is used, the content of the curing accelerator (C) in the composition (III-1) and the film for thermosetting resin film formation is the content of the thermosetting component (B) 100 The amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass with respect to the mass parts. The effect by using a hardening accelerator (C) is acquired more notably by the said content of a hardening accelerator (C) being more than the said lower limit. In addition, when the content of the curing accelerator (C) is equal to or less than the upper limit value, for example, the high-polarity curing accelerator (C) is contained in the film for thermosetting resin film formation under high temperature and high humidity conditions. In the above, the effect of suppressing migration and segregation to the adhesive interface side with the adherend becomes high. As a result, the reliability of the resin film-coated semiconductor chip obtained using the resin film-forming composite sheet 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 compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), it is possible to improve the adhesiveness and adhesion of the film for thermosetting resin film formation to an adherend it can. Moreover, water resistance improves the hardened | cured material (resin film) of the film for thermosetting resin film formation by using a coupling agent (E), without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group possessed by the polymer component (A), the thermosetting component (B) or the like, and is preferably a silane coupling agent. More preferable.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. Be

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

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for thermosetting resin film formation is the polymer component (A) and the thermosetting component The amount is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content of (B). Is particularly preferred. 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 adhesion of the film for thermosetting resin film formation to the adherend The effect by using a coupling agent (E), such as the improvement of the property, is more significantly obtained. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]
As the polymer component (A), those having 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 capable of binding to other compounds such as the above-mentioned acrylic resin When used, the composition (III-1) and the thermosetting resin film-forming film may contain a crosslinking agent (F). A crosslinking agent (F) is a component for making the said functional group in a polymer component (A) couple | bond with another compound, and bridge | crosslinking it, The film for thermosetting resin film formation is made by bridge | crosslinking in this way The initial adhesion and cohesion of can be adjusted.

As the crosslinking agent (F), for example, organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate type crosslinking agents (crosslinking agents having a metal chelate structure), aziridine type crosslinking agents (crosslinking agents having an aziridinyl group), etc. Can be 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 in some cases); trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Etc. The “adduct” includes the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and low contents such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil It means a reaction product with a molecule active hydrogen-containing compound. Examples of the adduct include xylylene diisocyanate adduct of trimethylolpropane as described later, and the like. In addition, the "terminal isocyanate urethane prepolymer" is as described above.

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

Examples of the organic polyhydric imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. -Tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridine carboxamide) triethylene melamine and the like.

When using an organic polyhydric isocyanate compound as a crosslinking agent (F), it is preferable to use a hydroxyl-containing polymer as a polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a film for thermosetting resin film formation can be obtained by the reaction of the crosslinking agent (F) with the polymer component (A). A crosslinked structure can be introduced easily.

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

When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (III-1) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer component (A). It is preferably part, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. The effect by using a crosslinking agent (F) is acquired more notably by the said content of a crosslinking agent (F) being more than the said lower limit. Moreover, the excess use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.

[Energy ray curable resin (G)]
The composition (III-1) and the thermosetting resin film-forming film may contain an energy ray curable resin (G). The film for thermosetting resin film formation can change a characteristic by irradiation of an energy ray by containing energy-beam curable resin (G).

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

Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxy penta ( Linear aliphatic skeleton-containing (meth) acrylates such as meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cycloaliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.

The 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, the combination and ratio thereof can be arbitrarily selected.

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

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

[Photoinitiator (H)]
When the composition (III-1) and the thermosetting resin film-forming film contain an energy ray-curable resin (G), light is efficiently transferred to efficiently promote the polymerization reaction of the energy ray-curable resin (G). You may contain the polymerization initiator (H).

As the photopolymerization initiator (H) in the composition (III-1), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal Benzoin compounds such as acetophenone; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,2, Acyl phosphine oxide compounds such as 4,6-trimethyl benzoyl) phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; benzyl phenyl sulfide, tetramethyl thiuram Sulfide compounds such as nosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Diketone compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone etc. Can be mentioned.
Further, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; and 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 type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.

When a photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is 100 parts by mass of the content of the energy ray-curable resin (G), The amount 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, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrilium dyes, and phthalocyanines. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, dioxazine dyes, naphthol dyes, azomethine dyes color , Benzimidazolone pigments, pyranthrone pigments and threne pigments, and the like.

Examples of the inorganic pigment include carbon black, cobalt dyes, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes and the like can be mentioned.

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

When the coloring agent (I) is used, the content of the coloring agent (I) in the film for thermosetting resin film formation may be appropriately adjusted depending on the purpose. For example, print visibility in the case of performing laser printing on a resin film by adjusting the content of the colorant (I) of the film for thermosetting resin film formation and adjusting the light transmittance of the resin film Can be adjusted. Further, by adjusting the content of the colorant (I) of the film for thermosetting resin film formation, it is possible to improve the design of the resin film or to make it difficult to see grinding marks on the back surface of the semiconductor wafer. Taking this point into consideration, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all the components other than the solvent (that is, in the film for thermosetting resin film formation) 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 mass%, and 0.1 to 7.5 mass%. Is more preferably 0.1 to 5% by mass. The effect by using coloring agent (I) is acquired more notably by the ratio of the above-mentioned content of coloring agent (I) being more than the above-mentioned lower limit. Moreover, the excessive fall of the light transmittance of the film for thermosetting resin film formation is suppressed because the ratio of the said content of coloring agent (I) is below the said upper limit.

[General purpose additive (J)]
The composition (III-1) and the thermosetting resin film-forming film may contain a general-purpose additive (J) within the range not impairing the effects of the present invention.
The general-purpose additive (J) may be a known one, can be optionally selected according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, etc. Can be mentioned.

The general-purpose additive (J) contained in the composition (III-1) and the thermosetting resin film-forming film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
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), 1-butanol and the like Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methyl pyrrolidone.
The solvent contained in the composition (III-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The solvent contained in the 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, for example, according to the types of components other than the solvent.

Preferred examples of the composition (III-1) include, for example, a polymer component (A), a thermosetting component (B) and a filler (D), and the content of each of these components is not particularly limited. Those included in any of the preferred numerical ranges described in the above are included.
As one embodiment of such a preferred 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 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 ratio of the content of the filler (D) to the total content of all the components other than the solvent is 25 to 75% by mass.
Moreover, as one embodiment of such a preferred 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 the components other than the solvent The proportion of the amount 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 the components other than the solvent is 28 to 72% by mass.

More preferable examples of composition (III-1) include polymer component (A), thermosetting component (B), curing accelerator (C), filler (D), coupling agent (E) , Crosslinker (F), energy ray curable resin (G) and photopolymerization initiator (H), and the contents of these components are all included in any of the preferable numerical ranges described above The thing is mentioned.
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) relative to the total content of all the components other than the solvent 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 the 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 is 0.01 to 10 parts by mass with respect to 100 parts by mass of (B), and the content of the coupling agent (E) is the polymer component (A) and the thermosetting component (B) 0.03 to 20 parts by mass with respect to 100 parts by mass of the total content of Is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (A), and the content of the photopolymerization initiator (H) is an energy ray-curable resin The content of the energy ray-curable resin (G) is 2 to 5 parts by mass with respect to 100 parts by mass of (G), and the total mass of the composition (III-1) is What is 1-10 mass% is mentioned.

<< Method of producing composition for thermosetting resin film formation >>
The composition for forming a thermosetting resin film such as the composition (III-1) can be obtained by blending the components for constituting the composition.
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

○ Film for forming energy beam curable resin film The film for forming energy beam curable resin film includes those containing energy beam curable component (a), and energy beam curable component (a) and filler What contains is preferable.
In the film for energy beam curable resin film formation, the energy beam curable component (a) is preferably uncured, preferably has tackiness, and is more preferably uncured and tacky. Here, "energy ray" and "energy ray curability" are as described above.

The film for energy beam curable resin film formation may be only one layer (single layer), or two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from one another. The combination of these multiple layers is not particularly limited.

