TWI783066B - Film for protective film formation, composite sheet for protective film formation, and method for forming semiconductor chip - Google Patents

Abstract

A film for protective film formation is an energy ray curable film for protective film formation, in which a pressure sensitive adhesiveness between the film for protective film formation and a silicon wafer is 3 N/25mm or more, and when the film for protective film formation is turned to be a protective film by irradiating with UV light, a shear strength of the protective film is 10.5 N/3mm□.

Description

Film for forming protective film, composite sheet for forming protective film, and method for producing semiconductor wafer

This invention relates to the manufacturing method of the composite sheet for protective film formation, and a semiconductor wafer. This application is based on Japanese Patent Application No. 2017-208432 filed in Japan on October 27, 2017 as the basis for claiming priority, and the contents thereof are incorporated herein by reference.

In recent years, the manufacture of semiconductor devices to which a mounting method called a so-called face-down method has been developed has been developed. In the face-down method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the aforementioned electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor wafer on the opposite side to the circuit surface is exposed.

A resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor wafer to be assembled in a semiconductor device as a semiconductor wafer with a protective film. The protective film is used to prevent cracks from occurring in the semiconductor wafer after a dicing step or packaging.

In order to form such a protective film, for example, the composite sheet for protective film formation provided with the film for protective film formation for forming a protective film on a support sheet can be used. The film for protective film formation can form a protective film by hardening. In addition, when dividing the semiconductor wafer provided with the film for protective film formation or a protective film on the back surface into semiconductor wafers, a support sheet can be used for fixing a semiconductor wafer. In addition, the support sheet can also be used as a dicing sheet, and the composite sheet for protective film formation can also be used as a composite sheet which integrated the film for protective film formation and a dicing sheet.

As such a composite sheet for forming a protective film, for example, a sheet provided with a film for forming a thermosetting protective film that is cured by heating to form a protective film is currently mainly used. However, heat curing of a film for forming a thermosetting protective film usually takes about several hours to as long as several hours, and therefore it is expected that the curing time can be shortened. On the other hand, when forming a protective film, the use of the film for protective film formation which can be cured by irradiation of the energy ray such as an ultraviolet ray (energy ray curability) has been considered.

On the other hand, as a method of obtaining a semiconductor wafer, a method of dicing the semiconductor wafer using a dicing blade is widely used. In this method, generally, a semiconductor wafer provided with a film for forming a protective film or a protective film on the back surface is divided and singulated by a dicing blade together with the film for forming a protective film or a protective film, and semiconductor wafers are obtained. .

In contrast, in recent years, various methods of dividing semiconductor wafers without using a dicing blade have been studied. For example, it is known to irradiate laser light so as to focus on a focal point set inside a semiconductor wafer to form a modified layer inside the semiconductor wafer, and then, to form this modified layer and stick it on the back surface The semiconductor wafer with the resin film is expanded in the surface direction of the resin film together with the resin film to cut the resin film and at the same time divide and singulate the semiconductor wafer at the position of the aforementioned modified layer, Further, a method of obtaining a semiconductor wafer. Unlike the method using a dicing blade, in this method, no cutting portion is formed on the semiconductor wafer due to the dicing blade, and thus has the advantage of being able to obtain more semiconductor wafers from the semiconductor wafer without generating cutting debris. As a material for bonding the semiconductor chip to the circuit-forming surface of the substrate, a film-like adhesive is mentioned, and the above-mentioned dividing method has been mainly used in the case of using the film-like adhesive as the aforementioned resin film until now. (Please refer to Patent Document 1).

Therefore, as long as the method of dividing by spreading as described above can be applied to a semiconductor wafer having an energy ray-curable protective film forming film or a protective film of its cured product as the aforementioned resin film, such a The method has very high practicality as a method of manufacturing a semiconductor wafer provided with a protective film. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-222002

[Problems to be Solved by the Invention]

However, when expanding the semiconductor wafer provided with the film for protective film formation or protective film, the problem that the obtained semiconductor wafer peeled off and floated from the film for protective film formation or protective film after dicing may arise. Among them, this problem occurs in the peripheral portion of the semiconductor wafer, and is particularly conspicuous in the corner portion.

