WO2019082959A1 - Film for protective film formation use, composite sheet for protective film formation use, and method for manufacturing semiconductor chip - Google Patents

Abstract

A film for protective film formation use according to the present embodiment contains a compound that is energy-ray-curable and has a carboxy group or a group that is a salt of a carboxy group and a polymerizable group per molecule. A composite sheet for protective film formation use according to the present embodiment is provided with a support sheet, wherein the film for protective film formation use is provided on the support sheet.

Description

Film for protective film formation, composite sheet for protective film formation, and method of manufacturing semiconductor chip

The present invention relates to a protective film-forming film, a protective film-forming composite sheet, and a method of manufacturing a semiconductor chip.
Priority is claimed on Japanese Patent Application No. 2017-208431, filed Oct. 27, 2017, the content of which is incorporated herein by reference.

In recent years, semiconductor devices have been manufactured to which a mounting method called a so-called face down method is applied. In the face-down method, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.

A resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and may be taken into a semiconductor device as a semiconductor chip with a protective film. The protective film is used to prevent the occurrence of cracks in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film comprising a support sheet and a film for forming a protective film for forming a protective film on the support sheet is used. Be done. The film for protective film formation can form a protective film by hardening. In addition, the support sheet can be used to fix the semiconductor wafer when dividing the semiconductor wafer provided with the protective film-forming film or the protective film on the back surface into semiconductor chips. Furthermore, the support sheet can also be used as a dicing sheet, and the composite sheet for protective film formation can also be used as an integrated film of the protective film formation film and the dicing sheet.

As such a composite sheet for protective film formation, for example, one provided with a thermosetting protective film-forming film that forms a protective film by curing by heating has been mainly utilized so far. However, since heat curing of a thermosetting protective film-forming film usually requires a long time of about several hours, shortening of the curing time is desired. On the other hand, using a film for protective film formation which can be cured (that is, energy beam curable) by irradiation of energy rays such as ultraviolet rays is being considered for formation of the protective film.

On the other hand, as a method of obtaining a semiconductor chip, a method of dicing a semiconductor wafer using a dicing blade is widely used. In this method, usually, a semiconductor wafer provided with a protective film-forming film or film on the back surface is divided by the dicing blade together with the protective film-forming film or protective film with a dicing blade to obtain semiconductor chips. .

On the other hand, in recent years, various methods of dividing a semiconductor wafer without using a dicing blade have been studied. For example, a modified layer is formed inside the semiconductor wafer by irradiating a laser beam so as to focus on a focal point set inside the semiconductor wafer, and then this modified layer is formed and the back surface is formed. By expanding the semiconductor wafer to which the resin film is attached together with this resin film in the surface direction of the resin film, the resin film is cut, and the semiconductor wafer is divided at the portion of the modified layer and separated into pieces Methods are known for obtaining semiconductor chips. Unlike the method using a dicing blade, this method has the advantage that in a semiconductor wafer, the formation of a cut portion by a dicing blade is not involved, more semiconductor chips can be obtained from the semiconductor wafer, and no cutting waste is generated. Have. Although there is a film-like adhesive as a device for die-bonding a semiconductor chip to a circuit formation surface of a substrate, the above dividing method is mainly used when the film-like adhesive is used as the resin film. (See Patent Document 1).

Therefore, if the above dividing method by expanding can be applied to a semiconductor wafer provided with a protective film that is an energy ray curable protective film or a cured product thereof as the resin film, such a method can be used. The method is extremely useful as a method of manufacturing a semiconductor chip provided with a protective film.

Japan JP 2012-222002

However, when a semiconductor wafer provided with a protective film-forming film or a protective film is expanded, the obtained semiconductor chip may be peeled off from the protective film-forming film or protective film after cutting and become floating. There was a problem of that. Above all, this problem is remarkable at the peripheral portion of the semiconductor chip, particularly at the corner portion.

In the present invention, a semiconductor wafer is provided with a protective film which is a cured film of a protective film-forming film or a protective film-forming film on the back surface thereof, and the semiconductor wafer is protected by expanding a modified layer formed therein. When a film for film formation or a protective film is cut, and the semiconductor wafer is divided into semiconductor chips, the film for protective film formation or the film for protective film formation which can suppress the floating of the semiconductor chip from the protective film, It aims at providing a composite sheet for protective film formation provided with a film for protective film formation, and a manufacturing method of the above-mentioned semiconductor chip.

The present invention is a film for forming an energy ray-curable protective film, wherein the film for forming a protective film has a group in which a carboxy group or a carboxy group has formed a salt in one molecule, and a polymerizable group. Provided is a film for forming a protective film, which contains a compound.

The present invention provides a composite sheet for protective film formation, which comprises a support sheet, and the protective film-forming film is provided on the support sheet.
In the present invention, a step of sticking the film for forming a protective film or the film for forming a protective film in the composite sheet for forming a protective film on a semiconductor wafer, and the film for forming the protective film after being stuck to the semiconductor wafer And forming a protective film by irradiating an energy beam onto the semiconductor wafer, and irradiating a laser beam through the protective film or the protective film-forming film so as to focus on a focal point set inside the semiconductor wafer. By forming a modified layer inside the semiconductor wafer, and the semiconductor wafer on which the modified layer is formed, together with the protective film or the protective film forming film, the protective film or the protective film forming film While expanding the protective film or the film for forming a protective film by expanding in the surface direction of the Dividing the, and a step of obtaining a plurality of semiconductor chips, and to provide a method of manufacturing a semiconductor chip.

When a semiconductor chip is produced by the method of the present invention using the protective film-forming film or the protective film-forming composite sheet of the present invention, a protective film-forming film or a protective film-forming film is formed on the back as a semiconductor wafer. The protective film, which is a cured product of the present invention, is provided with a reformed layer formed therein to expand the protective film-forming film or the protective film and to divide the semiconductor wafer into semiconductor chips. Occasionally, it is possible to suppress the floating of the semiconductor chip from the protective film or the protective film.

It is sectional drawing which shows typically the film for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip at the time of using the film for protective film formation which is not comprising the composite sheet for protective film formation. It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip at the time of using the film for protective film formation which is not comprising the composite sheet for protective film formation. It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip at the time of using the film for protective film formation which is not comprising the composite sheet for protective film formation. It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip at the time of using the composite sheet for protective film formation which integrated the protective film formation film with the support sheet previously, and was used. . It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip at the time of using the composite sheet for protective film formation which integrated the protective film formation film with the support sheet previously, and was used. . It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip at the time of using the composite sheet for protective film formation which integrated the protective film formation film with the support sheet previously, and was used. .

フ ィ ル ム Protective Film-Forming Film A protective film-forming film according to an embodiment of the present invention is an energy ray-curable protective film-forming film, and the protective film-forming film has a carboxy group or a carboxyl group in one molecule. The compound (it may be called "compound (p)" in this specification) which has the group which the carboxy group formed the salt, and the polymeric group is contained.
As described later, a composite sheet for forming a protective film can be configured by providing the film for forming a protective film on a support sheet.

The film for protective film formation is cured by irradiation of energy rays to be a protective film. This protective film is for protecting the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer or the semiconductor chip. The protective film-forming film is soft and can be easily attached to an object to be attached.
Since the film for protective film formation is energy ray curable, the protective film can be formed by curing in a shorter time than the thermosetting film for protective film formation.

In the present specification, the “protective film-forming film” means one before curing, and the “protective film” means one obtained by curing the protective film-forming film.

Examples of the protective film-forming film include those containing an energy ray-curable component (a) and a compound (p) described later. The film for protective film formation containing a compound (p) is not known conventionally.
The energy ray-curable component (a) is preferably uncured, preferably has tackiness, and is more preferably uncured and tacky.

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.
In the present specification, "energy ray curable" means the property of curing by energy ray irradiation, and "non energy ray curable" means the property of not curing even when energy ray is irradiated. Do.

When the protective film-forming film is used, the semiconductor wafer having the reformed layer formed therein is expanded in the direction of the front surface (for example, the back surface) to divide the semiconductor wafer at the site of the reformed layer. The semiconductor chip is manufactured.
In order to form the modified layer inside the semiconductor wafer, laser light may be irradiated so as to focus on the focal point set inside the semiconductor wafer. Unlike the other portions of the semiconductor wafer, the modified layer of the semiconductor wafer is denatured by laser light irradiation, and the strength is weak. Therefore, the semiconductor wafer on which the modified layer is formed is used as the semiconductor wafer of the semiconductor wafer. By expanding in the surface direction, a force is applied to the modified layer inside the semiconductor wafer, and the semiconductor wafer is broken at the portion of this modified layer, and a plurality of semiconductor chips are obtained.

The laser beam irradiated when forming the modified layer on the semiconductor wafer is preferably a laser beam in the infrared region, and more preferably a laser beam having a wavelength of 1342 nm.

Expanding the semiconductor wafer (sometimes referred to as "semiconductor wafer with protective film" in the present specification) provided with a protective film on the back surface because the protective film-forming film contains the compound (p) Therefore, when the protective film is cut and the semiconductor wafer is divided into semiconductor chips (sometimes referred to as “semiconductor chip with protective film” in the present specification), the semiconductor chip is lifted from the protective film. It can be suppressed. The same applies to a protective film-forming film, and expanding a semiconductor wafer (sometimes referred to as a "semiconductor wafer with a protective film-forming film" in this specification) having a protective film-forming film on its back surface By cutting the film for forming a protective film and dividing the semiconductor wafer into semiconductor chips (sometimes referred to as "semiconductor chip with film for forming a protective film" in this specification), the protective film is formed It is possible to suppress the floating of the semiconductor chip from the film.

The adhesion between the protective film-forming film and the silicon wafer measured by the following method is preferably 3 N / 25 mm or more. When the adhesive strength is at least the lower limit value, the effect of suppressing the floating of the semiconductor chip (not limited to the silicon chip) from the above-described protective film or the film for forming a protective film is further enhanced.
<Method of measuring adhesion between film for protective film formation and silicon wafer>
After affixing the protective film-forming film having a thickness of 25 μm to a silicon wafer, the peeling speed is 300 mm so that the surfaces of the protective film-forming film and the silicon wafer in contact with each other form an angle of 180 °. The peeling force (N / 25 mm) when peeling off the film for protective film formation from a silicon wafer is measured with 1 / min, and the measured value is the adhesion between the film for protective film formation and the silicon wafer and Do.

The adhesive strength is more preferably 3.3 N / 25 mm or more, and particularly preferably 3.6 N / 25 mm or more from the viewpoint that the above-described effect is further enhanced.

On the other hand, the upper limit value of the adhesive strength is not particularly limited. However, in the method of manufacturing a semiconductor device to be described later, the adhesive force is preferably 10 N / 25 mm or less in that it is easier to pick up a semiconductor chip with a protective film or a semiconductor chip with a film for protective film formation. It is more preferably 9 N / 25 mm or less, and particularly preferably 8 N / 25 mm or less.

The adhesive strength can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned preferable lower limit value and upper limit value. For example, the adhesive strength is preferably 3 to 10 N / 25 mm, more preferably 3.3 to 9 N / 25 mm, and particularly preferably 3.6 to 8 N / 25 mm. However, these are examples of the said adhesive force.

The adhesive strength can be adjusted, for example, by adjusting the type of the components of the protective film-forming film including the compound (p), and the content thereof, the thickness of the protective film-forming film, and the like.

When the protective film is irradiated with ultraviolet light to form a protective film, the shear strength of the protective film measured by the following method is preferably 10.5 N / 3 mm or more. When the shear strength is at least the lower limit value, the effect of suppressing the floating of the semiconductor chip from the above-described protective film or the film for forming a protective film is further enhanced.
<Shear strength of protective film>
The protective film-forming film having a thickness of 25 μm is attached to a silicon wafer, and then the protective film-forming film is irradiated with ultraviolet light under the conditions of an illuminance of 195 mW / cm ² and a light amount of 170 mJ / cm ^2. The forming film is cured to form a protective film, and the obtained protective film-coated silicon wafer is diced to form a protective film-coated silicon chip having a size of 3 mm × 3 mm. Of the obtained protective film-coated silicon chips, protection is provided. A force is applied to the surface of the protective film at a speed of 200 μm / s only to the film, and the maximum value (N / 3 mm □) of the force applied until the protective film is destroyed is the shear strength of the protective film. I assume.