The thickness of the film for forming an energy ray-curable resin film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. The uniformity of thickness becomes higher by the thickness of the film for energy-beam curable resin film formation being more than the said lower limit. In addition, when the thickness of the energy ray-curable resin film-forming film is equal to or less than the upper limit value, the amount of generation of cuttings of the oil film-forming film or resin film generated during blade dicing of the semiconductor wafer is suppressed. .
Here, "the thickness of the film for forming an energy ray curable resin film" means the thickness of the whole film for forming an energy ray curable resin film, and for example, an energy ray ray curable resin film formed of a plurality of layers is formed The thickness of the film means the total thickness of all the layers constituting the energy ray-curable resin film-forming film.

After the film for energy beam curable resin film formation is applied 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 curing degree sufficient to exhibit its function It may be appropriately selected according to the type of the film for forming a linear curable resin film.
For example, the illuminance of the energy ray is preferably 120 to 280 mW / cm ² at the time of curing of the film for forming an energy ray curable resin film. The light quantity of the energy ray at the time of curing is preferably 100 to 1000 mJ / cm ² .

<< Composition for forming energy ray curable resin film >>
The film for energy beam curable resin film formation can be formed using the composition for energy beam curable resin film formation containing the constituent material. For example, the composition for forming an energy ray-curable resin film is coated on the surface to be formed of the film for forming an energy ray-curable resin film, and dried as needed to form an energy ray-curable resin at a target site. A film for film formation can be formed.

The application of the composition for forming an energy ray-curable resin film can be performed, for example, by the same method as the application of the composition for forming a thermosetting resin film described above.

The drying conditions of the composition for forming an energy ray-curable resin film are not particularly limited, but when the composition for forming an energy ray-curable resin film contains a solvent to be described later, it is preferable to heat and dry. Then, the composition for forming an energy ray-curable resin film 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 film for forming an energy ray-curable resin film is not cured.

<Composition for forming an energy ray-curable resin film (IV-1)>
Preferred examples of the composition for forming an energy ray-curable resin film include, for example, a composition for forming an energy ray-curable resin film (IV-1) containing the energy ray-curable component (a) and a filler. And the like, which may be simply referred to as “composition (IV-1)”.

[Energy ray curable component (a)]
The energy ray curable component (a) is a component that cures upon irradiation with energy rays, and imparts film forming ability, flexibility, etc. to the energy ray curable resin film-forming film, and also a hard resin after curing. It is also a component for forming a film.
The energy ray curable component (a) includes, for example, an energy ray curable group, a polymer (a1) having a weight average molecular weight of 80000 to 2,000,000, and an energy ray curable group having a molecular weight of 100 to 80,000. Compound (a2) is mentioned. The polymer (a1) may be at least partially crosslinked by a crosslinking agent, or may be non-crosslinked.

(A polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray curable group and having 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 possessed by another compound, Acrylic resin (a1-1) formed by reaction of an energy ray curable compound (a12) having a group reactive with a functional group and an energy ray curable group such as an energy ray curable double bond .

Examples of the functional group capable of reacting with a group possessed by another compound include, for example, a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom Groups), epoxy groups and the like. However, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxy group.
Among these, the functional group is preferably a hydroxyl group.

. Acrylic polymers having functional groups (a11)
Examples of the acrylic polymer (a11) having a functional group include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to the monomers, monomers (non-acrylic monomers) other than acrylic monomers may be copolymerized.
Moreover, a random copolymer may be sufficient as the said acryl-type polymer (a11), a block copolymer may be sufficient, and it can employ | adopt a well-known method also about the superposition | polymerization method.

As an acryl-type monomer which has the said functional group, a hydroxyl-containing monomer, a carboxy-group containing monomer, an amino-group containing monomer, a substituted amino-group containing monomer, an epoxy-group containing monomer etc. are mentioned, for example.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non (meth) acrylics such as vinyl alcohol and allyl alcohol A saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl frame) etc. are mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citraconic Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like Be

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

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate and n (meth) acrylate -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate ( 2-ethylhexyl 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), ( Ta) tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples include alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester such as octadecyl (meth) acrylate (stearyl (meth) acrylate) is a chain structure having 1 to 18 carbon atoms.

Further, as the acrylic monomer having no functional group, for example, alkoxymethyl such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate and the like (Meth) acrylic acid esters having an aromatic group, including alkyl group-containing (meth) acrylic acid esters; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate etc .; non-crosslinkable (meth) acrylamides and Derivatives thereof; (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate .

The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.

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

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 same is 0.1 to 50 mass % Is preferable, 1 to 40% by mass is more preferable, and 3 to 30% by mass is particularly preferable. When the ratio is in such a range, in the acrylic resin (a1-1) obtained by the copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12), energy The content of the linear curable group can be easily adjusted to the preferable range of the degree of curing of the resin film.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of the components other than the solvent (that is, the total of the films in the energy beam 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 preferred.

・ Energy ray curable compound (a12)
The energy ray curable compound (a12) is one or two 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 possessed by the acrylic polymer (a11) What has the above is preferable, and what has an isocyanate group as said group is more preferable. When the energy beam 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, and more preferably 1 to 3 of the energy ray curable groups in one molecule.

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;
Acryloyl monoisocyanate compounds obtained by the reaction of diisocyanate compounds or polyisocyanate compounds with hydroxyethyl (meth) acrylate;
The acryloyl monoisocyanate compound etc. which are obtained by reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate are mentioned.
Among these, the energy ray curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy beam curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.

In the acrylic resin (a1-1), the content of the energy ray curable group derived from the energy ray curable compound (a12) relative to the content of the functional group derived from the acrylic polymer (a11) The proportion of is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. The adhesive force of the resin film after hardening becomes larger by the ratio of the said content being such a range. When the energy ray-curable compound (a12) is a monofunctional compound (having one of the above groups 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 of the 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 1,500,000.
Here, the "weight average molecular weight" is as described above.

In the case where the polymer (a1) is at least a part of which is crosslinked by a crosslinking agent, the polymer (a1) described above as constituting the acrylic polymer (a11) The monomer which does not correspond to any of the monomers and which has a group reactive with the crosslinking agent may be polymerized to be crosslinked in the group reactive with the crosslinking agent, or the energy ray curable compound ( The group derived from a12), which is reactive with the functional group, may be crosslinked.

The polymer (a1) contained in the composition (IV-1) and the energy beam curable resin film-forming film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.

(Compound (a2) having a molecular weight of 100 to 80,000, having an energy ray-curable group)
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 a group containing an energy ray-curable double bond, and preferred examples thereof Acryloyl group, a vinyl group etc. are mentioned.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, but 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 A phenol resin etc. are mentioned.

As a low molecular weight compound which has an energy ray curable group among the said compounds (a2), a polyfunctional monomer, an oligomer, etc. are mentioned, for example, The acrylate type compound which has 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) acrylic 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 ) 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) acrylate Dioxyfunctionals such as (oxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane and the like Meth) acrylate;
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 ( Multifunctional (meth) acrylates such as meta) acrylates;
Polyfunctional (meth) acrylate oligomers, such as a urethane (meth) acrylate oligomer, etc. are mentioned.

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

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

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

[Polymer having no energy ray curable group (b)]
When the composition (IV-1) and the energy beam curable resin film-forming film contain the compound (a2) as the energy beam curable component (a), a polymer further having no energy beam curable group It is preferable to also contain (b).
The polymer (b) may be at least partially crosslinked by a crosslinking agent, or may be non-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 sometimes abbreviated as “acrylic polymer (b-1)”).

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

Examples of the acrylic monomer constituting 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 hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters. Here, the "substituted amino group" is as described above.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) acrylate ) 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), ( Ta) tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples include alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester such as octadecyl (meth) acrylate (stearyl (meth) acrylate) is a chain structure having 1 to 18 carbon atoms.

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;
(Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyl oxyethyl ester and the like.

As said glycidyl group containing (meth) acrylic acid ester, glycidyl (meth) acrylate etc. are mentioned, for example.
Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy (meth) acrylate Propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like can be mentioned.
Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate and the like.