The object of the present invention is to provide a protective film by expanding a semiconductor wafer having a film for forming a protective film or a cured product of a film for forming a protective film on the back surface and forming a modified layer inside it, so as to protect the semiconductor wafer. Film for forming a protective film capable of suppressing the floating of semiconductor wafers from the film for forming a protective film or the protective film when the film for forming a film or the protective film is cut and at the same time dividing the semiconductor wafer into semiconductor wafers, and the film for forming the protective film A composite sheet for forming a protective film, and a method for manufacturing the aforementioned semiconductor wafer. [Means used to solve the problem]

In order to solve the above problems, the present invention provides a film for forming a protective film, which is an energy ray curable film for forming a protective film, wherein the adhesion between the film for forming a protective film and a silicon wafer measured by the following method The force is 3N/25mm or more, and when the above-mentioned film for protective film formation is irradiated with ultraviolet rays to form a protective film, the shear strength of the protective film measured by the following method is 10.5N/3mm□ or more, for protective film formation Adhesion between the film and the silicon wafer: After attaching the aforementioned film for forming a protective film with a thickness of 25 μm to the silicon wafer, the surface of the aforementioned film for forming a protective film and the surface of the silicon wafer that were originally in contact with each other were formed into each other. In the case of an angle of 180°, the protective film forming film was peeled off from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time was measured, and the measured value was used as Adhesion between the film for forming a protective film and the silicon wafer, and shear strength of the protective film: After attaching the film for forming a protective film with a thickness of ²⁵ μm to the silicon wafer, the Under the condition of light intensity of 170mJ/cm ² , by irradiating ultraviolet rays to the film for forming a protective film, the film for forming a protective film was cured into a protective film, and the silicon wafer with the obtained protective film was diced into a size of 3mm×3mm silicon wafer with a protective film, and only on the protective film in the obtained silicon wafer with a protective film, apply a force in the direction of the surface of the protective film at a speed of 200μm/s until the protective film The maximum value (N/3mm□) of the force applied until the film was broken was taken as the shear strength of the protective film.

Furthermore, this invention provides the composite sheet for protective film formation provided with the support sheet, and provided with the said film for protective film formation on the said support sheet. Furthermore, the present invention provides a method for manufacturing a semiconductor wafer, which includes the following steps: attaching the film for forming a protective film or the film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer; The film for forming a protective film attached to the semiconductor wafer is irradiated with energy rays to form a protective film; and the film for forming a protective film is placed through the protective film or the film for forming a protective film so as to focus on a focal point set inside the semiconductor wafer. The film is irradiated with laser light to form a modified layer inside the semiconductor wafer; the semiconductor wafer on which the modified layer is formed is formed on the protective film or the protective film together with the protective film or the film for protective film formation. Expanding in the surface direction of the film, the protective film or the film for forming a protective film is cut and the semiconductor wafer is divided at the position of the modified layer at the same time to obtain a plurality of semiconductor wafers. [Effect of the present invention]

According to the present invention, there is provided an expansion of a semiconductor wafer in which a modified layer is formed inside a protective film provided with a film for forming a protective film or a cured product of a film for forming a protective film on the back surface, so that the protective film can be protected. Film for forming a protective film capable of suppressing the floating of semiconductor wafers from the film for forming a protective film or the protective film when the film for forming a film or the protective film is cut and at the same time dividing the semiconductor wafer into semiconductor wafers, and the film for forming the protective film A composite sheet for forming a protective film, and a method for manufacturing the aforementioned semiconductor wafer.

◇Film for forming a protective film The film for forming a protective film according to an embodiment of the present invention is an energy ray curable film for forming a protective film, wherein the film for forming a protective film and silicon crystal are measured by the following method The adhesive force between circles is 3N/25mm or more, and when the protective film is formed by irradiating ultraviolet rays to the film for forming a protective film, the shear strength of the protective film measured by the following method is 10.5N/3mm□ or more . Adhesion between the film for forming a protective film and the silicon wafer: After attaching the film for forming a protective film with a thickness of 25 μm on the silicon wafer, the method was used to bring the film for forming a protective film and the silicon wafer into contact with each other. The surfaces of the surfaces form an angle of 180° with each other, and the film for forming a protective film is peeled away from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time is measured, and This measured value was taken as the adhesive force between the film for protective film formation and the silicon wafer. ^Shear strength of the protective film: After attaching the protective film forming film with a thickness of ²⁵ μm to the silicon wafer, the protective film was The film for forming was irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film, and the obtained silicon wafer with a protective film was diced into silicon wafers with a protective film with a size of 3mm×3mm, and only the The protective film in the obtained silicon wafer with protective film is applied to the surface direction of the protective film at a speed of 200 μm/s, and the maximum value of the force applied until the protective film is destroyed (N/3mm □) As the shear strength of the protective film.