The shear strength is more preferably 10.7 N / 3 mm 2 or more, and particularly preferably 11.0 N / 3 mm 2 or more from the viewpoint that the above-described effects are further enhanced.

On the other hand, the upper limit value of the shear strength is not particularly limited. For example, the shear strength is preferably 30.0 N / 3 mm 2 or less, more preferably 27.5 N / 3 mm 2 or less, and particularly preferably 25.0 N / 3 mm 2 or less. It may be 5N / 3 mm or less, 20.0 N / 3 mm or less, and 17.5 N / 3 mm or less.

The said shear strength can be suitably adjusted within the range set combining the above-mentioned lower limit and upper limit arbitrarily. For example, the shear strength is preferably 10.5 to 30.0 N / 3 mm, more preferably 10.7 to 27.5 N / 3 mm, particularly preferably 11.0 to 25.0 N / 3 mm. It may be any of 11.0 to 22.5 N / 3 mm, 11.0 to 20.0 N / 3 mm, and 11.0 to 17.5 N / 3 mm. However, these are examples of the said shear strength.

The shear strength can be adjusted, for example, by adjusting the type of the components of the protective film-forming film including the compound (p), and the content thereof, the thickness of the protective film-forming film, and the like.

The film for protective film formation preferably satisfies the conditions of both the adhesive strength and the shear strength.
As an example of such a protective film-forming film, preferably, the adhesive strength is 3 to 10 N / 25 mm, and the shear strength is 10.5 to 30.0 N / 3 mm □; more preferably, Having an adhesive strength of 3.3 to 9 N / 25 mm and a shear strength of 10.7 to 27.5 N / 3 mm □; particularly preferably, the adhesive strength is 3.6 to 8 N / 25 mm, The shear strength is, for example, 11.0 to 25.0 N / 3 mm □, the adhesive strength is 3.6 to 8 N / 25 mm, and the shear strength is 11.0 to 22.5 N / 3 mm □. The adhesive strength is 3.6 to 8 N / 25 mm, the shear strength is 11.0 to 20.0 N / 3 mm □, and the adhesive strength is 3.6 to 8 N / 25 mm Yes, the shear strength is 11 0 ~ 17.5N / 3mm □ a is one, may be either.
However, the combination of the adhesive strength and the shear strength shown here is an example.

Both the film for forming a protective film and the protective film which is a cured product thereof have an infrared range such as a laser beam (for example, a laser beam having a wavelength of 1342 nm) necessary for forming a modified layer of a semiconductor wafer. The thing with the high transmittance | permeability of (laser beam) of (1) is preferable. Both the protective film-forming film and the protective film usually show the same tendency with respect to the light transmittance.

For example, the transmittance of a laser beam having a wavelength of 1342 nm (which may be abbreviated as "film transmittance (1342 nm)" in the present specification) of the film for forming a protective film is 45% or more. Is more preferably 50% or more, and particularly preferably 55% or more. When the film transmittance (1342 nm) is equal to or more than the lower limit value, the modified layer can be more easily formed on the semiconductor wafer in the method of manufacturing a semiconductor chip described later.
The upper limit of the film transmittance (1342 nm) is not particularly limited, and may be, for example, 100%.

The transmittance of a laser beam having a wavelength of 1342 nm (sometimes abbreviated as “protective film transmittance (1342 nm)” in the present specification) of the protective film is preferably 45% or more, 50 % Or more is more preferable, and 55% or more is particularly preferable. When the protective film transmittance (1342 nm) is equal to or higher than the lower limit value, the modified layer can be more easily formed on the semiconductor wafer in the method of manufacturing a semiconductor chip described later.
The upper limit of the protective film transmittance (1342 nm) is not particularly limited, and may be, for example, 100%.

The film transmittance (1342 nm) can be adjusted, for example, by adjusting the type of the components contained in the protective film-forming film, and the content thereof, the thickness of the protective film-forming film, and the like.
The protective film transmittance (1342 nm) can be adjusted, for example, by adjusting the type of the component contained in the protective film, the content thereof, the thickness of the protective film, and the like.

The film for protective 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 is not particularly limited.
In addition, in this specification, not only in the case of the film for protective film formation, "all layers may be the same, and all layers may be the same" It means that the layers may be different, and only some of the layers may be the same. Further, “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is mutually different. It means "different".

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the film for protective film formation is more than the said lower limit, a protective film with higher protective ability can be formed. In addition, when the thickness of the protective film-forming film is equal to or less than the upper limit value, excessive thickness can be suppressed.
Here, "the thickness of the film for protective film formation" means the thickness of the whole film for protective film formation, for example, the thickness of the film for protective film formation which consists of multiple layers is a film for protective film formation. Means the total thickness of all the layers that make up.

The curing conditions for curing the protective film-forming film to form a protective film are not particularly limited as long as the protective film has a curing degree sufficient to exhibit its function, and the type of protective film-forming film Depending on the situation, it may be selected appropriately.
For example, the illuminance of the energy ray is preferably 4 to 280 mW / cm ² at the time of curing of the protective film-forming film. The light quantity of the energy ray at the time of curing is preferably 3 to 1000 mJ / cm ² .

FIG. 1 is a cross-sectional view schematically showing a protective film-forming film according to an embodiment of the present invention. 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.

The film 13 for protective film formation shown here is provided with the 1st peeling film 151 on one surface (it may be called a "1st surface" in this specification) 13a, and the said 1st surface 13a A second release film 152 is provided on the other side (which may be referred to herein as the “second side”) 13b of the opposite side.
Such a protective film-forming film 13 is suitable, for example, for storage as a roll.

The film 13 for protective film formation can be formed using the composition for protective film formation mentioned later.
The protective film-forming film 13 is energy ray curable and contains the compound (p).

Both the first release film 151 and the second release film 152 may be known ones.
The first release film 151 and the second release film 152 may be identical to each other, or may be different from each other, for example, the release forces necessary for releasing from the protective film-forming film 13 may be different from each other. May be

In the protective film-forming film 13 shown in FIG. 1, one of the first release film 151 and the second release film 152 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the resulting exposed surface. And the other of the remaining of the 1st exfoliation film 151 and the 2nd exfoliation film 152 is removed, and the generated exposed side turns into the sticking side of a support sheet.

<< Composition for protective film formation >>
The film for protective film formation can be formed using the composition for protective film formation containing the constituent material. For example, the composition for protective film formation may be coated on the formation target surface of the film for protective film formation, and dried as needed, so that the film for protective film formation can be formed on the target site. The ratio of the content of components which do not vaporize at normal temperature in the composition for forming a protective film is usually the same as the ratio of the content of the components of the film for forming a protective film. In the present specification, “normal temperature” means a temperature which is not particularly cooled or heated, ie, a normal temperature, and includes, for example, a temperature of 15 to 25 ° C. and the like.

Coating of the composition for forming a protective film may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, Examples include methods using various coaters such as a screen coater, a Mayer bar coater, and a kiss coater.

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

<Composition for forming protective film (IV-1)>
Examples of the composition for forming a protective film include a composition for forming a protective film (IV-1) containing the energy ray curable component (a) and the compound (p). The composition for protective film formation containing a compound (p) is not known conventionally.

[Compound (p)]
The compound (p) has, in one molecule thereof, a carboxy group (—C (= O) —O—H) or a group in which the carboxy group has formed a salt, and a polymerizable group.
Examples of the group in which the carboxy group has formed a salt include, for example, a group in which a carboxylate anion (—C (-O) —O ⁻ ) formed by dissociation of a proton (H ⁺ ) from the carboxy group forms a salt with a cation. Can be mentioned.

In the composition for forming a protective film (IV-1) and the compound (p) in the film for forming a protective film, the carboxy group may be undissociated from protons (in other words, the carboxy group may be left as it is) And protons may be released to form carboxylate anions.

It is speculated that the compound (p) improves the interaction between the protective film-forming film or the protective film and the semiconductor wafer or the semiconductor chip by having a carboxy group or a group in which a carboxy group forms a salt. Be done. As a result, it is assumed that the floating of the semiconductor chip from the protective film or the film for protective film formation is suppressed.

In addition, the compound (p) is incorporated in any of the polymer components in the protective film (in other words, forms a copolymer) by having a polymerizable group, and thus the protective film It is presumed that the migration to the layer (film) adjacent to the protective film is suppressed. Since the protective film-forming film finally forms a protective film by curing, the semiconductor derived from the protective film is formed by the stable presence of such a copolymer derived from the compound (p) in the protective film. It is presumed that the effect of suppressing the lift of the chip is exhibited stably.

The compound (p) having a group in which a carboxy group has formed a salt comprises one or more anion moieties and one or more cations. The anion moiety has one or more carboxylate anions per one.

That is, the number of carboxylate anions in one molecule of the compound (p) may be only one or two or more.
Similarly, the number of the anion moiety in one molecule of the compound (p) may be only one, may be two or more, and when it is two or more, all of these anion moieties are They may be the same, all different, or only some of them may be the same. That is, the anion moiety in one molecule of the compound (p) 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 not particularly limited. .
The carboxylate anion in one molecule of the compound (p) may have a group in which a carboxy group forms a salt, or only a part of a carboxy group may form a group in which a salt is formed. Usually, it is preferred that all carboxy groups constitute a salt-formed group.

The valence number of the cation in the compound (p) is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more.
The number of cations in one molecule of the compound (p) may be only one, or two or more, and in the case of two or more, these cations may be all identical. Or all of them may be different, or only part of them may be identical. That is, the cation in one molecule of the compound (p) 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 not particularly limited.
The cation in one molecule of the compound (p) may form a group in which a carboxy group forms a salt, or only a part of the cation may form a group in which a salt is formed. Preferably, all the carboxy groups constitute a salt-formed group.

In one molecule of the compound (p), the group in which the carboxy group formed a salt may be only one, may be two or more, or two or more, all of these groups are They may be the same, all different, or only some of them may be the same. That is, in one molecule of the compound (p), the group in which the carboxy group formed a salt 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 is not particularly limited.

As a compound (p) which has the group which the carboxy group formed the salt, various forms are mentioned according to the kind and valence of a cation. As such compound (p), more specifically, for example, one composed of one anion moiety and one cation; composed of two or more anion moieties and one cation And those composed of one anion moiety and two or more cations; and those composed of two or more anion moieties and two or more cations.

The compound (p) having a group in which a carboxy group has formed a salt is electrically neutral as a whole molecule, that is, the total value of the valences of cations in one molecule of the compound (p) and the valences of anions It is preferable that the total value of is the same.

The cation is not particularly limited, and may be any of an inorganic cation and an organic cation.

Among the above cations, as inorganic cations, for example, ions of alkali metals such as lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), etc .; magnesium ion (Mg ²⁺ ), calcium ion (Ca ²⁺ ) Ions of alkaline earth metals such as ²⁺ ) and barium ions (Ba ²⁺ ); ions of typical metals such as aluminum ions (Al ³⁺ ), zinc ions (Zn ²⁺ ) and tin ions (Sn ²⁺ and Sn ⁴⁺ ); copper ions Ions of transition metals such as Cu ⁺ , Cu ²⁺ ), iron ions (Fe ²⁺ , Fe ³⁺ ), manganese ions, nickel ions; and nonmetal ions such as ammonium ion (NH ₄ ⁺ ).
For example, when the cation is a sodium ion, the group in which the carboxy group has formed a salt is represented by the formula “—C (= O) —O ⁻ Na ⁺ ”.

Among the cations, examples of the organic cation include cations derived from an amine compound, quaternary ammonium cations and the like.
Examples of the cation derived from the amine compound include cations in which a primary amine, a secondary amine or a tertiary amine is protonated.
Examples of the quaternary ammonium cation include cations in which four monovalent hydrocarbon groups are bonded to one nitrogen atom.

Among the above cations, preferred examples of inorganic cations which are nonmetallic ions and organic cations are, for example, the general formula “(Z ¹ ) ₄ N ⁺ (wherein Z ¹ is a hydrogen atom, an alkyl group Or a plurality of Z ^{1 s} may be the same or different from each other, and when two or more Z ^{1 s} are alkyl groups, these alkyl groups may combine with each other to form a ring And the cation represented by "is good".
The group formed by such a cation, in which the carboxy group has formed a salt, has a general formula “—C (= O) —O ⁻ N ⁺ (Z ¹ ) ₄ (wherein Z ¹ is as defined above) It is represented by ".)".