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

As the polymer (b) having no energy ray-curable group at least partially crosslinked by a crosslinking agent, for example, one having a reactive functional group in the polymer (b) reacted with the crosslinking agent It can be mentioned.
The reactive functional group may be appropriately selected depending on the type of the crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group and an amino group. Among these, a hydroxyl group having high reactivity with the 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 the like, and among these, a carboxy group having high reactivity with an epoxy group is preferable. . However, it is preferable that the reactive functional group is a group other than a carboxy group in terms of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip.

As a polymer (b) which does not have an energy ray curable group which has the said reactive functional group, the thing obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as the monomer constituting the polymer It may be used. As said polymer (b) which has a hydroxyl group as a reactive functional group, what was obtained by polymerizing a hydroxyl-containing (meth) acrylic acid ester is mentioned, for example, In addition to this, the said acrylics mentioned above What is obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted by the reactive functional group among the system monomer or the non-acrylic monomer is mentioned.

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 constituent units constituting the polymer is 1 to 20 It is preferably mass%, more preferably 2 to 10 mass%. When the ratio is in such a range, in the polymer (b), the degree of crosslinking 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) is further improved. More preferably, it is 100000 to 1.500000. Here, the "weight average molecular weight" is as described above.

The polymer (b) having no energy ray curable group contained in the composition (IV-1) and the film for forming an energy ray curable resin film may be only one type, or two or more types, and 2 When it is species or more, their combination and ratio can be arbitrarily selected.

As the composition (IV-1), those containing one or both of the polymer (a1) and the compound (a2) can be mentioned. And when it contains the said compound (a2), it is preferable that a composition (IV-1) also contains the polymer (b) which does not have an energy ray curable group, and, in this case, it further contains the said (a1) It is also preferable to contain 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, the composition (IV-1) contains the polymer The content of the compound (a2) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray curable group. And 30 to 350 parts by mass are more preferable.

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 (ie, A 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 in the energy ray curable resin film-forming film And 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 such a range, the energy ray curability of the film for forming an energy ray curable resin film becomes better.

[Filling material]
The film for energy beam curable resin film formation containing a filler exhibits the same effect as the film for thermosetting resin film formation containing a filler (D).

As the filler contained in the composition (IV-1) and the film for energy beam curable resin film formation, the filler (D) contained in the composition (III-1) and the film for thermosetting resin film formation and The same thing is 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 two or more types, and in the case of two or more types, the combination and ratio thereof are It can be selected arbitrarily.

In the composition (IV-1), the ratio of the content of the filler to the total content of all the components other than the solvent (that is, the filler relative to the total mass of the film in the energy beam curable resin film-forming film) The ratio of the content of (H) is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass. Since the filler is significantly less likely to absorb water than the other components, it is easier to make the water absorption rate 0.55% or less when the ratio is at least the lower limit value. And when picking up a semiconductor chip with a resin film with a small size from a support sheet, the effect which controls residual of a resin film on a support sheet becomes high. Moreover, the intensity | strength of the film for resin film formation and the resin film which is its hardened | cured material improves more because the said ratio is below the said upper limit.

Composition (IV-1) contains, according to the purpose, a thermosetting component, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant and a general-purpose additive, in addition to the energy ray-curable component and the filler. It may contain one or more selected from the group consisting of

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

For example, the film for forming an energy ray curable resin 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. The strength of the resin film formed from the energy beam curable resin film-forming film is also improved.
Further, the film for forming an energy ray curable resin film formed by using the composition (IV-1) containing the energy ray curable component and the colorant has the thermosetting resin film formed as described above. The same effect as in the case where the film for coloring contains the colorant (I) is exhibited.

In the composition (IV-1), one of each of the thermosetting component, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive may be used alone, or two of them may be used. The above may be used in combination, and when using 2 or more types together, the combination and ratio of those can be selected arbitrarily.

The content of the thermosetting component, the coupling agent, the crosslinking 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. .

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

<< Method for producing a composition for forming an 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 the components for constituting the composition.
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

○ Film for forming non-hardening resin film The film for forming non-hardening resin film does not show a change in properties due to hardening, but in the present invention, the film is stuck to a target location such as the back surface of a semiconductor wafer. It is considered that a resin film has been formed at a stage.

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 preferred.

The film for forming the non-curable resin film may be only one layer (single layer), or two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from one another. The combination of multiple layers is not particularly limited.

The thickness of the film for forming a non-curable resin film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. The uniformity of thickness becomes higher by the thickness of the film for non-hardening resin film formation being more than the above-mentioned lower limit. In addition, when the thickness of the non-hardening resin film-forming film is equal to or less than the upper limit value, the generation amount of cuttings of the oil film-forming film or resin film generated at the time of blade dicing of the semiconductor wafer is suppressed.
Here, "the thickness of the film for forming a non-curable resin film" means the thickness of the entire film for forming a non-curable resin film, and for example, the film for forming a non-curable resin film formed of a plurality of layers The thickness means the total thickness of all the layers constituting the non-curable resin film-forming film.

<< Composition for forming non-curable resin film >>
The film for non-hardening resin film formation can be formed using the composition for non-hardening resin film formation containing the constituent material. For example, a composition for forming a non-curable resin film is coated on the surface to be formed of a film for forming a non-curable resin film, and dried as needed to form a non-curable resin film on a target site It can form a film.

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

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

<Composition for forming a non-curable resin film (V-1)>
As a preferred composition for forming a non-curable resin film, for example, a composition for forming a non-curable resin film (V-1) containing the thermoplastic resin and the filler (in the present specification, simply “the composition (V-1) "and the like.

[Thermoplastic resin]
The thermoplastic resin is not particularly limited.
More specifically, as the thermoplastic resin, for example, the curing properties of acrylic resins, polyesters, polyurethanes, phenoxy resins, polybutenes, polybutadienes, polystyrenes, etc. listed as components of the above-mentioned composition (III-1) And the same resins as those mentioned above.

The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.

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 heat relative to the total mass of the film in the film for forming a non-curable resin film) The proportion 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 film for non-curable resin film formation containing a filler has the same effect as the film for thermosetting resin film formation containing a filler (D).

The filler contained in the composition (V-1) and the film for forming a non-curable resin film is the same as the filler (D) contained in the composition (III-1) and a film for forming a thermosetting resin film The thing is mentioned.

The filler contained in the composition (V-1) and the film for forming a non-curable resin film may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary Can be selected.

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, the filler relative to the total mass of the film in the film for forming a non-curable resin film) The content ratio) is preferably 25 to 75% by mass, and more preferably 28 to 72% by mass. Since the filler is significantly less likely to absorb water than the other components, it is easier to make the water absorption rate 0.55% or less when the ratio is at least the lower limit value. And when picking up a semiconductor chip with a resin film with a small size from a support sheet, the effect which controls residual of a resin film on a support sheet becomes high. Moreover, the intensity | strength of the film (resin film) for resin film formation improves more because the said ratio is below the said upper limit.

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 film for forming a non-curable resin film formed by using the composition (V-1) containing the thermoplastic resin and the colorant is the film for forming a thermosetting resin film described above. The same effect as in the case of containing the colorant (I) is exhibited.

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

The content of the other components in the composition (V-1) may be appropriately adjusted depending on the purpose, and is not particularly limited.

The composition (V-1) preferably further contains a solvent because the handling thereof is improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same as the solvents in the above-mentioned composition (III-1).
The solvent contained in the composition (V-1) may be only one type, or two or more types.

<< Method for Producing Composition for Forming Non-Curable Resin Film >>
The composition for forming a non-curable resin film such as the composition (V-1) can be obtained by blending the components for constituting the composition.
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

複合 Composite sheet for resin film formation The composite sheet for resin film formation of the present invention comprises a support sheet, and comprises a film for resin film formation on the support sheet, and the film for resin film formation is the above-mentioned present It is a film for forming a resin film of the invention.