As another aspect, a film for forming a protective film according to an embodiment of the present invention is an energy ray curable film for forming a protective film, and the film for forming a protective film has a protective film formation measured by the following method: The adhesive force between the film and the silicon wafer is 3N/25mm or more, and the film for forming a protective film has the following method when the film for forming a protective film is irradiated with ultraviolet rays to form a protective film. The shear strength of the said protective film is the characteristic of 10.5N/3mm□ or more. Adhesion between the film for forming a protective film and the silicon wafer: After attaching the film for forming a protective film with a thickness of 25 μm on the silicon wafer, the method was used to bring the film for forming a protective film and the silicon wafer into contact with each other. The surfaces of the surfaces form an angle of 180° with each other, and the film for forming a protective film is peeled away from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time is measured, and This measured value was taken as the adhesive force between the film for protective film formation and the silicon wafer. ^Shear strength of the protective film: After attaching the protective film forming film with a thickness of ²⁵ μm to the silicon wafer, the protective film was The film for forming was irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film, and the obtained silicon wafer with a protective film was diced into silicon wafers with a protective film with a size of 3mm×3mm, and only the The protective film in the obtained silicon wafer with protective film is applied to the surface direction of the protective film at a speed of 200 μm/s, and the maximum value of the force applied until the protective film is destroyed (N/3mm □) As the shear strength of the protective film.

The film for forming a protective film in one aspect of the present invention may have the aforementioned adhesive force of 3 N/25 mm or more and the aforementioned shear strength of 10.5 N/3 mm when the aforementioned adhesive force and shear strength are measured by the aforementioned method. □Chemical composition of the film for forming a protective film having the above characteristics The film for forming a protective film having the same chemical composition may have a thickness different from the thickness of the film for forming a protective film evaluated by the following method.

Here, the adhesive force between the film for forming a protective film and the silicon wafer is 3N/25mm or more, which means that the film for forming a protective film having a width of 25mm and the silicon wafer is 3N. In addition, the shear strength of the protective film is 10.5N/3mm□ or more, which means that the shear strength of a square protective film with a side length of 3mm is 10.5N.

A composite sheet for protective film formation can be formed by providing the said film for protective film formation on a support sheet as mentioned later.

The film for forming a protective film is cured by irradiation with energy rays to form a protective film. This protective film is used to protect the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The film for protective film formation is flexible and can be easily attached to an object to be attached. Since the film for forming a protective film has energy ray curability, it can form a protective film by curing in a shorter time than a film for forming a thermosetting protective film.

In addition, in this specification, "the film for protective film formation" means the film before hardening, and "protective film" means the film obtained by hardening the film for protective film formation.

In the present invention, the term "energy ray" refers to a ray having energy quanta in electromagnetic waves or charged particle beams, and examples thereof include ultraviolet rays, radiation rays, and electron beams. For example, ultraviolet rays can be irradiated by using a high pressure mercury lamp, fusion-H lamp, xenon lamp, black-light, LED lamp, etc. as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like. In the present invention, "energy ray curability" refers to the property of being cured by irradiating energy ray, and "non-energy ray curability" refers to the property of not curing even when irradiated with energy ray.

In the case of using the aforementioned film for forming a protective film, by spreading the semiconductor wafer in which the modified layer is formed in the direction of its surface (for example, the back surface), the semiconductor wafer is divided at the position of the aforementioned modified layer , and then produce a semiconductor wafer. In order to form the reformed layer inside the semiconductor wafer, it is possible to irradiate laser light so as to focus on a focal point set inside the semiconductor wafer. Since the strength of the modified layer of the semiconductor wafer is weakened, the modified layer inside the semiconductor wafer can be exerted force by expanding the semiconductor wafer formed with the modified layer in the surface direction of the semiconductor wafer, so that the semiconductor The wafer is broken at the location of the modification layer, and then a plurality of semiconductor wafers are obtained.

The aforementioned laser light irradiated when forming the aforementioned modified layer in the semiconductor wafer is preferably a laser light in the infrared region, and preferably a laser light with a wavelength of 1342 nm.

Since the adhesive force between the protective film forming film and the silicon wafer measured by the aforementioned method is 3N/25mm or more, and the shear strength of the protective film measured by the aforementioned method is 10.5N/3mm□ In the above, therefore, the semiconductor wafer with the protective film on the back surface (in this specification, sometimes referred to as "semiconductor wafer with protective film") is expanded, and the protective film is cut and the semiconductor wafer is simultaneously cut. When the circle is divided into semiconductor wafers (in this specification, sometimes referred to as "semiconductor wafers with a protective film"), it is possible to suppress the semiconductor wafer from floating from the protective film. The same applies to the case of a film for forming a protective film, and by taking a semiconductor wafer provided with a film for forming a protective film on the back surface (in this specification, sometimes referred to as a "semiconductor wafer with a film for forming a protective film") When the film for forming a protective film is cut and at the same time the semiconductor wafer is divided into semiconductor wafers (in this specification, sometimes referred to as "semiconductor wafers with a film for forming a protective film"), it is possible to suppress The semiconductor wafer floats from the film for protective film formation.

The aforementioned adhesive force is preferably 3.3N/25mm or higher, and more preferably 3.6N/25mm or higher. When the said adhesive force is more than the said lower limit value, the effect of suppressing the floating of a semiconductor wafer (not limited to a silicon wafer) from the said protective film or the film for protective film formation becomes more remarkable.