In the general formula, a plurality (ie, four) of Z ¹ may be all the same, all may be different, or only some of them may be the same.

The alkyl group for Z ¹ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.
The aryl group in Z ¹ may be monocyclic or polycyclic.

The carbon number of the linear or branched alkyl group in Z ¹ is preferably 1 to 10. As such an alkyl group having a carbon number, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-ethyl -1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methyl group Hexyl, 5-methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 4 , 4-Dimethylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 4-ethylpentyl, 2,2,3-trimethylbutyl, 1-propylbutyl, n-octyl Group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dime Hexyl group, 4,4-dimethyl hexyl group, 5,5-dimethyl hexyl group, 1-propyl pentyl group, 2-propyl pentyl group, nonyl group, decyl group.
The carbon number of the linear or branched alkyl group for Z ¹ may be, for example, any of 1 to 8, 1 to 5, and 1 to 3, and these are examples of the carbon number. is there.

The carbon number of the cyclic alkyl group for Z ¹ is preferably 3 to 10. As such an alkyl group having a carbon number, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group And 2-adamantyl group and tricyclodecyl group.
The carbon number of the cyclic alkyl group for Z ¹ may be, for example, any of 3 to 8 and 3 to 6, but these are examples of the carbon number.

When two or more (that is, two, three or four) Z ^{1 s} are the alkyl groups, the nitrogen atoms to which these two or more alkyl groups are bound to each other and these alkyl groups are bound And may form a ring together with The bonding position of two or more alkyl groups in this case is not particularly limited, and the ring formed may be either monocyclic or polycyclic.

The carbon number of the aryl group in Z ¹ is preferably 6 to 20. As the aryl group having such a carbon number, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (alias: dimethylphenyl group) And the like, and those in which one or more hydrogen atoms of these aryl groups are further substituted by these aryl groups or the above-mentioned alkyl group in Z ¹ are also mentioned. The aryl group having such a substituent preferably has 6 to 20 carbon atoms including the substituent.

The compound (p) may have only a carboxy group in one molecule, or may have only a group in which a carboxy group has formed a salt, and a carboxy group and a carboxy group have a salt. It may have both of the formed groups.

The number of groups in which a carboxy group and a carboxy group have formed a salt in one molecule of the compound (p) may be only one or two or more.
The total number of carboxy groups and groups in which carboxy groups have formed a salt in one molecule of the compound (p) is not particularly limited, but is preferably 1 to 3, and more preferably 1 to 2. preferable.

In the compound (p), the position of the carboxy group and the group in which the carboxy group formed a salt is not particularly limited. For example, in the compound (p) having a chain structure, these groups may be bonded to the end of the main chain (in other words, they may be the end of the main chain) or non-terminal It may be done. In the present specification, the “main chain” means a chain backbone having the largest number of atoms constituting it.

In the compound (p), the number of carboxy groups or groups in which a carboxy group forms a salt, which is bonded to one atom, may be only one, or two or more (for example, the atoms And when it is a carbon atom, it may be 2 to 4).

Examples of the polymerizable group in the compound (p) include a group having a polymerizable unsaturated bond, and a group having an ethylenically unsaturated bond (that is, a double bond, C = C) is particularly preferable. .

The number of the polymerizable groups in one molecule of the compound (p) may be only one, or two or more, but it is preferably one to three, and one to two. It is more preferable that

In the compound (p), the position of the polymerizable group is not particularly limited. For example, in the compound (p) having a chain structure, the polymerizable group may be at the terminal or non-terminal of the main chain. However, usually, the polymerizable group is preferably at the end of the main chain.

The compound (p) preferably has a carboxy group or a group in which a carboxy group has formed a salt, and a polymerizable group, and further preferably has an ester bond in addition to these groups, and as the ester bond, a carboxylic acid ester It is more preferable to have a bond (ie, a group represented by the formula “—C (= O) —O—”, a carbonyloxy group). By using such a compound (p), the effect of suppressing the floating of the semiconductor chip from the protective film or the film for protective film formation is further enhanced.

The number of ester bonds in one molecule of the compound (p) may be only one, or two or more, but is preferably 1 to 4, and is preferably 1 to 3. It is more preferable that

Preferred examples of the compound (p) include aliphatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester (in other words, a hydrogen atom of one carboxy group of aliphatic dicarboxylic acid is a (meth) acryloyloxyalkyl group) A compound substituted with a) an aromatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester (in other words, a compound in which a hydrogen atom of one carboxy group of an aromatic dicarboxylic acid is substituted with a (meth) acryloyloxyalkyl group) A compound in which the carboxy group of the aliphatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester is substituted by a group in which the above-mentioned carboxy group has formed a salt; and the above-mentioned aromatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester The carboxy group is the above-mentioned carboxy group Compounds substituted with groups forming a salt.

The aliphatic dicarboxylic acid is a compound having two carboxy groups, and the moiety other than these carboxy groups is a linear, branched or cyclic non-aromatic divalent hydrocarbon group. means.
The carbon number of the hydrocarbon group is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 6, and for example, any of 2 to 5 and 2 to 4 It may be
The hydrocarbon group is preferably an alkylene group.

The aromatic dicarboxylic acid means a compound having two carboxy groups, and the moiety other than these carboxy groups is a divalent aromatic hydrocarbon group (that is, an arylene group).
The aromatic hydrocarbon group may be monocyclic or polycyclic.
As said aromatic hydrocarbon group, the bivalent group (namely, arylene group) of the structure which remove | eliminated 1 hydrogen atom from the said aryl group in Z ¹ is mentioned, for example.
The carbon number of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 12.

An aliphatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester and an alkyl group in which the carboxy group is bonded to a (meth) acryloyloxy group in a compound in which the above-mentioned carboxy group is substituted by a group forming a salt ( In other words, the alkylene group in the (meth) acryloyloxyalkyl group) may be linear, branched or cyclic, and may have both a chain structure and a cyclic structure, It is preferably linear or branched.

The carbon number of the linear or branched alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 6, For example, it may be any of 2 to 5 and 2 to 4.
The carbon number of the cyclic alkyl group is not particularly limited, but is preferably 3 to 10, more preferably 4 to 8, and particularly preferably 5 to 6.

The compound (p) has a chain structure, and the carboxy group or the group in which the carboxy group formed a salt, and the polymerizable group are both terminal portions of the main chain, and an ester is added to the non-terminal portion of the main chain. Those having a bond are preferred.

As such a preferable compound (p), aliphatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester; carboxy group of the aliphatic dicarboxylic acid mono (meth) acryloyloxyalkyl ester forms a salt with the above-mentioned carboxy group And compounds substituted by the substituted group.

Particularly preferable compounds (p) are 1- [2- (acryloyloxy) ethyl] succinic acid (that is, mono (2-acryloyloxyethyl) succinic acid), CH ₂ CHCH—C (= O) —O —CH ₂ CH ₂ —O—C (= O) —CH ₂ CH ₂ —C (= O) —OH); succinic acid 1- [2- (methacryloyloxy) ethyl] (ie, CH ₂ CC (— _{CH 3) -C (= O)} -O-CH 2 CH 2 -O-C (= O) -CH 2 CH 2 -C (= O) -OH); glutaric acid l- [2- (acryloyloxy) Ethyl] (ie, CH ₂ CHCH—C (= O) —O—CH ₂ CH ₂ —O—C (= O) —CH ₂ CH ₂ CH ₂ —C (= O) —OH); Succinic acid The carboxy group of-[2- (acryloyloxy) ethyl] is Compound in which a carboxy group is substituted by a salt-formed group; compound in which a carboxy group of succinic acid 1- [2- (methacryloyloxy) ethyl] is substituted by the above-mentioned carboxy group by a salt-formed group; glutaric acid The compound by which the carboxy group of 1- [2- (acryloyloxy) ethyl] was substituted by the group which the above-mentioned carboxy group formed the salt is mentioned.

The molecular weight of the compound (p) is not particularly limited, but is preferably 100 to 1000, more preferably 100 to 700, still more preferably 100 to 500, and still more preferably 100 to 300. Particularly preferred.

The composition (IV-1) for forming a protective film and the compound (p) contained in the film for forming a protective 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 ratio of the content of the compound (p) to the total content of components other than the solvent in the protective film-forming composition (IV-1) (that is, the total mass of the protective film-forming film in the protective film-forming film) The ratio of the content of the compound (p) to is preferably 0.15% by mass or more, more preferably 0.2% by mass or more, particularly preferably 0.25% by mass or more preferable. When the ratio of the content is equal to or more than the lower limit value, the effect of suppressing the floating of the semiconductor chip from the protective film or the film for protective film formation becomes higher.

On the other hand, the upper limit of the ratio of the content (the ratio of the content of the compound (p) to the total mass of the film for protective film formation in the film for protective film formation) is not particularly limited. However, the effect of the excessive use of the compound (p) is avoided, with the result that the curing degree of the protective film becomes higher and the characteristic of the protective film is further improved, the content ratio is 3% by mass or less Is preferable, 2% by mass or less is more preferable, and 1% by mass or less is particularly preferable.

The ratio of the content (the ratio of the content of the compound (p) to the total mass of the protective film-forming film in the protective film-forming film) is set by arbitrarily combining the above-described preferable lower limit value and upper limit value. It can adjust suitably within the limits. For example, the content ratio is preferably 0.15 to 3% by mass, more preferably 0.2 to 2% by mass, and particularly preferably 0.25 to 1% by mass. However, these are examples of the ratio of the said content.

[Energy ray curable component (a)]
The energy ray curable component (a) is a component which is cured by irradiation of energy rays, and is also a component for imparting film forming property, flexibility and the like to the protective film forming 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. At least a part of the polymer (a1) may or may not be crosslinked by a crosslinking agent (f) described later.
In the present specification, weight-average molecular weight means polystyrene equivalent value measured by gel permeation chromatography (GPC) unless otherwise noted.

(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 polymerizing 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 contained in another compound include, for example, a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (in other words, one or two hydrogen atoms of amino group are other than hydrogen atoms) And the like, an epoxy group 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 other than acrylic monomers (in other words, non-acrylic monomers) may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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 Saturated alcohol (in other words, unsaturated alcohol having no (meth) acryloyl skeleton) and the like can be 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.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (that is, monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid and maleic acid And ethylenically unsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate Ester etc. are mentioned.

The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, and more 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 protective 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) for forming a protective film, the ratio of the content of the acrylic resin (a1-1) to the total mass of the composition (IV-1) for forming a protective film is 1 to 40 mass%. The content is preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

・ 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;
An acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound 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 protective film formed by hardening becomes larger because the ratio of the said content is such a range. In the case where the energy ray curable compound (a12) is a monofunctional compound (ie, having one group in one molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (ie, having two or more of the groups in one molecule), the upper limit of the content ratio exceeds 100 mol%. There is.

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.

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

The composition (IV-1) for forming a protective film and the polymer (a1) contained in the film for forming a protective 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 Meta) 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 (tri) Cyclodecane dimethylol di (meth) a 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2 , 2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydro Difunctional (meth) acrylates such as shea 1,3-di (meth) acryloxy propane;
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 (h) described later, but in the present invention, it is handled as the compound (a2).

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

The composition for forming a protective film (IV-1) and the compound (a2) contained in the film for forming a protective 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.

[Polymer having no energy ray curable group (b)]
When the composition for forming a protective film (IV-1) and the film for forming a protective film contain the compound (a2) as the energy ray curable component (a), a polymer further having no energy ray curable group It is preferable to also contain (b).
The polymer (b) may be at least a part of which is crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.

As a polymer (b) which does not have an energy ray curable group, for example, an acrylic polymer, phenoxy resin, urethane resin, polyester, rubber resin, acrylic urethane resin, polyvinyl alcohol (PVA), butyral resin, polyester urethane Resin etc. are mentioned.
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 be a copolymer of one or more acrylic monomers and a monomer other than one or more acrylic monomers (that is, a non-acrylic monomer).

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 the crosslinking agent (f), for example, the reactive functional group in the polymer (b) is a crosslinking agent (f What reacted with) is mentioned.
The reactive functional group may be appropriately selected depending on the type of the crosslinking agent (f) and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, a hydroxyl group having high reactivity with the isocyanate group. Is preferred. When the crosslinking agent (f) is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amido group and the like, among which a carboxy having a high reactivity with the epoxy group Groups are preferred. 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 25 The content is preferably in the range of 2% by mass to 20% by 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 from 10000 to 2,000,000 from the viewpoint that the film forming property of the composition for forming a protective film (IV-1) becomes better. Is preferable, and 100000 to 1.500000 is more preferable.