The composite sheet for resin film formation of the present invention is suitable for use by being attached to the back surface of a semiconductor wafer when the semiconductor wafer is singulated (divided) into small semiconductor chips by blade dicing. The film for resin film formation in the composite sheet for resin film formation can be used to form a resin film on the back surface of the semiconductor wafer or the semiconductor chip, and the support sheet can be used as a dicing sheet. The semiconductor chip with a film for resin film formation with a small size or the semiconductor chip with a resin film obtained by blade dicing is excellent in the pickup aptitude from the support sheet, and at the time of pickup, the film or resin film for resin film formation on the support sheet. Survival is suppressed.
Hereinafter, the structure other than the film for resin film formation of the composite sheet for resin film formation of this invention is demonstrated in detail.

Support Sheet The support sheet may be formed of one layer (single layer) or may be formed of two or more layers. When a support sheet consists of multiple layers, the constituent material and thickness of these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited unless the effect of this invention is impaired.
In the present specification, not only in the case of a support sheet, but “a plurality of layers may be the same as or different from each other” means that “all layers may be the same or all layers are different. Means that only some of the layers may be the same, and the phrase "plural layers are different from each other" means that "at least one of the constituent material and thickness of each layer is different from each other". Means

As a preferable support sheet, for example, a substrate is provided, and an adhesive layer is laminated on the substrate; a substrate is provided, an intermediate layer is laminated on the substrate, and adhesion is performed on the intermediate layer. Those obtained by laminating the agent layer; and those formed only of the base material.

Hereinafter, examples of the composite sheet for resin film formation of the present invention will be described with reference to the drawings for each type of such a support sheet. Note that the drawings used in the following description may be enlarged for convenience, in order to make the features of the present invention intelligible. Not necessarily.

FIG. 1 is a cross-sectional view schematically showing an embodiment of a composite sheet for resin film formation of the present invention.
The composite sheet 101 for resin film formation shown here is provided with the adhesive layer 12 on the base material 11, and is provided with the film 13 for resin film formation on the adhesive layer 12. The support sheet 1 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12. In other words, the resin film formation film 13 is laminated on one surface 1 a of the support sheet 1. Have the following configuration. The resin film-forming composite sheet 101 further includes a peeling film 15 on the resin film-forming film 13.

In the composite sheet 101 for resin film formation, the adhesive layer 12 is laminated on one surface 11 a of the substrate 11, and the resin film formation film 13 is laminated on the entire surface of one surface 12 a of the adhesive layer 12. The adhesive layer 16 for jigs is laminated on a part of one surface 13 a of the film 13 for film formation, that is, the region in the vicinity of the peripheral portion, and the adhesive for jigs of the surface 13 a of the resin film forming film 13 A release film 15 is laminated on the surface on which the layer 16 is not laminated and 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 the above-described conditions of the water absorption rate and the adhesive force change rate.

The jig adhesive layer 16 may have, for example, a single layer structure containing an adhesive component, or a plurality of layers in which layers containing the adhesive component are laminated on both sides of a sheet to be a core material. It may be of a structure.

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

FIG. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for resin film formation of the present invention. In the drawings after FIG. 2, the same components as those shown in the already described drawings are denoted by the same reference numerals as in the already explained drawings, and the detailed description thereof will be omitted.

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

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

FIG. 3: is sectional drawing which shows typically other embodiment of the composite sheet for resin film formation of this invention.
The composite sheet for resin film formation 103 shown here is the same as the composite sheet for resin film formation 101 shown in FIG. 1 except that the adhesive layer 12 is not provided. That is, in the composite sheet 103 for resin film formation, the support sheet 1 is made of only the base material 11. And film 13 for resin film formation is laminated on one surface 11a of base material 11 (in other words, one surface 1a of support sheet 1), and a part of surface 13a of film 13 for resin film formation, ie, a periphery The jig adhesive layer 16 is laminated in the area 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 peeling film 15 is laminated | stacked on the surface 16a (upper surface and side surface) of this.

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

FIG. 4: is sectional drawing which shows typically other embodiment of the composite sheet for resin film formation of this invention.
The composite sheet for resin film formation 104 shown here is the same as the composite sheet for resin film formation 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 11a of the substrate 11, and the release film 15 is laminated on the entire surface 13a of the resin film-forming film 13. It is done.

The composite sheet 104 for resin film formation shown in FIG. 4 is the same as the composite sheet 102 for resin film formation shown in FIG. 2, with the release film 15 removed, in the surface 13 a of the film 13 for resin film formation The back surface of the 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 the area in the vicinity of the peripheral portion of the resin film forming film 13 .

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

In the composite sheet 105 for resin film formation, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11, and a part of the one surface 12 a of the pressure-sensitive adhesive layer 12, that is, the width direction of the support sheet 1 The film 23 for resin film formation is laminated | stacked on the area | region of the center side in the left-right direction in 5. Then, on the surface 12 a of the pressure-sensitive adhesive layer 12 on which the resin film-forming film 23 is not laminated and the one surface 23 a (upper surface and side surface) of the resin film-forming film 23, the peeling film 15 is It is stacked.

When the resin film-forming composite sheet 105 is viewed from above from above and viewed in plan, the resin film-forming film 23 has a surface area smaller than that of the pressure-sensitive adhesive layer 12 and has, for example, a circular shape.

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

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

In the composite sheet 105 for resin film formation shown in FIG. 5, the surface 12 a of the pressure-sensitive adhesive layer 12 is the same as that shown in FIGS. 1 and 3 on the surface on which the resin film formation film 23 is not laminated. A jig adhesive layer may be laminated on the substrate (not shown). The composite sheet 105 for resin film formation provided with such an adhesive layer for jigs is a ring frame on the surface of the adhesive layer for jigs in the same manner as the composite sheet for resin film formation shown in FIGS. 1 and 3. Jig etc. are stuck and used.

The composite sheet for resin film formation of the present invention may be provided with an adhesive layer for jig regardless of the form of the support sheet and the film for resin film formation.

The composite sheet for resin film formation of the present invention is not limited to those shown in FIG. 1 to FIG. 5, and the configuration of a part of those shown in FIG. It may be one that has been deleted or another configuration added to those described above.

For example, in the composite sheet for resin film formation shown in FIGS. 3 and 4, an intermediate layer may be provided between the substrate 11 and the film 13 for resin film formation. The intermediate layer can be selected arbitrarily according to the purpose.
Moreover, in the composite sheet for resin film formation shown in FIG.1, FIG2 and FIG.5, the intermediate | middle layer may be provided between the base material 11 and the adhesive layer 12. As shown in FIG. That is, in the composite sheet for resin film formation of the present invention, the support sheet may be formed by laminating the base material, the intermediate layer and the pressure-sensitive adhesive layer in this order. Here, the intermediate layer is the same as the intermediate layer which may be provided in the composite sheet for resin film formation shown in FIGS. 3 and 4.
In the composite sheet for resin film formation shown in FIGS. 1 to 5, the layer other than the intermediate layer may be provided at an arbitrary position.
Further, in the composite sheet for resin film formation of the present invention, a partial gap may be generated between the release film and the layer in direct contact with the release film.
Moreover, in the composite sheet for resin film formation of this invention, the magnitude | size and shape of each layer can be arbitrarily adjusted according to the objective.

○ Base Material The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE); polyethylene other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene and norbornene resin Polyolefins; Ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer Copolymers obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer), polystyrene, polycycloolefin, polyethylene terephthalate, polyethylene Nafta Polyesters such as polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, wholly aromatic polyesters in which all constituent units have an aromatic cyclic group; Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluorocarbons; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are also mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin obtained by crosslinking one or more of the above-described resins exemplified so far; modification of an ionomer using one or more of the above-described resins exemplified so far Resin is also mentioned.

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

The base material may consist of one layer (a single layer), or may consist of a plurality of layers of two or more layers, and in the case of a plurality of layers, these plural layers may be the same or different from each other, and these plural The combination of layers is not particularly limited.

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 140 μm. When the thickness of the base material is in such a range, the flexibility of the composite sheet for resin film formation and the adhesion to a semiconductor wafer or a semiconductor chip are further improved.
Here, "the thickness of the substrate" means the thickness of the entire substrate, for example, the thickness of the substrate comprising a plurality of layers means the total thickness of all the layers constituting the substrate means.

The substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which the thickness variation is suppressed regardless of the part. Among the above-mentioned constituent materials, as materials which can be used to construct a substrate having such a high thickness accuracy, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc. Can be mentioned.

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

The substrate may be transparent or opaque, or may be colored according to the purpose, or other layers may be deposited.
When the resin film-forming film is energy ray curable, the substrate preferably transmits energy rays.

The base material is roughened by sand blasting, solvent treatment, etc. in order to improve the adhesion to a layer (for example, a pressure-sensitive adhesive layer, an intermediate layer or a film for forming a resin film) provided thereon; corona discharge treatment The surface may be subjected to oxidation treatment such as electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and the like. In addition, the substrate may be one whose surface is primed.

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

○ Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is in the form of a sheet or a film, and contains a pressure-sensitive adhesive.
Examples of the pressure-sensitive adhesive include pressure-sensitive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Acrylic resins are preferable. .

In the present invention, the term "adhesive resin" is a concept including both an adhesive resin and an adhesive resin, and for example, the resin itself is not limited to one having adhesiveness. It also includes a resin that exhibits tackiness when used in combination with other components such as additives, and a resin that exhibits adhesion due to the presence of a trigger such as heat or water.

The pressure-sensitive adhesive layer may be formed of one layer (single layer) or may be formed of two or more layers, and in the case of two or more layers, these layers may be the same or different from one another. The combination of multiple 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 thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means 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, or may be colored according to the purpose.
When the resin film-forming film is energy ray curable, the pressure-sensitive 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 layer can be formed on a target site by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying it as necessary. The more specific formation method of an adhesive layer is demonstrated in detail later with the formation method of another layer.

The application of the pressure-sensitive adhesive composition can be performed, for example, by the same method as the application of the composition for forming a thermosetting resin film described above.

In the case of providing the pressure-sensitive adhesive layer on the substrate, for example, the pressure-sensitive adhesive composition may be coated on the substrate and dried as necessary to laminate the pressure-sensitive adhesive layer on the substrate. When the pressure-sensitive adhesive layer is provided on the substrate, for example, the pressure-sensitive adhesive composition is applied on the release film, and dried as needed to form the pressure-sensitive adhesive layer on the release film. Alternatively, the pressure-sensitive adhesive layer may be laminated on the substrate by bonding the exposed surface of the pressure-sensitive adhesive layer to one surface of the substrate. The release film in this case may be removed at any time during the manufacturing process of the composite sheet for resin film formation.

The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferable to heat and dry. The solvent-containing pressure-sensitive adhesive composition 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, a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive, that is, an energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable tackiness Pressure-sensitive adhesive composition (I-1) containing resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; non-energy Energy ray curable adhesive resin (I-2a) (hereinafter referred to as “adhesive resin (I-2a)”) wherein an unsaturated group is introduced into the side chain of the linear curable adhesive resin (I-1a) Pressure-sensitive adhesive composition (I-2) containing the abbreviation); pressure-sensitive adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound, etc. Can be mentioned.

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

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
The structural unit which the said acrylic resin has may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combination and ratio can be selected arbitrarily.

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

It is preferable that the said acryl-type polymer has a structural unit derived from the (meth) acrylic-acid alkylester whose carbon number of the said alkyl group is 4 or more from the point which the adhesive force of an adhesive layer improves. The carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8, in order to further improve the adhesion of the pressure-sensitive adhesive layer. The (meth) acrylic acid alkyl ester in which the number of carbon atoms of the alkyl group is 4 or more 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, reaction of the functional group with a crosslinking agent described later becomes a crosslinking origin, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later And those which make it possible to introduce an unsaturated group into the side chain of the acrylic polymer.

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. are mentioned, for example.
That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxy group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

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

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

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, and more preferably 2 to 32% by mass, with respect to the total amount of the structural units. And 3 to 30% by mass is particularly preferable.

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

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

The acrylic polymer can be used as the above-mentioned non-energy ray curable tackifying resin (I-1a).
On the other hand, those in which the unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) is reacted with the functional group in the acrylic polymer have 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 type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the 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% by mass is more preferable, and 15 to 90% by 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 which have an energy ray-polymerizable unsaturated group and can be cured by irradiation of energy rays.
Among the energy ray-curable compounds, as a monomer, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4 -Multivalent (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 ( Meta) acrylate etc. are mentioned.
Among the energy ray-curable compounds, examples of the oligomers include oligomers formed by polymerization of the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly reduced.

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

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass. The content 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 a structural unit derived from a (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( It is preferable that I-1) further contains a crosslinking agent.

The crosslinking agent, for example, reacts with the functional group to crosslink the adhesive resin (I-1a).
Crosslinking agents include, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based crosslinking agents such as adducts of these diisocyanates (crosslinking agents having an isocyanate group); epoxy-based crosslinking agents such as ethylene glycol glycidyl ether ( Crosslinking agent having glycidyl group); Aziridine type crosslinking agent such as hexa [1- (2-methyl) -aziridinyl] trifosphatriazine (crosslinking agent having aziridinyl group); Metal chelate type crosslinking agent such as aluminum chelate (metal Crosslinkers having a chelate structure); isocyanurate crosslinkers (crosslinkers having an isocyanuric acid skeleton) and the like.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoint of improving the cohesion of the pressure-sensitive adhesive to improve the adhesion of the pressure-sensitive adhesive layer and being easy to obtain.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally 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), The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

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

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl phosphine Oxides, acyl phosphine oxide compounds such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide Substances; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
Further, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone and the like; photosensitizers such as amine and the like can also be used.

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

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 The content is more preferably in the range of 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 which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agent, antioxidant, softener (plasticizer), filler (filler), rust inhibitor, coloring agent (pigment, dye), sensitizer, tackifier Well-known additives, such as a reaction retarder, a crosslinking accelerator (catalyst), etc. are mentioned.
The reaction retarder means, for example, an unintended cross-linking reaction in the adhesive composition (I-1) during storage by the action of a catalyst mixed in the adhesive composition (I-1). It is to control progress. The reaction retarder includes, for example, those which form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule It can be mentioned.

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

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

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

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

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

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

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

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

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with the functional group in the adhesive resin (I-1a) in addition to the energy beam 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 a functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of binding to a hydroxyl group or an amino group, and a hydroxy group and amino group capable of binding to a carboxy group or an epoxy group. Etc.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

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

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

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) 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-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.

In the pressure-sensitive adhesive composition (I-2), 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-2a), The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

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

The photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) may be the same as the photopolymerization initiator 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 two or more types, and in the case of two or more types, the combination and ratio thereof 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) The amount 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-2) may contain other additives which do not correspond to any of the components described above, 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).
The other additives contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as the pressure-sensitive adhesive composition (I-1).
The solvent in the pressure-sensitive adhesive composition (I-2) may be the same as the solvent 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 two or more types, and in the case of two or more types, the combination and ratio thereof 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.

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

In the pressure-sensitive adhesive composition (I-3), the ratio of the content of the 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% by mass is more preferable, and 15 to 90% by 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 which have an energy ray-polymerizable unsaturated group and can be cured by irradiation of energy rays, and the pressure-sensitive adhesive composition The same as the energy ray-curable compound contained in the compound (I-1) can be mentioned.
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .

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

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

The photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) may be the same as the photopolymerization initiator 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 two or more types, and in the case of two or more types, the combination and ratio thereof 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 relative to the total content of the adhesive resin (I-2a) and the energy ray-curable compound. The amount 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 which do not correspond to any of the components described above, 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).
The other additives contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.

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

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

<Adhesive Composition Other than Adhesive Composition (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, but those described as the components thereof are General pressure-sensitive adhesive compositions other than these three pressure-sensitive adhesive compositions (herein referred to as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)") But it can be used as well.

As the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable pressure-sensitive adhesive composition, non-energy ray-curable pressure-sensitive adhesive compositions can also be mentioned.
As a non-energy ray curable pressure-sensitive adhesive composition, for example, non-energy ray curing such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. And the pressure-sensitive adhesive composition (I-4) containing the adhesive resin (I-1a), and those containing an acrylic resin are preferable.