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

Examples of the composition for forming a protective film (IV-1) include those containing any one or both of the polymer (a1) and the compound (a2) in addition to the compound (p). And when the composition for protective film formation (IV-1) contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an energy ray curable group, and in this case, It is also preferable to contain the above (a1). The composition for forming a protective film (IV-1) contains neither the compound (a2) but the polymer (a1) and the polymer (b) having no energy ray curable group. It may be

When composition (IV-1) for protective film formation contains the said polymer (a1), the said compound (a2), and the polymer (b) which does not have an energy beam curable group, the composition for protective film formation In (IV-1), the content of the compound (a2) is 10 to 100 parts by mass relative to the total content of the polymer (a1) and the polymer (b) having no energy ray curable group. The amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.

In the composition for forming a protective film (IV-1), the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group relative to the total content of components other than the solvent Ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group with respect to the total mass of the film for protection film formation in the film for formation of a protection film The proportion) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass, for example, 20 to 60% by mass, and 25 to 50% by mass. It may be any of 50% by mass. The energy ray curability of the film for protective film formation becomes more favorable because the ratio of the said total content is such a range.

When the composition for forming a protective film (IV-1) contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the composition for forming a protective film (IV-1) In the film for protective film formation, the content of the polymer (b) is preferably 50 to 400 parts by mass with respect to 100 parts by mass of the content of the energy ray curable component (a), The amount is more preferably up to 350 parts by mass, and particularly preferably 150 to 300 parts by mass. When the content of the polymer (b) is in such a range, the energy ray curability of the film for protective film formation becomes better.

The composition (IV-1) for forming a protective film is a photopolymerization other than the energy ray curable component (a), the polymer (b) having no energy ray curable group and the compound (p) according to the purpose. Initiator (c), filler (d), coupling agent (e), crosslinking agent (f), colorant (g), thermosetting component (h), curing accelerator (i), and general purpose additives You may contain 1 type, or 2 or more types selected from the group which consists of (z).
For example, the film for protective film formation formed by using the composition (IV-1) for protective film formation containing the said energy beam curable component (a) and the thermosetting component (h) is heated by heating The adhesion to the adherend is improved, and the strength of the protective film formed from the protective film-forming film is also improved.

[Photoinitiator (c)]
Examples of the photopolymerization initiator (c) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acyl phosphine oxide compounds such as phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide Compounds; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime Peroxide compounds; Diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methyl) Vinyl) phenyl] propanone; 2-chloro anthraquino And the like.
Further, as the photopolymerization initiator (c), for example, quinone compounds such as 1-chloroanthraquinone and the like; photosensitizers such as amine and the like can also be used.

The composition (IV-1) for forming a protective film may contain only one type of photoinitiator, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.

When a photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the composition for forming a protective film (IV-1) is 100 parts by mass of the energy ray curable compound (a) The amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 15 parts by mass, and particularly preferably 0.05 to 10 parts by mass.

[Filler (d)]
When the film for protective film formation contains a filler (d), adjustment of a thermal expansion coefficient of the protective film obtained by hardening the film for protective film formation becomes easy. And the reliability of the package obtained using the composite sheet for protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation object of a protective film. Moreover, when the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced and heat dissipation can also be improved.
As a filler (d), what consists of heat conductive materials is mentioned, for example.

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.

The average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. . When the average particle diameter of the filler (d) is in such a range, it is possible to suppress the decrease in the light transmittance of the protective film while maintaining the adhesiveness to the object on which the protective film is to be formed.
In the present specification, “average particle size” means the value of particle size (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve determined by the laser diffraction scattering method, unless otherwise specified. .

The composition (IV-1) for forming a protective film and the filler (d) contained in the film for forming a protective 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 filler (d) is used, in the composition (IV-1) for forming a protective film, the ratio of the content of the filler (d) to the total content of all the components other than the solvent The ratio of the content of the filler (d) to the total mass of the protective film-forming film in the film is preferably 10 to 85 mass%, more preferably 20 to 80 mass%, It is particularly preferable that it is ̃75 mass%, and it may be, for example, 40 ̃70 mass%, and any of 45 ̃65 mass%. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.

[Coupling agent (e)]
By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesiveness of the protective film-forming film to the adherend can be improved. Further, by using the coupling agent (e), the protective film obtained by curing the protective film-forming film is improved in water resistance without impairing the heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy ray curable component (a), the polymer (b) having no energy ray curable group, etc. It is more preferable that it is a silane coupling agent.
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 composition (IV-1) for forming a protective film and the coupling agent (e) contained in the film for forming a protective 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 the coupling agent (e) is used, the content of the coupling agent (e) in the protective film-forming composition (IV-1) and the film for protective film formation is the energy ray-curable component (a) and the energy The amount is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the total content of the polymer (b) having no linear curable group. 0.1 to 5 parts by mass 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 protective film formation to the adherend is improved. The effect of using the coupling agent (e) can be obtained more remarkably. 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)]
By crosslinking the energy beam curable component (a) described above and the polymer (b) having no energy beam curable group using the crosslinking agent (f), the initial adhesion and cohesion of the film for protective film formation You can adjust the power.

Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate type crosslinking agents (that is, crosslinking agents having a metal chelate structure), and aziridine type crosslinking agents (that is, aziridinyl groups). Crosslinking agents) and the like.

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 reactant with a molecule active hydrogen-containing compound. Examples of the adduct include xylylene diisocyanate adduct of trimethylolpropane as described later, and the like. Also, "terminated isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at the terminal of the molecule.

More specifically, examples of the organic polyvalent isocyanate compound include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane- 4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; Any of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate in the hydroxyl groups of all or part of a polyol such as methylolpropane Compounds or species or two or 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 polyvalent isocyanate compound as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group. When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the energy ray-curable group-free polymer (b) has a hydroxyl group, the crosslinking agent (f) and energy ray-curable A crosslinked structure can be simply introduced into the protective film-forming film by the reaction with the component (a) or the polymer (b) having no energy ray-curable group.

The composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective 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 for forming a protective film (IV-1) is a weight having no energy ray curable component (a) and no energy ray curable group The amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total content of the combined (b). Being particularly preferred. When the content of the crosslinking agent (f) is equal to or more than the lower limit value, the effect of using the crosslinking agent (f) can be more remarkably obtained. 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.

[Colorant (g)]
Examples of the colorant (g) 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, naphthol dyes, azomethine dyes, benzimidazo The Systems dyes, pyranthrone pigments and threne dyes.

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 composition (IV-1) for forming a protective film and the colorant (g) contained in the film for forming a protective 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 colorant (g) is used, the content of the colorant (g) in the composition for forming a protective film (IV-1) and the film for forming a protective film may be appropriately adjusted according to the purpose. For example, in the case of adjusting the printing visibility by adjusting the content of the coloring agent (g) and adjusting the light transmittance of the protective film, the composition (IV-1) for forming a protective film may be other than the solvent. The ratio of the content of the colorant (g) to the total content of all the components (that is, the ratio of the content of the colorant (g) to the total mass of the film for protective film formation in the film for protective film formation) is The content is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass. The effect by using a coloring agent (g) is acquired more notably by the said content of a coloring agent (g) being more than the said lower limit. Moreover, the excess use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.

[Thermosetting component (h)]
The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, The combination and ratio of can be selected arbitrarily.

As a thermosetting component (h), 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 (h1) and a thermosetting agent (h2).
The composition for forming a protective film (IV-1) and the epoxy thermosetting resin contained in the film for forming a protective film may be only one type, or two or more types, in the case of two or more types, Combinations and ratios can be selected arbitrarily.

・ Epoxy resin (h1)
As an epoxy resin (h1), 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 (h1), 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 package obtained using the composite sheet for protective 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 (h1) is not particularly limited, but is preferably 300 to 30000, and is 400 to 10000, from the viewpoint of the curability of the film for protective film formation and the strength and heat resistance of the protective film. And more preferably 500 to 3,000.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.

As the epoxy resin (h1), one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be optionally selected.

・ Heat curing agent (h2)
The heat curing agent (h2) functions as a curing agent for the epoxy resin (h1).
As a thermosetting agent (h2), 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 thermosetting agents (h2), as a phenol-based curing agent having a phenolic hydroxyl group, for example, polyfunctional phenol resin, biphenol, novolak-type phenol resin, dicyclopentadiene-based phenol resin, aralkyl phenol resin and the like can be mentioned.
Among the thermosetting agents (h2), examples of amine-based curing agents having an amino group include dicyandiamide.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (h2) 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 unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenol-based curing agent is used as the heat-curing agent (h2), the heat-curing agent (h2) preferably has a high softening point or glass transition temperature, from the viewpoint that the removability of the protective film from the support sheet is improved. .

Among thermosetting agents (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl phenol resin and the like is preferably 300 to 30,000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
Among the thermosetting agents (h2), for example, the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

A thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combination and ratio can be selected arbitrarily.

When the thermosetting component (h) is used, the content of the thermosetting agent (h2) in the composition for forming a protective film (IV-1) and the film for forming a protective film is the content of the epoxy resin (h1) 100 The amount is preferably 0.01 to 20 parts by mass with respect to the parts by mass.

When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, epoxy resin (h1) and heat) in the composition for forming a protective film (IV-1) and the film for forming a protective film The total content of the curing agent (h2) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b) having no energy ray curable group.

[Hardening accelerator (i)]
A hardening accelerator (i) is a component for adjusting the hardening speed of the film for protective film formation.
Preferred curing accelerators (i) 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; tributylphosphine, diphenylphosphine, triphenylphosphine and the like Organic phosphines; tetraphenylboronium salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

As the curing accelerator (i), one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be optionally selected.
When the curing accelerator (i) is used, the content of the protective film-forming composition (IV-1) and the content of the curing accelerator (i) of the protective film-forming film are not particularly limited, and it depends on the components used in combination. It may be selected as appropriate.

[General purpose additive (z)]
The general purpose additive (z) may be a known one and can be optionally selected according to the purpose, and is not particularly limited. Preferred examples of the general-purpose additive (z) include plasticizers, antistatic agents, antioxidants, gettering agents and the like.

The composition (IV-1) for forming a protective film and the general-purpose additive (z) contained in the film for forming a protective 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 the general-purpose additive (z) is used, the content of the protective film-forming composition (IV-1) and the content of the general-purpose additive (z) of the protective film-forming film are not particularly limited, and may be appropriately selected depending on the purpose. do it.

[solvent]
The composition for forming a protective film (IV-1) preferably further contains a solvent. The composition for forming a protective film (IV-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (alias: 2-methylpropan-1-ol), 1-butanol and the like Alcohols such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides such as dimethylformamide and N-methyl pyrrolidone (ie, compounds having an amide bond).
The solvent contained in the composition for forming a protective film (IV-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 composition (IV-1) for forming a protective film is methyl ethyl ketone, toluene, ethyl acetate or the like in that the components contained in composition (IV-1) for forming a protective film can be mixed more uniformly. Is preferred.

<< Method of producing composition for forming protective film >>
The composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending the respective 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.

製造 Method of Producing Protective Film-Forming Film The protective film-forming film can be produced by coating the protective film-forming composition on a release film (preferably the release-treated surface thereof) and drying it as required. . The manufacturing method at this time is as described above.
In addition, for example, as shown in FIG. 1, the film for protective film formation is normally stored in the state in which the peeling film was bonded together by the both surfaces. To that end, a release film (preferably a release-treated surface) is preferably formed on the exposed surface (surface opposite to the side provided with the release film) of the protective film-forming film formed on the release film as described above. You just need to paste

使用 Method of Use of Protective Film-Forming Film As described above, the protective film-forming film can be formed on a support sheet to form a protective film-forming composite sheet. The composite sheet for protective film formation is stuck on the back surface (surface on the opposite side to the electrode formation surface) of the semiconductor wafer by the protective film formation film. Thereafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.