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

<Pressure-sensitive adhesive composition (I-4)>
Preferred examples of the pressure-sensitive adhesive composition (I-4) include those containing the above-mentioned 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 ones 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 type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the 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% by mass is more preferable, and 15 to 90% by mass is particularly preferable.

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

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same as the crosslinking agents in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally 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), The amount 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 which do not correspond to any of the components described above, 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).
The other additives contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.

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

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

In the composite sheet for resin film formation of the present invention, when the film for resin film formation to be described later is energy ray curable, the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy beam curable, when the resin film-forming film is cured by irradiation with energy rays, it may not be possible to suppress the pressure-sensitive adhesive layer from being cured simultaneously. When the pressure-sensitive adhesive layer is cured simultaneously with the resin film-forming film, the cured product of the resin film-forming film and the pressure-sensitive adhesive layer may stick to such an extent that they can not be peeled off at these interfaces. In that case, it becomes difficult to peel off 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 a resin film) from the support sheet provided with the cured product of the pressure sensitive adhesive layer. The resin film-coated semiconductor chip can not be properly picked up. By making the adhesive layer non-energy ray curable in the support sheet of the present invention, such a defect can be reliably avoided, and the semiconductor chip with a resin film can be picked up more easily.

Here, although the effect when the pressure-sensitive adhesive layer is non-energy ray curable has been described, even if the layer 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 radiation curable, the same effect can be obtained.

<< Method of producing pressure-sensitive adhesive composition >>
Pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3) and pressure-sensitive adhesive compositions (I-1) to (I-3) such as pressure-sensitive adhesive composition (I-4) It is obtained by blending the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition, such as components other than the pressure-sensitive adhesive.
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

Method for Producing Composite Sheet for Forming Resin Film The composite sheet for forming a resin film of the present invention can be produced by sequentially laminating the above-described layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.
For example, in the case of laminating a pressure-sensitive adhesive layer on a substrate when manufacturing a support sheet, the above-mentioned pressure-sensitive adhesive composition may be coated on the substrate and dried as necessary.

On the other hand, for example, in the case of further laminating a film for resin film formation on the pressure-sensitive adhesive layer laminated on the substrate, the composition for resin film formation is coated on the pressure-sensitive adhesive layer, and the resin film is formed. It is possible to form the forming film directly. A layer other than the film for resin film formation can also laminate this layer on an adhesive layer by the same method using the composition for forming this layer. As described above, in the case of forming a continuous two-layer laminated structure using any of the compositions, the composition is further coated on the layer formed of the composition to form a new layer. It is possible to form However, of these two layers, the layer to be laminated later is formed in advance using the composition on another release film, and the side of the formed layer in contact with the release film is It is preferable to form a continuous two-layered laminated structure by bonding the opposite exposed surface 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 necessary after the formation of the laminated structure.

For example, a composite sheet for resin film formation in which an adhesive layer is laminated on a substrate and a film for resin film formation is laminated on the adhesive layer (in other words, a support sheet is a laminate of a substrate and an adhesive layer) In the case of producing a composite sheet for forming a resin film), the pressure-sensitive adhesive composition is coated on a substrate, and dried as needed, thereby laminating the pressure-sensitive adhesive layer on the substrate Every time, separately, the composition for resin film formation is coated on the release film, and dried as needed, thereby forming the film for resin film formation on the release film. Then, the exposed surface of the resin film-forming film is attached to the exposed surface of the pressure-sensitive adhesive layer laminated on the substrate, and the resin film-forming film is laminated on the pressure-sensitive adhesive layer to form a resin film. Composite sheet is obtained.

In addition, when laminating an adhesive layer on a base material, it replaces with the method of coating an adhesive composition on a base material as mentioned above, and applies an adhesive composition on a peeling film. If necessary, the pressure-sensitive adhesive layer is formed on the release film, and the exposed surface of this layer is bonded to one surface of the substrate to form the pressure-sensitive adhesive layer on the substrate. It may be stacked.
In any of the methods, the release film may be removed at any timing after formation of the intended 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 composite sheet for resin film formation is attached to the back surface of the semiconductor wafer by the film for resin film formation.

Then, when the resin film-forming film is energy ray curable, the resin film forming film is energy ray cured by irradiation of energy rays to form a resin film or as it is without energy ray curing. However, when 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 formation film or the resin film by blade dicing to obtain a semiconductor chip. At this time, it is preferable to adjust the size of the semiconductor chip to be smaller. 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, or 2.5 mm or less.

Next, the semiconductor chip is separated from the support sheet with the resin film-forming film or the resin film attached to the back surface (that is, as a resin film-forming film-attached semiconductor chip or resin film-attached semiconductor chip) and picked up Do. At this time, by using the film for resin film formation of the present invention, even when the semiconductor chip with a film for resin film formation or the resin film with a resin film having a small size is picked up from the support sheet, It is possible to suppress the remaining of the resin film-forming film or the resin film on the support sheet.

In addition, when the film for resin film formation is thermosetting (For example, when the film for resin film formation is not energy ray curable but thermosetting, or the characteristic of both energy ray curing and thermosetting) In the case where the semiconductor film is formed, it is preferable not to thermally cure the resin film-forming film or the resin film which has not been thermally cured, which is attached to the semiconductor chip, until the end of the pickup. That is, it is preferable that the thermosetting resin film-forming film of the present invention be thermally cured after picking up the semiconductor chip.
Moreover, when blade dicing is performed without energy ray curing the film for energy ray curable resin film formation, resin film formation stuck on the back surface of the semiconductor chip at any stage after blade dicing. The film for energy may be energy ray cured to be a resin film or may not be energy ray cured.

After that, the target semiconductor device may be manufactured according to the application of the resin film by the same method as the conventional method.
For example, in the case of using a film for resin film formation or a resin film as a film-like adhesive, the semiconductor chip is die-bonded to the circuit surface of the substrate with a film-like adhesive, and if necessary, the semiconductor chip is further semiconductor chip After laminating one or more pieces and performing wire bonding, the whole is sealed with a resin to obtain a semiconductor package. Then, using this semiconductor package, a target semiconductor device is manufactured.
For example, when using a film for resin film formation as a film for protective film formation (in other words, a resin film as a protective film), a semiconductor chip with a protective film is flip chip connected to the circuit surface of the substrate, Do. Then, a target semiconductor device may be manufactured using this semiconductor package. In this case, the formation of the resin film (protective film) by curing of the film for resin film formation can be performed at any timing before and after blade dicing.

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

<Production raw material of composition for resin film formation>
The raw materials used for the production of the composition for resin film formation are shown below.
[Polymer component (A)]
(A) -1: A copolymer of n-butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) Acrylic resin (weight average molecular weight 800000, glass transition temperature-28 ° C).
[Thermosetting component (B)]
・ Epoxy resin (B1)
(B1) -1: A mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles (Nippon Kayaku Co., Ltd. "BPA 328", epoxy equivalent 235 g / eq)
(B1) -2: dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "XD-1000-L", epoxy equivalent 248 g / eq)
(B1) -3: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC, epoxy equivalent: 255 to 260 g / eq)
・ Heat curing agent (B2)
(B2) -1: Dicyandiamide (Thermally active latent epoxy resin curing agent, "ADEKA HARDNER EH-3636 AS" manufactured by ADEKA, active hydrogen content 21 g / eq)
[Hardening accelerator (C)]
(C) -1: 2-phenyl-4,5-dihydroxymethylimidazole ("Cuazole 2PHZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.)
[Filler (D)]
(D) -1: Spherical silica (AD MATEX Corporation "SC 2050")
[Coupling agent (E)]
(E) -1: a 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 ("BHS 8515" manufactured by Toyochem Co., Ltd.)
[Energy ray curable resin (G)]
(G) -1: tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., UV curable resin)
[Photoinitiator (H)]
Photopolymerization initiator (H) -1: 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184" manufactured by BASF Japan Ltd.)

<Manufacture of composite sheet for resin film formation>
Example 1
(Production of composition for forming thermosetting resin film (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 curable Resin (G) -1 (6.37 parts by mass) and photopolymerization initiator (H) -1 (0.20 parts by mass) are mixed, and the concentration of solids in methyl ethyl ketone is 55% by mass. The composition was diluted to obtain a thermosetting resin film-forming composition (III-1). In addition, the compounding quantity of components other than methyl ethyl ketone shown here is all solid content.

(Production of film for resin film formation)
The composition obtained in the above (III) was applied to the release-treated side of a release film (“SP-PET 381031” manufactured by Lintec, thickness 38 μm) in which one side of a polyethylene terephthalate (PET) film was release-treated by silicone treatment The resin composition for forming a resin film having a thickness of 20 μm was formed by coating the above No. 1) and drying at 100 ° C. for 1 minute.
In addition, on the exposed surface of the film for resin film formation (the surface opposite to the side provided with the above-mentioned release film), separately, the release is carried out by silicone treatment of one side of the polyethylene terephthalate (PET) film. The release-treated surface of a film ("SP-PET 502150" manufactured by Lintec Corp., thickness 50 μm) was laminated to prepare a laminated film in which the release film was laminated on both sides of the resin film-forming film.

(Manufacture of composite sheet for resin film formation)
The peeling film stuck afterward was removed from the laminated film obtained above, and the film for resin film formation was exposed.
A two-layer film (total thickness of 90 μm of two layers) comprising a film (thickness 40 μm) made of ethylene-methacrylic acid copolymer (EMAA) and a film (thickness 50 μm) made of polypropylene (PP) The substrate (support sheet) and the resin film-forming film are laminated by bonding the newly exposed surface of the above-mentioned resin film-forming film to the surface on the polypropylene film side, which is used as the substrate. A composite sheet for resin film formation was obtained.

<Evaluation of film for resin film formation>
(Water absorption of first test piece)
The plurality of resin film-forming films obtained above were laminated and bonded to prepare a laminate having a total thickness of 200 μm. Next, this laminate was punched (cut) to a size of 50 mm × 50 mm to produce a first laminate having a size of 50 mm × 50 mm and a thickness of 200 μm. Then, the first laminate is irradiated with ultraviolet light using an ultraviolet irradiation apparatus ("RAD-2000 m / 12" manufactured by Lintec Corporation) under the conditions of an illuminance of 220 mW / cm ² and a light quantity of 120 mJ / cm ² . The first laminate was UV-cured to produce a first cured product which was not thermally cured. This first cured product was used as a first test piece, and its mass W _A was measured immediately. Next, the first test piece is immersed in pure water at 23 ° C. for 2 hours, taken out of the pure water, and after removing excess water droplets adhering to the surface, the mass of the first test piece after this immersion W _B was measured. Subsequently, the water absorption (%) of the first test piece was calculated by the formula “(W _B −W _A ) / W _A × 100”. When immersing 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.

(% Change in adhesion of second test piece)
The resin film-forming film obtained above was attached by heating to 40 ° C. on 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. Furthermore, a 25-mm-wide, 200-mm-long, 70-μm-thick strong adhesive tape is attached to multiple locations on the exposed surface of the resin film-forming film (in other words, the surface opposite to the silicon mirror wafer side). Then, cuts were formed in the resin film-forming film along the outer periphery of the strong adhesive tape. By the above, the 2nd laminated body was produced. Next, using a UV irradiation apparatus ("RAD-2000 m / 12" manufactured by LINTEC Corporation), UV light is applied to the resin film-forming film in the second laminate under the conditions of illuminance 220 mW / cm ² and light quantity 120 mJ / cm ² The film for resin film formation was ultraviolet-cured by irradiating the resin film to obtain a second cured product which was not thermally cured. A second laminate (cured second laminate) including the second cured product is used as a second test piece, and the second test piece is immediately treated for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Let stand and let it age. Then, immediately after the passage of time between the second cured product and the silicon mirror wafer, the adhesion (immersion (immersion) between the second cured product and the silicon mirror wafer in an environment of 23.degree. Pre-adhesiveness) _PA1 was measured. Then, the second test piece after this aging was immersed in pure water at 23 ° C. for 2 hours. Next, the second test piece is taken out of pure water, excess water droplets adhering to the surface are removed, and immediately after the immersion, the other one of the second test pieces is stuck with another strong adhesive tape. in places, under 23 ° C. environment was measured after immersion adhesive strength P _B1 between the second cured silicon mirror wafer. Subsequently, the adhesive force change rate (%) of the second test piece was calculated by the formula “(| P _B1 −P _A1 |) / P _A1 × 100”. Thus, the pre-immersion adhesion and the post-immersion adhesion were measured continuously at different points in the same second test piece. In addition, when immersing the second test piece 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 the measurement of the adhesive force before immersion and the adhesive force after immersion, the two peeling surfaces which are produced when the second cured product is peeled off using the universal tensile tester “Autograph” manufactured by Shimadzu Corporation. The laminate of the second cured product and the strong pressure-sensitive adhesive tape was peeled off from the second test piece at a peeling speed of 300 mm / min so that the formed angle was 180 °, so-called 180 ° peeling was performed. And the peeling force (mN / 25 mm) at this time was measured, and this was made into the adhesion power before immersion, and the adhesion power after immersion, respectively. The results are shown in Table 1.

(Young's modulus, breaking elongation and breaking stress of the third test piece)
The plurality of resin film-forming films obtained above were laminated to prepare a laminate having a total thickness of 200 μm. Next, the laminate was punched (cut) to a size of 15 mm × 150 mm to produce a third laminate having a size of 15 mm × 150 mm and a thickness of 200 μm. Then, the third laminate is irradiated with ultraviolet light using an ultraviolet irradiation apparatus ("RAD-2000 m / 12" manufactured by Lintec Corporation) under the conditions of an illuminance of 220 mW / cm ² and a light quantity of 120 mJ / cm ² . The third laminate was subjected to ultraviolet curing to prepare a third cured product which was not thermally cured. Using this third cured product as a third test piece, the third test piece is subjected to a tensile test at a test speed of 200 mm / min in an environment of 23 ° C. in accordance with JIS K 7127 to obtain a 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, a tensile test was immediately performed on the third test piece after this immersion in the same method under an environment of 23 ° C., and Young's modulus (Young's modulus after immersion) (MPa) was measured. When immersing 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 immersion and the Young's modulus after immersion of the third test piece described above, the elongation before breakage before immersion of the third test piece from the elongation of the third test piece when the third test piece breaks %) And the breaking elongation (%) after immersion, 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) For each). The results are shown in Table 1.

<Evaluation of composite sheet for resin film formation>
(Pick-up aptitude of semiconductor chip with resin film (production aptitude of semiconductor chip with resin film))
A back grind tape ("ADWILL E-8180 HR" manufactured by Lintec Corporation) was attached to an 8-inch silicon mirror wafer using a tape laminator ("RAD 3510" manufactured by Lintec Corporation). Next, using a grinder (DCP "DGP 8760"), the surface of the 8-inch silicon mirror wafer opposite to the side on which the back grind tape is attached was ground to make the silicon mirror wafer 350 μm thick. . Then, the silicon mirror wafer was left to stand for 72 hours after grinding. Next, using the wafer mounter (“RAD 2700” manufactured by Lintec Corporation), the composite sheet for resin film formation obtained above is heated to 40 ° C. on the ground surface of the silicon mirror wafer after this standing and the resin film It stuck by the film for formations at the sticking speed of 20 mm / sec. Next, after removing the back grind tape, using a UV irradiation apparatus ("RAD-2000 m / 12" manufactured by LINTEC Corporation), for forming this resin film under the conditions of illuminance 230 mW / cm ² and light quantity 120 mJ / cm ² The resin film-forming film in the composite sheet was irradiated with ultraviolet rays to cause ultraviolet curing of the resin film-forming film, thereby producing a resin film which was not thermally cured. Then, using a dicing apparatus (“DFD6361” manufactured by Disco Corporation), the silicon mirror wafer is diced together with a resin film while applying cooling water at a flow rate of 1.0 L / min to form silicon of 2 mm × 2 mm in size. It was separated into chips.