On the other hand, the protective film-forming film may be provided first on the back surface of the semiconductor wafer, not on the support sheet. For example, first, a protective film-forming film is attached to the back surface of the semiconductor wafer, and a supporting sheet is attached to the exposed surface of the protective film-forming film (the surface opposite to the side attached to the semiconductor wafer) Or, the film for forming a protective film in the attached state is irradiated with energy rays to be cured to form a protective film, and then the exposed surface of this protective film (the surface on the opposite side to the side attached to the semiconductor wafer) The support sheet is pasted together to make a composite sheet for forming a protective film. Thereafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.

複合 Composite Sheet for Forming Protective Film The composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet, and the film for forming a protective film is provided on the support sheet.

In the present invention, even after the protective film-forming film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film-forming film (in other words, the support sheet and the protective film) is maintained, This laminated structure is referred to as a "protective film-forming composite sheet".

The thickness of the semiconductor wafer to be used for the composite sheet for protective film formation of the present invention is not particularly limited, but is preferably 30 to 1000 μm from the viewpoint of easier division into semiconductor chips described later. More preferably, it is 100 to 400 μm.
Hereinafter, the configuration of the protective film-forming composite sheet will be described in detail.

Support Sheet The support sheet may be formed of a single layer (single layer), or may be formed of two or more layers. When the support sheet comprises a plurality of layers, the plurality of layers may be identical to or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

As a preferable support sheet, for example, a substrate is provided, and a pressure-sensitive adhesive layer is laminated in direct contact on the substrate (in other words, the substrate and the pressure-sensitive adhesive layer are laminated in direct contact in this order) A substrate, an intermediate layer and a pressure-sensitive adhesive layer laminated in this order in direct contact with each other in the thickness direction; and those consisting only of a substrate.
Examples of the composite sheet for protective film formation of the present invention will be described below for each type of such a support sheet, with reference to the drawings.

FIG. 2: is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this 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 1A for protective film formation shown here is provided with the base material 11, the adhesive layer 12 is provided on the base material 11, and the protective film formation film 13 is provided on the adhesive layer 12. The support sheet 10 is a laminate of the base 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming composite sheet 1A is one side of the support sheet 10 (herein, "first side" And a protective film-forming film 13 is laminated on the substrate 10a). In addition, the protective film-forming composite sheet 1A further includes a peeling film 15 on the protective film-forming film 13.

In the composite sheet 1A for protective film formation, the pressure-sensitive adhesive layer 12 is laminated on one surface (sometimes referred to as “first surface” in the present specification) 11 a of the substrate 11. A protective film-forming film 13 is laminated on the entire surface 12a of one surface (that is, the surface on the side opposite to the substrate 11, which may be referred to as "first surface" in this specification). The jig adhesive layer 16 is laminated on a part of the first surface 13 a of the film 13, that is, the area near the peripheral portion, and the jig adhesive of the first surface 13 a of the protective film formation film 13. A release film 15 is laminated on the side on which the layer 16 is not laminated and the side 16 a (upper surface and side surface) of the jig adhesive layer 16 not in contact with the protective film-forming film 13.

In the protective film-forming composite sheet 1A, the protective film-forming film 13 is energy beam curable and contains the compound (p).

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 1A for protective film formation shown in FIG. 2 has the back surface of a semiconductor wafer (not shown) attached to the first surface 13a of the protective film formation film 13 with the release film 15 removed. The upper surface of the surface 16 a of the tool adhesive layer 16 is used by being attached to a jig such as a ring frame.

FIG. 3 is a cross-sectional view schematically showing a composite sheet for protective film formation according to another embodiment of the present invention.
The composite sheet 1B for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film-forming film 13 is laminated on the entire first surface 12a of the pressure-sensitive adhesive layer 12 The release film 15 is laminated on the entire surface of the first surface 13 a of the protective film-forming film 13.

In the protective film-forming composite sheet 1B, the protective film-forming film 13 is energy beam curable and contains the compound (p).

The composite sheet 1B for protective film formation shown in FIG. 3 is a semiconductor wafer (not shown) on the central region of the first surface 13a of the protective film formation film 13 with the release film 15 removed. And the area in the vicinity of the peripheral portion is used by being attached to a jig such as a ring frame.

FIG. 4 is a cross-sectional view schematically showing a composite sheet for protective film formation according to still another embodiment of the present invention.
The composite sheet 1C for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for protective film formation, the support sheet 10 consists only of the base material 11. Then, the protective film-forming film 13 is laminated on the first surface 11 a of the substrate 11 (the first surface 10 a of the support sheet 10), and a part of the first surface 13 a of the protective film-forming film 13, that is, the peripheral portion The jig adhesive layer 16 is laminated in the vicinity area, and the area where the jig adhesive layer 16 is not laminated in the first surface 13a of the protective film forming film 13, and the jig adhesive layer A release film 15 is laminated on the 16 surfaces 16a (upper surface and side surface).

In the protective film-forming composite sheet 1C, the protective film-forming film 13 is energy beam curable and contains the compound (p).

Similar to the composite sheet 1A for protective film formation shown in FIG. 2, the composite sheet 1C for protective film formation shown in FIG. 4 is on the first surface 13a of the film 13 for protective film formation with the release film 15 removed. The back surface of a semiconductor wafer (not shown) is attached, and the upper surface of the surface 16a of the adhesive layer 16 for a jig is used by being attached to a jig such as a ring frame.

FIG. 5 is a cross-sectional view schematically showing a composite sheet for protective film formation according to still another embodiment of the present invention.
The composite sheet for protective film formation 1D shown here is the same as the composite sheet for protective film formation 1C shown in FIG. 4 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1D, the protective film-forming film 13 is laminated on the first surface 11a of the substrate 11, and the release film 15 is laminated on the entire first surface 13a of the protective film-forming film 13. It is done.

In the protective film-forming composite sheet 1D, the protective film-forming film 13 is energy beam curable and contains the compound (p).

The composite sheet 1D for protective film formation shown in FIG. 5 is the same as the composite sheet 1B for protective film formation shown in FIG. 3 with the release film 15 removed, on the first surface 13a of the film 13 for protective film formation. Among them, the back surface of a semiconductor wafer (not shown) is attached to a partial region on the center side, and the region in the vicinity of the peripheral portion is attached to a jig such as a ring frame and used.

FIG. 6 is a cross-sectional view schematically showing a composite sheet for protective film formation according to still another embodiment of the present invention.
The composite sheet 1E for protective film formation shown here is the same as the composite sheet 1B for protective film formation shown in FIG. 3 except that the shape of the film for protective film formation is different. That is, the composite sheet 1E for protective film formation is provided with the base material 11, the adhesive layer 12 is provided on the base material 11, and the protective film formation film 23 is provided on the adhesive layer 12. The support sheet 10 is a laminate of the base 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming film 23 is laminated on the first surface 10 a of the support sheet 10. Have the following configuration. Further, the protective film-forming composite sheet 1E further includes a peeling film 15 on the protective film-forming film 23.

In the protective film-forming composite sheet 1E, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and a protective film is formed on a part of the first surface 12a of the pressure-sensitive adhesive layer 12, ie, the central region. Film 23 is laminated. Then, in the first surface 12 a of the pressure-sensitive adhesive layer 12, the area 23 a of the protective film formation film 23 that is not in contact with the pressure-sensitive adhesive layer 12 (the upper surface The release film 15 is laminated on the side surface).

When the protective film-forming composite sheet 1E is viewed from above from above and planarly viewed, the protective film-forming film 23 has a smaller surface area than the pressure-sensitive adhesive layer 12, and has, for example, a circular shape.

In the protective film-forming composite sheet 1E, the protective film-forming film 23 is energy beam curable and contains the compound (p).

The composite sheet 1E for protective film formation shown in FIG. 6 has the back surface of a semiconductor wafer (not shown) attached to the surface 23a of the protective film formation film 23 in a state where the release film 15 is removed. The area | region where the film 23 for protective film formation is not laminated | stacked among 12 1st surface 12a is stuck on jigs, such as a ring frame, and is used.

In addition, in the composite sheet 1E for protective film formation shown in FIG. 6, in the area | region where the film 23 for protective film formation is not laminated | stacked among the 1st surfaces 12a of the adhesive layer 12, what is shown in FIG. The adhesive layer for jig | tool may be laminated | stacked similarly to (not shown). Similar to the composite sheet for protective film formation shown in FIGS. 2 and 4, the composite sheet 1E for protective film formation provided with such an adhesive layer for jigs has a ring frame for the surface of the adhesive layer for jigs. It is stuck on a jig etc. and used.

Thus, the composite sheet for protective film formation may be provided with the adhesive layer for jigs, regardless of the form of the support sheet and the film for protective film formation. However, generally, as shown in FIGS. 2 and 4, as a composite sheet for protective film formation provided with a jig adhesive layer, one provided with a jig adhesive layer on a protective film formation film Is preferred.

The composite sheet for protective film formation which concerns on one Embodiment of this invention is not limited to what is shown in FIGS. 2-6, A part of what is shown in FIGS. 2-6 in the range which does not impair the effect of this invention The configuration of the above may be changed or deleted, or another configuration may be added to those described above.

For example, in the composite sheet for protective film formation shown in FIGS. 4 and 5, an intermediate layer may be provided between the substrate 11 and the protective film formation film 13. That is, in the composite sheet for protective film formation of the present invention, the support sheet may be configured such that the base material and the intermediate layer are laminated in this thickness direction in this order. The intermediate layer can be selected arbitrarily according to the purpose.
Moreover, in the composite sheet for protective film formation shown in FIG.2, FIG3 and FIG.6, 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 protective 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 in the thickness direction. Here, the intermediate layer is the same as the intermediate layer which may be provided in the composite sheet for protective film formation shown in FIGS. 4 and 5.
In the composite sheet for protective film formation shown in FIGS. 2 to 6, the layer other than the intermediate layer may be provided at an arbitrary place.
Moreover, in the composite sheet for protective film formation, a clearance may be partially generated between the release film and the layer in direct contact with the release film.
Moreover, in the composite sheet for protective film formation, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

In the protective film-forming composite sheet of the present invention, as described later, it is preferable that the layer such as the pressure-sensitive adhesive layer which is in direct contact with the protective film-forming film of the support sheet be non-energy ray curable. . Such a composite sheet for protective film formation enables easier pickup of the semiconductor chip with a protective film.

The support sheet may be transparent or opaque, and may be colored according to the purpose.
Among them, in the present invention in which the protective film-forming film has energy ray curability, it is preferable that the support sheet transmits energy rays.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, when the protective film-forming film is irradiated with energy rays (ultraviolet light) through the support sheet, the degree of curing of the protective film-forming film is further improved.
On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 375 nm is not particularly limited. For example, the light transmittance may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the protective film-forming film or protective film is irradiated with a laser beam through the support sheet, and printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit of the transmittance of light of wavelength 532 nm is not particularly limited. For example, the light transmittance may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the protective film-forming film or protective film is irradiated with a laser beam through the support sheet, and printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit value of the transmittance of light with a wavelength of 1064 nm is not particularly limited. For example, the light transmittance may be 95% or less.

In the support sheet, the transmittance of light with a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the semiconductor wafer is irradiated with laser light through the support sheet and the protective film-forming film or protective film, and the modified layer is formed on the semiconductor wafer. It can be formed more easily.
On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 1342 nm is not particularly limited. For example, the light transmittance may be 95% or less.
Next, each layer constituting the support sheet will be described in more detail.

○ 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-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ie, monomers Copolymers obtained using ethylene as a), vinyl chloride resins such as polyvinyl chloride, vinyl chloride copolymers (ie, resins obtained using vinyl chloride as a monomer); polystyrene; polycycloolefins; polyethylene terephthalate Polyesters such as polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all constituent units have an aromatic cyclic group; Two or more of the above polyesters Copolymers: 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 100 μm. When the thickness of the substrate is in such a range, the flexibility of the composite sheet for protective 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 optical properties of the substrate are preferably such as to satisfy the optical properties of the support sheet described above. For example, the substrate may be transparent or opaque, or may be colored according to the purpose, or other layers may be deposited.
And in the present invention in which the film for protective film formation has energy ray curability, the base material is preferably one which transmits energy rays.

The substrate is roughened by sand blasting, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment, etc., in order to improve the adhesion to other layers such as the pressure-sensitive adhesive layer provided thereon. The surface may be subjected to oxidation treatment such as ozone / ultraviolet radiation treatment, flame treatment, chromic acid treatment, hot air treatment or the like.
Moreover, the surface of the substrate may be subjected to primer treatment.
In addition, the base material prevents adhesion of the base material to another sheet and adhesion of the base material to the suction table when the antistatic coating layer and the composite sheet for protective film formation are stacked and stored. It may have a layer or the like.

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 optical properties of the pressure-sensitive adhesive layer preferably satisfy the optical properties of the support sheet described above. For example, the pressure-sensitive adhesive layer may be transparent or opaque, or may be colored according to the purpose.
And in the present invention in which the protective film-forming film has energy ray curability, 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. The pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive 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 ratio of the contents of the components which do not vaporize at normal temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components of the pressure-sensitive adhesive layer.

The application of the pressure-sensitive adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater And methods using various coaters such as a Mayer bar coater and a kiss coater.

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. Moreover, it is preferable that the (meth) acrylic-acid alkyl ester whose carbon number of the said alkyl group is 4 or more is methacrylic 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.

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 Saturated alcohol (that is, unsaturated alcohol having no (meth) acryloyl skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (that is, monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid and maleic acid And ethylenically unsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate Ester etc. are mentioned.

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).
Examples of the crosslinking agent include isocyanate crosslinking agents such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, adducts of these diisocyanates (that is, crosslinking agents having an isocyanate group); epoxy crosslinking such as ethylene glycol glycidyl ether Agents (ie, crosslinkers having glycidyl groups); aziridine crosslinkers such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (ie, crosslinkers having aziridinyl groups); metals such as aluminum chelates Chelate-based crosslinking agents (i.e., crosslinking agents having a metal chelate structure); isocyanurate-based crosslinking agents (i.e., crosslinking agents 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.

When a crosslinking agent is used, the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-1) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a) Is 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.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound. Part is preferable, 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.

[Other additives]
The 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.

When other additives are used, 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 (for example, carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as hexane; 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.

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

<Pressure-sensitive 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 (alias: ethenyl group), allyl group (alias: 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.

When a crosslinking agent is used, the content of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a) Is 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.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) is 0.01 to 100 parts by mass with respect to the content of the adhesive resin (I-2a). 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-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.

When other additives are used, 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.
When a solvent is used, the content of the solvent of 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.

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

[Other additives]
The 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.

When other additives are used, 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.
When a solvent is used, 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.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total content of all components other than the solvent (that is, based on the total weight of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer) The content of the adhesive resin (I-1a) is preferably 50 to 98% by mass, and may be, for example, 65 to 98% by mass and 80 to 98% 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-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 20 parts by mass, and particularly preferably 0.3 to 15 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.

When other additives are used, 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.
When a solvent is used, the content of the solvent of the pressure-sensitive adhesive composition (I-4) is not particularly limited, and may be appropriately adjusted.

In the composite sheet for protective film formation, 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 film for forming a protective film is cured by irradiation with energy rays, it may not be possible to simultaneously cure the pressure-sensitive adhesive layer. If the pressure-sensitive adhesive layer is cured simultaneously with the protective film-forming film, the cured product of the protective film-forming film and the cured product of 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 protective film-forming film, that is, the semiconductor chip having the protective film on the back surface (that is, the semiconductor chip with a protective film) from the support sheet provided with the cured product of the pressure sensitive adhesive layer. The semiconductor chip with the protective film can not be picked up properly. By making the pressure-sensitive adhesive layer non-energy ray curable in the support sheet, such a defect can be reliably avoided, and the semiconductor chip with a protective film can be picked up more easily.

Here, the effect when the pressure-sensitive adhesive layer is non-energy ray curable has been described, but even if the layer in direct contact with the protective 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.

製造 Method of Producing Protective Film-Forming Composite Sheet The protective film-forming composite sheet can be produced by laminating the above-described respective 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, when a film for protective film formation is further laminated on the pressure-sensitive adhesive layer laminated on the substrate, the composition for protective film formation is coated on the pressure-sensitive adhesive layer to form a protective film. It is possible to form the forming film directly. Layers other than the protective film-forming film can be laminated on the pressure-sensitive adhesive layer in the same manner 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 protective film formation, in which an adhesive layer is laminated on a substrate and a protective film-forming film 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 protective film, which is a product, the pressure-sensitive adhesive composition is coated on a base material, and dried as needed to laminate the pressure-sensitive adhesive layer on the base material. The film for protective film formation is separately formed on the peelable film by coating the composition for protective film formation separately on the peelable film and drying it as needed. Then, the exposed surface of the protective film-forming film is attached to the exposed surface of the pressure-sensitive adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the pressure-sensitive adhesive layer to form a protective 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.

As described above, any layers other than the base material constituting the composite sheet for forming a protective film can be formed in advance on the peelable film and laminated on the surface of the intended layer, as required. A layer adopting such a process may be appropriately selected to manufacture a composite sheet for forming a protective film.

In addition, the composite sheet for protective film formation is normally stored in the state in which the peeling film was bonded together on the surface of the outermost layer (for example, film for protective film formation) on the opposite side to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is coated on the release film (preferably, the release-treated surface thereof), and dried as necessary. Then, the layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated by any of the methods described above on the exposed surface of the layer opposite to the side in contact with the release film. The composite film for forming a protective film can also be obtained by leaving the release film in place without removing it.

Method of Manufacturing Semiconductor Chip The film for forming a protective film and the composite sheet for forming a protective film can be used for manufacturing a semiconductor chip.
As a method for manufacturing a semiconductor chip at this time, for example, a film for forming a protective film which does not constitute the composite sheet for forming a protective film, or a film for forming a protective film in the composite sheet for forming a protective film is used as a semiconductor wafer. Of forming a protective film by applying an energy ray to the step of attaching to a semiconductor (hereinafter sometimes abbreviated as “adhering step”) and the film for forming a protective film after being attached to the semiconductor wafer ( Hereinafter, it may be abbreviated as “protective film formation process” and laser light is irradiated through the protective film or the protective film formation film so as to focus on the focal point set inside the semiconductor wafer. Of forming a modified layer inside the semiconductor wafer (hereinafter sometimes abbreviated as “modified layer forming step”), and the semiconductor wafer having the modified layer formed thereon. Together with the protective film or the protective film-forming film by expanding the protective film or the protective film-forming film in the surface direction (direction parallel to the surface) of the protective film or the protective film-forming film. What has the process (It may abbreviate as a "division | segmentation process" hereafter) of dividing | segmenting the said semiconductor wafer in the site | part of the said modification layer while cutting | disconnecting, and obtaining several semiconductor chips.

Here, although the direction of expansion of the semiconductor wafer is specified as the surface direction of the protective film or the film for forming a protective film, generally, this surface direction is the surface direction of the semiconductor wafer (for example, the direction of the back surface). It is the same.

Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. FIGS. 7 to 9 are cross-sectional views for schematically describing one embodiment of a method of manufacturing a semiconductor chip in the case of using a film for forming a protective film which does not constitute a composite sheet for forming a protective film. is there. 10 to 12 schematically show an embodiment of a method of manufacturing a semiconductor chip in the case of using a composite sheet for protective film formation in which a protective film-forming film is integrated with a support sheet in advance. It is sectional drawing for demonstrating to FIG.

<< Method of manufacturing semiconductor chip when using a film for forming a protective film which does not constitute a composite sheet for forming a protective film >>
First, in one embodiment of a method of manufacturing a semiconductor chip in the case of using a film for forming a protective film which does not constitute the composite sheet for forming a protective film, the case where the film for forming a protective film is as shown in FIG. This will be described by way of example (this embodiment may be referred to as “manufacturing method (1) -1”).

In the attaching step of the manufacturing method (1) -1, as shown in FIG. 7A, a film for forming a protective film is formed on the back surface (in other words, the surface opposite to the electrode formation surface) 9b of the semiconductor wafer 9. Stick 13 Here, the case where the first release film 151 is removed from the protective film formation film 13 and the first surface 13a of the protective film formation film 13 is bonded to the back surface 9b of the semiconductor wafer 9 is shown. Further, in the semiconductor wafer 9, illustration of bumps and the like on the circuit surface is omitted here.

As shown in FIG. 7 (b), after applying the manufacturing method (1) -1, in the protective film forming step, the protective film forming film 13 after being attached to the semiconductor wafer 9 is irradiated with an energy beam. As described above, the protective film 13 ′ is formed on the semiconductor wafer 9. The irradiation of the energy rays may be performed after removing the second release film 152 from the protective film-forming film 13.

In addition, after the attaching process of the manufacturing method (1) -1, the laser beam is passed through the protective film 13 ′ so as to focus on the focal point set inside the semiconductor wafer 9 in the modified layer forming process. By irradiation, as shown in FIG. 7C, the modified layer 91 is formed inside the semiconductor wafer 9. The irradiation of the laser beam is performed after removing the second peeling film 152 from the protective film 13 ′.

After the modified layer forming step of the manufacturing method (1) -1, prior to the dividing step, as shown in FIG. 7D, the surface of the protective film 13 ′ on the side to which the semiconductor wafer 9 is attached In the present specification, the support sheet 10 is provided on a surface (sometimes referred to as “second surface” herein) 13 b ′ opposite to the “first surface” 13 a ′. Stick the The support sheet 10 is shown in FIG. 2 and the like, and is attached to the protective film 13 ′ by the pressure-sensitive adhesive layer 12.

Next, in the dividing step of the manufacturing method (1) -1, the semiconductor wafer 9 on which the modified layer 91 is formed is, together with the protective film 13 ′, the surface of the protective film 13 ′ (that is, the first surface 13a ′ or the second By expanding in the direction of the surface 13b '), the protective film 13' is cut, and the semiconductor wafer 9 is divided at the portion of the modified layer 91, and a plurality of semiconductor chips 9 is obtained as shown in FIG. Get '. At this time, the protective film 13 'is cut (divided) at a position along the dividing portion of the semiconductor wafer 9, in other words, the peripheral portion of the semiconductor chip 9'. The protective film 13 'after this cutting is indicated by reference numeral 130'.
In the dividing step, the semiconductor wafer 9 and the protective film 13 ′ are expanded (expanded) in the direction indicated by the arrow I in FIG. 9 and the protective film 13 'are divided.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a protective film.

In addition, in FIG. 7, after performing a protective film formation process and a modification layer formation process, it shows about the case where the support sheet 10 is stuck on protective film 13 '. However, in the production method (1) -1, after the support sheet 10 is attached to the film 13 for forming a protective film, the process of forming a protective film and the process of forming a modified layer may be performed. After the support sheet 10 is attached to the protective film 13 ′, the modified layer forming step may be performed.

In the manufacturing method (1) -1, when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the protective film-forming film 13, the protective film 13 ′ or the cutting is performed. It is possible to suppress floating of the semiconductor chip 9 'from the later protective film 130'.

In the manufacturing method (1) -1, the modified layer forming step is performed after the protective film forming step, but in the semiconductor chip manufacturing method according to the present embodiment, the protective film forming step is performed after the modified layer forming step. (This embodiment may be referred to as “production method (1) -2”).
FIG. 8 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing such a semiconductor chip.

In the attaching step of the manufacturing method (1) -2, as in the case of the manufacturing method (1) -1, as shown in FIG. 8A, the film 13 for forming a protective film is formed on the back surface 9b of the semiconductor wafer 9. Stick it.

After the attaching step of the manufacturing method (1) -2, in the modified layer forming step, the laser beam is applied via the protective film formation film 13 so as to focus on the focal point set inside the semiconductor wafer 9 By irradiation, as shown in FIG. 8B, the modified layer 91 is formed inside the semiconductor wafer 9. The irradiation of the laser beam is performed after removing the second peeling film 152 from the film 13 for forming a protective film.

Moreover, after the sticking process of manufacturing method (1) -2, in the said protective film formation process, the energy beam is irradiated to the film 13 for protective film formation after sticking to the semiconductor wafer 9, and FIG. 8 (c) As shown in FIG. 2, a protective film 13 ′ is formed on the semiconductor wafer 9. By performing this step, after completion of the modified layer forming step of the manufacturing method (1) -1, a semiconductor wafer with a protective film in the same state as that of FIG. 7C can be obtained.