The work in which a large number of silicon chips with a resin film after dicing were immobilized on a support sheet was immersed in pure water at 23 ° C. for 2 hours. Then, using a pick-up / die bonding apparatus ("BESTEM-D02" manufactured by CANON MACHINERY CO., LTD.), In the work after this immersion, an operation of pulling away the silicon chip with a resin film from the support sheet (the base material) I went there. The pickup at this time was a method in which one silicon chip with a resin film was pushed up with one pin, the rising speed was 20 mm / s, and the amount of rising was 200 μm. Then, using an optical microscope ("VHX-100" manufactured by Keyence Corporation), the surface on the side provided with the silicon chip with a resin film in the support sheet after the operation was observed to confirm the presence or absence of the resin film remaining. . Then, on the surface of the support sheet, the number of places where the resin film remains out of the 100 places provided with the silicon chip with a resin film indicates the number of times the pickup was not performed normally, that is, the pickup aptitude The number of defects of was identified. On the surface of the support sheet, it is determined that the resin film-coated silicon chip could not be properly picked up at the portion where the resin film remains. The results are shown in Table 1. Of the evaluation result columns in Table 1, the evaluation results of this item are shown in the "number of defects in pickup aptitude" column.

<Production and evaluation of resin film-forming film and resin film-forming composite sheet>
[Examples 2 to 3, Comparative Examples 1 to 2]
A film for resin film formation was the same method as in Example 1 except that the content of each component of the composition for thermosetting resin film formation (film for resin film formation) was as shown in Table 1. And the composite sheet for resin film formation was manufactured and evaluated. The results are shown in Table 1.
In addition, the description of "-" in the column of the component in Table 1 means that the composition for thermosetting resin film formation does not contain the component.

As is clear from the above results, in Examples 1 to 3, the number of defects in pick-up suitability of the silicon chip with a 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 strength change rate of the second test piece was 16.5 to 38.4%. Between the second cured product and the silicon mirror wafer, and the measurement of immersion before adhesion (after aging adhesive force) P _A1, when measuring after immersion adhesive strength P _B1, the peeling off of the second specimen visually As observed, in Examples 1 to 3, cohesive failure occurred in the second cured product of the second test piece before and after immersion.
That is, the energy ray cured product of the film for forming a resin film of Examples 1 to 3 has a low water absorption rate, and the change in adhesive strength before and after immersion (water absorption) is suppressed, and the pickup aptitude is improved even after immersion. It was excellent.

Moreover, in Examples 1 to 3, the Young's modulus after immersion of the third test piece is 20.7 to 104.5 MPa, and the energy ray cured product of the film for forming a resin film of Examples 1 to 3 is intended for pickup Cleavage at the outside location was less likely to occur and had more desirable properties. Furthermore, 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 aptitude of the silicon chip with a resin film was 56, and the pick-up aptitude was clearly inferior.

In Comparative Example 1, the water absorption of the first test piece was 0.96%, which was a high level.
On the other hand, as in the case of Examples 1-3, and the measurement of immersion before adhesion (after aging adhesive force) P _A1, when measuring after immersion adhesive strength P _B1, the peeling off of the second specimen visually According to the observation, interface failure occurred between the second cured product and the silicon mirror wafer after immersion, but interface failure occurred between the second cured product and the strong adhesive tape before immersion. 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 adhesion between the second cured product and the silicon mirror wafer, and the measured value of the peeling force was 23584 (mN / 25 mm). From the above, it is confirmed that the adhesion between the second cured product and the silicon mirror wafer is larger than 23584 (mN / 25 mm), and the change in adhesion of the second test piece is larger than 66.0%. The However, it was confirmed that the change rate of the adhesive strength was high.
That is, the energy ray cured product of the film for forming a resin film of Comparative Example 1 has a high water absorption coefficient, and the change in adhesive strength before and after immersion (water absorption) is not suppressed, and the pickup aptitude after immersion In terms of point, it did not have favorable characteristics.

Moreover, in Comparative Example 1, the Young's modulus after immersion of the third test piece is 1.0 MPa, and the energy ray-cured product of the film for resin film formation of Comparative Example 1 is cut at an unintended location during pickup. It was easy and did not have favorable characteristics in this respect either.

Also in Comparative Example 2, the number of defects in the pick-up suitability of the semiconductor chip with a resin film was 45, and the pick-up suitability was clearly inferior.

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, also in Comparative Example 2, as in the case of Comparative Example 1, interface breakage occurred between the second cured product and the silicon mirror wafer after immersion, but before immersion, the second cured product An interfacial failure occurred between the second adhesive and the strong adhesive tape, and the second cured product and the silicon mirror wafer remained in close contact with each other. That is, even in Comparative Example 2, the peeling force before immersion did not represent the adhesion between the second cured product and the silicon mirror wafer, and the measured value of the peeling force was 25877 (mN / 25 mm). From the above, it is confirmed that the adhesion between the second cured product and the silicon mirror wafer is larger than 25877 (mN / 25 mm), and the change in adhesion of the second test piece is larger than 69.0%. The However, it was confirmed that the change rate of the adhesive strength was high.
That is, the energy ray cured product of the film for resin film formation of Comparative Example 2 also has a high water absorption coefficient, and the change in the adhesive strength before and after immersion (water absorption) is not suppressed, and the pickup suitability after immersion In terms of point, it did not have favorable characteristics.

Further, in Comparative Example 2, the Young's modulus after immersion of the third test piece is 5.1 MPa, and the energy beam cured product of the film for resin film formation of Comparative Example 2 is also cut at an unintended location during pickup. It was easy and did not have favorable characteristics in this respect either.

The present invention is applicable to the manufacture of semiconductor devices.

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

Claims

It is a film for resin film formation,
Producing a first laminate having a size of 50 mm × 50 mm and a thickness of 200 μm, in which a plurality of films for resin film formation are laminated;
When the film for resin film formation is energy ray curable, a first cured product obtained by energy ray curing the first laminate is used as a first test piece, and the film for resin film formation is non-energy ray cured When the first test piece is immersed in pure water for 2 hours using the first laminate as a first test piece, the water absorption of the first test piece is 0.55% or less. Yes, and
Producing a second laminate in which the resin film-forming film is attached to a silicon mirror wafer;
In the case where the resin film-forming film is energy beam curable, a cured second laminate after the resin film-forming film in the second laminate is energy beam 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 under an environment of a temperature of 23.degree. C. and a relative humidity of 50% for 30 minutes. The adhesion after the aging was measured, and the adhesion after the immersion between the second cured product and the silicon mirror wafer was measured when the second specimen after the aging was immersed in pure water for 2 hours. When the change in adhesion strength of the second test piece calculated from the adhesion after aging and the adhesion after immersion is 60% or less, or
When the film for resin film formation is non-energy ray curable, the second laminate is used as a second test piece, and the second test piece is heated for 30 minutes under an environment of a temperature of 23 ° C. and a relative humidity of 50%. The adhesion after the aging of the resin film-forming film and the silicon mirror wafer was measured after standing and aging, and the second test piece after aging was immersed in pure water for 2 hours. When the adhesion after immersion between the resin film-forming film and the silicon mirror wafer is measured, the change in adhesion of the second test piece calculated from the adhesion after time and the adhesion after immersion The film for resin film formation whose rate is 60% or less.
A third laminate having a size of 15 mm × 150 mm and a thickness of 200 μm, in which a plurality of the resin film-forming films are laminated, is prepared, and the resin film-forming film is energy beam curable. The third cured product obtained by energy beam curing the third laminate is used as a third test piece, and when the resin film-forming film is non-energy beam curable, the third laminate is As a test piece, when the third test piece is immersed in pure water for 2 hours, it is a tensile test based on JIS K 7127, and the test speed is measured as 200 mm / min. The film for resin film formation of Claim 1 whose Young's modulus is 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 to the total mass of the film for resin film formation is 25 to 75% by mass. .
A support sheet is provided, and a film for resin film formation is provided on the support sheet,
The composite sheet for resin film formation, wherein the film for resin film formation is a film for resin film formation according to any one of claims 1 to 3.