Thereafter, as shown in FIGS. 8 (d) to 8 (e), as in the case of the manufacturing method (1) -1, (more specifically, in FIGS. 7 (d) to 7 (e)) As shown), by attaching the support sheet 10 to the second surface 13b ′ of the protective film 13 ′ and then performing the dividing step, the protective film 13 ′ is cut and at the site of the modified layer 91 The semiconductor wafer 9 is divided to obtain a plurality of semiconductor chips 9 '.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a protective film.

In addition, in FIG. 8, after performing a modification layer formation process and a protective film formation process, it shows about the case where the support sheet 10 is stuck on protective film 13 '. However, in the production method (1) -2, after the support sheet 10 is attached to the film 13 for forming a protective film, the step of forming a modified layer and the step of forming a protective film may be performed. Thereafter, after the support sheet 10 is attached to the protective film-forming film 13, the protective film-forming step may be performed.

Also in the manufacturing method (1) -2, when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the protective film-forming film 13, the protective film 13 ′ or the cutting is performed. It is possible to suppress floating of the semiconductor chip 9 'from the later protective film 130'.

In the manufacturing methods (1) -1 and (1) -2, the dividing step is performed after the protective film forming step, but in the semiconductor chip manufacturing method according to the present embodiment, the dividing step is not performed. And the protective film forming step may be performed after the dividing step (this embodiment may be referred to as “manufacturing method (1) -3”).
FIG. 9 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing such a semiconductor chip.

As shown in FIGS. 9 (a) to 9 (b), the attaching process and the modified layer forming process of the manufacturing method (1) -3 are the attaching process and the modified layer formation of the manufacturing method (1) -2. It can be carried out by the same method as the process (more specifically, as shown in FIG. 8A to FIG. 8B).

After the modifying layer forming step of production method (1) -3, prior to the dividing step, as shown in FIG. 9C, the supporting sheet 10 is formed on the second surface 13b of the protective film-forming film 13. Stick it.

Next, in the dividing step of the manufacturing method (1) -3, the semiconductor wafer 9 on which the modified layer 91 is formed is, together with the protective film forming film 13, the surface of the protective film forming film 13 (that is, the first surface 13 a Alternatively, the protective film-forming film 13 is cut by expanding in the direction of the second surface 13b), and the semiconductor wafer 9 is divided at the portion of the modified layer 91, as shown in FIG. The semiconductor chip 9 'is obtained. At this time, the protective film-forming film 13 is cut (divided) at a position along the dividing portion of the semiconductor wafer 9, in other words, the peripheral portion of the semiconductor chip 9 ′. The film 13 for protective film formation after this cutting | disconnection is shown by code | symbol 130. FIG. In the dividing step, a force (that is, a tensile force) is applied in this direction by expanding (expanding) the semiconductor wafer 9 and the film 13 for forming a protective film in the direction indicated by the arrow I in FIG. 9C. The semiconductor wafer 9 and the protective film forming film 13 are divided.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a film for protective film formation.

In addition, in FIG. 9, after performing a modification layer formation process, it shows about the case where the support sheet 10 is stuck on the film 13 for protective film formation. However, in the production method (1) -3, after the support sheet 10 is attached to the protective film-forming film 13, the modified layer forming step may be performed.

In the manufacturing method (1) -3, when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the film 13 for forming a protective film, the film 13 for forming a protective film is used. Or floating of semiconductor chip 9 'from film 130 for protective film formation after a cut can be controlled.

In the manufacturing method (1) -3, after the dividing step, the protective film-forming film 130 is irradiated with an energy beam through the support sheet 10, as shown in FIG. The protective film 130 'may be formed on the
Although FIG. 9E shows the case where the protective film 130 'is formed before picking up the semiconductor chip 9', the protective film 130 'is formed after the division process such as after picking up the semiconductor chip 9'. It can be done at any time.

<< Method of manufacturing semiconductor chip in the case of using a composite sheet for protective film formation in which a film for protective film formation is previously integrated with a support sheet >>
Next, the composite sheet for protective film formation is a figure about one embodiment of the manufacturing method of a semiconductor chip at the time of using the composite sheet for protective film formation which integrated the film for protective film formation beforehand with the support sheet, and was constituted. A case shown in FIG. 2 will be described as an example (this embodiment may be referred to as “manufacturing method (2) -1”).

In the attaching process of the manufacturing method (2) -1, as shown in FIG. 10A, the film 13 for forming a protective film in the composite sheet 1A for forming a protective film is attached to the back surface 9b of the semiconductor wafer 9 . The protective film-forming composite sheet 1A is used after removing the release film 15.

As shown in FIG. 10B, after applying the manufacturing method (2) -1, in the protective film forming step, the protective film forming film 13 after being attached to the semiconductor wafer 9 is irradiated with an energy beam. As described above, the protective film 13 ′ is formed on the semiconductor wafer 9. At this time, the energy ray is irradiated to the film 13 for protective film formation through the support sheet 10.
In addition, the composite sheet for protective film formation after the film 13 for protective film formation becomes protective film 13 'is shown with code | symbol 1 A' here. This is the same in the following figures.

After the attaching process of the manufacturing method (2) -1, the protective film 13 '(in other words, a composite sheet for forming a protective film) is focused so as to focus on the focal point set inside the semiconductor wafer 9 in the modified layer forming process. By irradiating a laser beam through 1A ′), as shown in FIG. 10C, a modified layer 91 is formed inside the semiconductor wafer 9.

Next, in the dividing step of the manufacturing method (2) -1, the semiconductor wafer 9 on which the modified layer 91 is formed is, together with the protective film 13 ′, the surface of the protective film 13 ′ (that is, the first surface 13a ′ or the second By expanding in the direction of the surface 13b '), the protective film 13' is cut, and the semiconductor wafer 9 is divided at the portion of the modified layer 91, and a plurality of semiconductor chips 9 is obtained as shown in FIG. Get '. At this time, the protective film 13 'is cut (divided) at a position along the dividing portion of the semiconductor wafer 9, in other words, the peripheral portion of the semiconductor chip 9', to form a protective film 130 '. In the dividing step, the semiconductor wafer 9 and the protective film 13 ′ are expanded (expanded) in the direction indicated by the arrow I in FIG. 9 and the protective film 13 'are divided.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a protective film.

In the production method (2) -1, when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the protective film-forming film 13, the protective film 13 ′ or the cutting is performed. It is possible to suppress the floating of the semiconductor chip 9 ′ from the later protective film 130 ′.

In the manufacturing method (2) -1, the modified layer forming step is performed after the protective film forming step, but in the method of manufacturing the semiconductor chip according to the present embodiment, the protective film forming step is performed after the modified layer forming step. (This embodiment may be referred to as “production method (2) -2”).
FIG. 11 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing such a semiconductor chip.

In the production method (2) -2, as in the production method (2) -1, as shown in FIG. 11 (a), protection on the back surface 9b of the semiconductor wafer 9 in the composite sheet 1A for protective film formation The film forming film 13 is attached.

After the attaching process of the manufacturing method (2) -2, the protective film-forming film 13 (a composite sheet for forming a protective film is formed so as to focus on the focal point set inside the semiconductor wafer 9 in the modified layer forming process. By irradiating a laser beam through 1A), as shown in FIG. 11B, the modified layer 91 is formed inside the semiconductor wafer 9.

Moreover, after the sticking process of manufacturing method (2) -2, in the said protective film formation process, the energy beam is irradiated to the film 13 for protective film formation after sticking to the semiconductor wafer 9, FIG.11 (c) As shown in FIG. 2, a protective film 13 ′ is formed on the semiconductor wafer 9. By performing this step, after completion of the modified layer forming step of production method (2) -1, that is, a semiconductor wafer with a protective film in the same state as FIG. 10 (c) can be obtained.

Thereafter, as shown in FIG. 11 (d), the division step is performed as in the case of the manufacturing method (2) -1 (more specifically, as shown in FIG. 10 (d)). The protective film 13 'is cut, and the semiconductor wafer 9 is divided at the portion of the modified layer 91 to obtain a plurality of semiconductor chips 9'.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a protective film.

Also in the manufacturing method (2) -2, when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the protective film-forming film 13, the protective film 13 ′ or the cutting is performed. It is possible to suppress the floating of the semiconductor chip 9 ′ from the later protective film 130 ′.

In the manufacturing methods (2) -1 and (2) -2, the dividing step is performed after the protective film forming step, but in the semiconductor chip manufacturing method according to the present embodiment, the dividing step is not performed. And the protective film forming step may be performed after the dividing step (this embodiment may be referred to as “manufacturing method (2) -3”).
FIG. 12 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing such a semiconductor chip.

As shown in FIGS. 12 (a) to 12 (b), the attaching process and the modifying layer forming process of the producing method (2) -3 are the attaching process and the modifying layer formation of the producing method (2) -2. It can be carried out by the same method as the process (more specifically, as shown in FIGS. 11 (a) to 11 (b)).

Next, in the dividing step of the manufacturing method (2) -3, the semiconductor wafer 9 on which the modified layer 91 is formed is, together with the protective film forming film 13, the surface of the protective film forming film 13 (that is, the first surface 13a Alternatively, the protective film-forming film 13 is cut by expanding in the direction of the second surface 13b), and the semiconductor wafer 9 is divided at the portion of the modified layer 91, as shown in FIG. 12C. The semiconductor chip 9 'is obtained. At this time, the protective film-forming film 13 is cut (divided) at a position along the dividing portion of the semiconductor wafer 9, in other words, the peripheral portion of the semiconductor chip 9 ′. In the dividing step, a force (that is, a tensile force) is applied in this direction by expanding (expanding) the semiconductor wafer 9 and the film 13 for forming a protective film in the direction indicated by the arrow I in FIG. The semiconductor wafer 9 and the protective film forming film 13 are divided.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a film for protective film formation.

In the manufacturing method (2) -3, when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the film 13 for forming a protective film, the film 13 for forming a protective film is used. Or floating of semiconductor chip 9 'from film 130 for protective film formation after cutting can be controlled.

In the manufacturing method (2) -3, after the dividing step, the protective film 130 is irradiated with an energy beam to form a protective film 130 'on the semiconductor wafer 9 as shown in FIG. 12 (d). do it.
Although FIG. 12D shows the case where the protective film 130 'is formed before picking up the semiconductor chip 9', the protective film 130 'is formed after the division process such as after picking up the semiconductor chip 9'. It can be done at any time.

So far, the method of manufacturing a semiconductor chip has been described using the film 13 for forming a protective film shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the composite sheet 1A for forming a protective film shown in FIG. The manufacturing method of the semiconductor chip of the present invention is not limited to these.
For example, in the case of using a composite sheet for forming a protective film, as shown in FIGS. 3 to 6, composite sheets 1B to 1E for forming a protective film and a composite sheet for forming a protective film further comprising the intermediate layer A semiconductor chip can be manufactured similarly even if using other than composite sheet 1A for protective film formation shown to these.
In addition, as the support sheet, even if the support sheet shown in FIG. 2 is used other than the support sheet 10 shown in FIG. Can produce chips.
Thus, when using the composite sheet for protective film formation of other embodiment and support sheet of other embodiments, based on the difference in the structure of these sheets, in the above-mentioned manufacturing method, addition, change, deletion of a process, etc. are carried out suitably. To manufacture a semiconductor chip.

Method of Manufacturing Semiconductor Device After a semiconductor chip is obtained by the above-described manufacturing method, the semiconductor chip is supported as it is with the protective film after division (ie, as a semiconductor chip with a protective film). Pull away from and pick up (not shown).
Thereafter, the obtained semiconductor chip of the semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate by a method similar to that of the conventional method to form a semiconductor package. Then, the target semiconductor device may be manufactured using this semiconductor package (not shown).

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.

<Manufacturing raw material of composition for protective film formation>
The raw materials used for the production of the composition for forming a protective film are shown below.
[Energy ray curable component (a2)]
(A2) -1: ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-9300-1CL”, trifunctional UV-curable compound)
[Polymer having no energy ray curable group (b)]
(B) -1: an acrylic polymer (weight average molecular weight copolymerized with methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass) 300000, glass transition temperature 6 ° C.).
[Photoinitiator (c)]
(C) -1: 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone ("Irgacure (registered trademark) 369" manufactured by BASF)
[Filler (d)]
(D) -1: silica filler (fused silica filler, average particle size 8 μm)
[Coupling agent]
(E) -1: 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical "KBM-503", silane coupling agent)
[Colorant (g)]
(G) -1: 32 parts by mass of phthalocyanine-based blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone-based red pigment (Pigment Red 177) And the pigment obtained by pigmenting so that the total amount of the three dyes / the styrene acrylic resin amount = 1/3 (mass ratio).
[Compound (p)]
(P) -1: succinic acid mono (2-acryloyloxyethyl)

Example 1
<Manufacture of composite sheet for protective film formation>
(Production of composition for forming a protective film (IV-1))
Energy ray curable component (a2) -1, polymer (b) -1, photopolymerization initiator (c) -1, filler (d) -1, coupling agent (e) -1, colorant (g) ) And compound (p) -1 are dissolved or dispersed in methyl ethyl ketone such that their contents (solid content, parts by mass) become the values shown in Table 1, and the mixture is stirred at 23 ° C. A composition (IV-1) for forming a protective film having a concentration of 50% by mass was prepared. In addition, the description of "-" in the column of the component in Table 1 means that the composition for forming a protective film (IV-1) does not contain the component.

(Production of Pressure-Sensitive Adhesive Composition (I-4))
Acrylic polymer (100 parts by mass, solid content) and isocyanate crosslinking agent ("Coronato L" manufactured by Nippon Polyurethane Industry Co., Ltd., tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content) A non-energy ray curable pressure-sensitive adhesive composition (I-4) having a solid content concentration of 30% by mass was prepared, which further contains methyl ethyl ketone as a solvent. The acrylic polymer is a copolymer having a weight average molecular weight of 600,000, which is obtained by copolymerizing 2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
The pressure-sensitive adhesive composition obtained above was used on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, 38 μm thick) whose release treatment was performed on one side of a polyethylene terephthalate film by silicone treatment I-4) was coated and dried by heating at 120 ° C. for 2 minutes to form a non-energy ray curable pressure-sensitive adhesive layer having a thickness of 10 μm.
Then, a base material, an adhesive layer and a release film are laminated in this order in the thickness direction by laminating a polypropylene film (80 μm in thickness) as a substrate on the exposed surface of the adhesive layer. Support sheet was obtained.

(Manufacture of composite sheet for protective film formation)
A release film (second release film, "SP-PET 382150" manufactured by Lintec Corporation, 38 μm thick), one surface of which is a polyethylene terephthalate film, was treated by silicone treatment, and the above-mentioned release-treated surface was obtained above The composition for forming a protective film (IV-1) was applied and dried at 100 ° C. for 2 minutes to produce a 25 μm-thick film for forming a protective film for energy ray curing.
Furthermore, the exfoliation process of the exfoliation film (the 1st exfoliation film, the lintec "SP-PET 38 1031", 38 micrometers in thickness) is carried out to the exposure side of the side which is not equipped with the 2nd exfoliation film of the film for protective film formation obtained. By laminating the surfaces, a laminated film including the first release film on one surface of the protective film-forming film and the second release film on the other surface was obtained.

Next, the release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above. Moreover, the 1st peeling film was removed from the laminated film obtained above. And a base material and adhesion are obtained by sticking together the exposed surface of the pressure-sensitive adhesive layer produced by removing the above-mentioned release film and the exposed surface of the film for protective film formation produced by removing the above-mentioned first release film. The composite sheet for protective film formation in which an agent layer, the film for protective film formation, and the 2nd exfoliation film are laminated in this thickness direction in this order was produced.

<Evaluation of film for protective film formation>
(Adhesive force between film for protective film formation and silicon wafer)
The first release film was removed from the laminated film obtained above, and an adhesive tape ("D-841" manufactured by Lintec Corporation) was attached to the exposed surface of the protective film-forming film produced thereby. And the test piece was produced by cutting | judged what was obtained to the magnitude | size of 25 mm x 140 mm.
Next, the second peelable film is removed from the protective film-forming film of the obtained test piece, and the exposed surface of the protective film-forming film thus formed is a # 2000 polished surface of a 6-inch silicon wafer (300 μm thick) It was stuck on the plate and left to stand for 30 minutes.

Then, using the precision universal tester ("Autograph AG-IS" manufactured by Shimadzu Corporation) under the condition of 23 ° C, the laminate of the film for protective film formation and the adhesive tape from the silicon wafer is for protective film formation. So-called 180 ° peeling was performed such that peeling was performed at a peeling speed of 300 mm / min so that the surfaces of the film and the silicon wafer in contact with each other had an angle of 180 °. And the peeling force (load, N / 25 mm) at this time was measured, and this measured value was employ | adopted as an adhesive force between the film for protective film formation, and a silicon wafer. The results are shown in Table 1.

<Evaluation of protective film>
(Suppressing of semiconductor chips)
The first release film was removed from the laminated film obtained above, and the exposed surface of the protective film-forming film thus formed was attached to the # 2000 polished surface of an 8-inch silicon wafer (300 μm in thickness).
Then, the second release film was removed from the protective film-forming film to expose the protective film-forming film. Moreover, the peeling film was removed from the adhesive layer of the support sheet obtained above, and the adhesive layer was exposed. Then, the exposed surface of the pressure-sensitive adhesive layer is attached to the exposed surface of the protective film-forming film and attached to the ring frame, whereby the substrate, the adhesive layer, the protective film-forming film, and the silicon wafer are in this order. The laminated body laminated | stacked in these thickness direction was fixed to the ring frame, and was left still for 30 minutes.

Then, using a UV irradiation device ("RAD 2000 m / 8" manufactured by LINTEC Corporation), under the conditions of an illuminance of 195 mW / cm ² and a light amount of 170 mJ / cm ^2, a film for protective film formation By irradiating ultraviolet rays, the film for protective film formation is cured to form a protective film. Hereinafter, the product obtained by this, that is, the product in which the protective film-forming film in the laminate becomes a protective film is referred to as a “cured after curing laminate”.
Next, the laminate after curing and the ring frame were placed on a laser saw (“DFL7361” manufactured by Disco Corporation) while adjusting their positions so that the silicon wafer could be irradiated with a laser beam through the protective film.

Then, a modified layer was formed inside the silicon wafer by irradiating a laser beam having a wavelength of 1342 nm through the support sheet and the protective film so as to focus on the focal point set inside the silicon wafer. .
Next, the post-curing laminate and ring frame are placed in a die separator ("DDS 2300" manufactured by Disco Corporation), and the post-curing laminate is applied to the surface direction (on the surface) of the protective film under conditions of 0 ° C. The protective film was cut by expanding in the direction along the above, and the silicon wafer was divided at the site of the modified layer to obtain a plurality of silicon chips having a size of 3 mm × 3 mm.

Next, the division state of the obtained silicon chip on the protective film is visually observed, and when there is no silicon chip in which the floating from the protective film is generated, it is determined as “A”, and from the protective film When one or more silicon chips in which a float of the silicon wafer occurred were present, it was determined as "B". The results are shown in Table 1.

(Shear strength of protective film)
In the same manner as in the above-mentioned "suppression of semiconductor chip floating", except that a 6 inch silicon wafer (300 μm thick) was used instead of the 8 inch silicon wafer (300 μm thick), a substrate, A laminate comprising an adhesive layer, a protective film-forming film and a silicon wafer laminated in this order in the thickness direction was fixed to a ring frame and allowed to stand for 30 minutes. The protective film-forming film was attached to the # 2000 polished surface of a 6-inch silicon wafer.

Then, using a UV irradiation apparatus ("RAD 2000 m / 8" manufactured by LINTEC Corporation), under the conditions of an illuminance of 195 mW / cm ² and a light quantity of 170 mJ / cm ^2, a film for protective film formation is provided via the substrate and the pressure-sensitive adhesive layer. The film for protective film formation was hardened by irradiating an ultraviolet ray, it was made into a protective film, and the silicon wafer with a protective film was obtained.
Then, using a dicing blade, the silicon wafer is diced together with the protective film (that is, the silicon wafer with protective film is diced), and a silicon chip with a protective film having a size of 3 mm × 3 mm (that is, A plurality of silicon chips with a protective film were obtained.

Next, using a universal bond tester ("DAGE 4000" manufactured by Nordson Advanced Technology), only the protective film of the protected silicon chip at a speed of 200 μm / s with a shear tool under conditions of 23 ° C. Force was applied to the surface of the protective film. Then, the maximum value of the force applied until the protective film was broken was confirmed, and this was adopted as the shear strength (N / 3 mm □). The results are shown in Table 1.

<Production of Composite Sheet for Forming Protective Film, and Evaluation of Film and Protective Film for Forming Protective Film>
[Example 2, Comparative Example 1]
A protective film-forming film and a protective film-forming composite were prepared in the same manner as in Example 1 except that the amounts of the compounding components at the time of production of the protective film-forming composition (IV-1) were as shown in Table 1. The sheet was manufactured, and the film for protective film formation and the protective film were evaluated. The results are shown in Table 1.

As is clear from the above results, in Examples 1 and 2, when the protective film is cut by expanding the silicon wafer with the protective film, and the silicon wafer is divided into silicon chips, The lift of the silicon chip has been suppressed. In Examples 1 to 2, in the composition for forming a protective film (IV-1), the ratio of the content of the compound (p) to the total content of the components other than the solvent (that is, the protection in the film for forming a protective film) The ratio of the content of the compound (p) to the total mass of the film for film formation was 0.3 to 0.5 mass%. In Examples 1 and 2, the adhesion between the protective film-forming film and the silicon wafer was as high as 3.8 N / 25 mm or more (3.8 to 4.5 N / 25 mm). Furthermore, in Examples 1 and 2, the shear strength of the protective film was as large as 11.3 N / 3 mm □ or more (11.3 to 11.4 N / 3 mm □). Thus, the protective film-forming film and the protective film of Examples 1 and 2 had favorable characteristics.

On the other hand, in Comparative Example 1, the floating of the silicon chip from the protective film was not suppressed. In Comparative Example 1, the compound (p) was not used in the composition for forming a protective film (that is, the film for forming a protective film did not contain the compound (p)). In Comparative Example 1, the adhesion between the protective film-forming film and the silicon wafer was 2.6 N / 25 mm, which is lower than in Examples 1 and 2. Furthermore, in Comparative Example 1, the shear strength of the protective film was smaller than that of Examples 1 and 2 at 10.1 N / 3 mm □. Thus, the film for protective film formation of Comparative Example 1 and the protective film did not have favorable characteristics.

From the results of these Examples and Comparative Examples, it was clearly confirmed that the presence or absence of floating of the silicon chip is affected by the presence or absence of the use of the compound (p).

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

1A, 1A ', 1B, 1C, 1D, 1E ... composite sheet for protective film formation, 10 ... support sheet, 10a ... surface of support sheet (first surface), 11 ... base material, 11a: surface of substrate (first surface) 12: adhesive layer 12a: surface of adhesive layer (first surface) 13, 23: protective film-forming film 130 ... Film for protective film formation after cutting, 13a, 23a ... surface (first surface) of film for protective film formation, 13b ... surface (second surface) for film for protective film formation, 13 ′ ... Protective film, 130 '... Protective film after cutting, 15 ... Peeling film, 151 ... First peeling film, 152 ... Second peeling film, 16 ... Bonding for jig Agent layer, 16a: surface of adhesive layer for jig, 9: semiconductor wafer, 9b: semiconductor wafer Surface modified layer of 91 ... semiconductor wafer, 9 '... semiconductor chip

Claims (3)

1. An energy ray curable protective film-forming film,
   The film for protective film formation is a film for protective film formation, which contains a compound having a carboxyl group or a group in which a carboxy group has formed a salt in one molecule, and a polymerizable group.
2. A composite sheet for forming a protective film, comprising a support sheet, and the film for forming a protective film according to claim 1 on the support sheet.
3. Attaching the film for protective film formation according to claim 1 or the film for protective film formation in the composite sheet for protective film formation according to claim 2 to a semiconductor wafer;
   Forming a protective film by irradiating the film for forming a protective film after being attached to the semiconductor wafer with an energy ray;
   Forming a modified layer inside the semiconductor wafer by irradiating a laser beam through the protective film or the protective film-forming film so as to focus on a focal point set inside the semiconductor wafer; ,
   The protective film or film for forming a protective film is expanded by expanding the semiconductor wafer having the modified layer formed thereon, along with the protective film or a film for forming a protective film, in the surface direction of the protective film or the film for forming a protective film And dividing the semiconductor wafer at a portion of the modified layer to obtain a plurality of semiconductor chips.

Images