On the other hand, the upper limit of the aforementioned adhesive force is not particularly limited. However, considering that it becomes easier to pick up a semiconductor wafer with a protective film or a semiconductor wafer with a film for forming a protective film in the method of manufacturing a semiconductor device described later, the aforementioned adhesive force is preferably 10N/25mm or less, It is better to be below 9N/25mm, and especially preferably below 8N/25mm.

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

For example, the aforementioned adhesive force can be adjusted by adjusting the types and contents of components contained in the film for forming a protective film described later, the thickness of the film for forming a protective film, and the like. In particular, the aforementioned adhesive force can be easily adjusted by adjusting the content of the compound (p) and the like in the film for protective film formation described later.

The aforementioned shear strength is preferably at least 10.7N/3mm□, and more preferably at least 11.0N/3mm□. When the said shear strength is more than the said lower limit, the effect of suppressing the floating of a semiconductor wafer from the said protective film or the film for protective film formation becomes more remarkable.

On the other hand, the upper limit of the aforementioned shear strength is not particularly limited. For example, it is preferably not more than 30.0N/3mm□, more preferably not more than 27.5N/3mm□, and most preferably not more than 25.0N/3mm□.

The aforementioned shear strength can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, the aforementioned shear strength is preferably 10.5-30.0 N/3mm□, more preferably 10.7-27.5 N/3mm□, and particularly preferably 11.0-25.0 N/3mm□, but these are just examples.

For example, the aforementioned shear strength can be adjusted by adjusting the types and contents of components contained in the film for forming a protective film described later, the thickness of the film for forming a protective film, and the like. In particular, the aforementioned shear strength can be easily adjusted by adjusting the content of the compound (p) and the like in the film for protective film formation described later.

As an example of the aforementioned film for protective film formation, a film for protective film formation with the aforementioned adhesive force of 3 to 10 N/25 mm and the aforementioned shear strength of 10.5 to 30.0 N/3 mm□ is preferred; The film for protective film formation is preferably 3.3-9N/25mm and the aforementioned shear strength is 10.7-27.5N/3mm□; and the aforementioned adhesive force is 3.6-8N/25mm and the aforementioned shear strength is 11.0-25.0N /3mm□ protective film forming film is especially good. However, the aforementioned combination of adhesion and shear strength shown here is only one example.

As the above-mentioned film for forming a protective film that satisfies the conditions of the above-mentioned adhesive force and shear strength, for example, a compound containing a carboxyl group in one molecule or a group that forms a salt with a carboxyl group, and a polymerizable group (in this paper) In the specification, a film for forming a protective film may be referred to as "compound (p)"), and a film for forming a protective film containing an energy ray-curable component (a) and a compound (p) described later is preferable. A film for forming a protective film containing the compound (p) has not been known in the prior art. The energy ray curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.

The above-mentioned protective film forming film and the above-mentioned protective film of its cured product are used to react to the above-mentioned laser light (for example, laser light in the infrared region such as laser light with a wavelength of 1342nm) required for forming the modified layer of the semiconductor wafer. ) have high light transmittance. Both the film for protective film formation and the protective film generally show the same tendency with respect to light transmittance. In addition, the light transmittance in this specification is the value measured using the spectrophotometer without using an integrating sphere.

For example, the light transmittance of the above-mentioned film for forming a protective film with respect to laser light having a wavelength of 1342 nm (in this specification, sometimes simply referred to as "film light transmittance (1342 nm)") is preferably 45% or more, and 50% or more. The above is preferred, and more than 55% is particularly preferred. When the light transmittance (1342 nm) of the film is equal to or greater than the aforementioned lower limit value, the modified layer can be more easily formed on the semiconductor wafer in the method for manufacturing the semiconductor wafer described later. The upper limit of the film light transmittance (1342 nm) is not particularly limited, and may be, for example, 100%.

The light transmittance of the aforementioned protective film for laser light with a wavelength of 1342nm (in this specification, sometimes simply referred to as "protective film light transmittance (1342nm)") is preferably at least 45%, and more preferably at least 50%. , and more than 55% is especially good. When the light transmittance (1342 nm) of the protective film is equal to or greater than the aforementioned lower limit value, the modified layer can be more easily formed on the semiconductor wafer in the method for manufacturing the semiconductor wafer described later. The upper limit of the light transmittance (1342 nm) of the protective film is not particularly limited, for example, it may be 100%.

For example, the light transmittance (1342 nm) of the film can be adjusted by adjusting the types and contents of components contained in the film for forming a protective film, the thickness of the film for forming a protective film, and the like. For example, the light transmittance (1342 nm) of the protective film can be adjusted by adjusting the types and contents of components contained in the protective film, the thickness of the protective film, and the like.

The film for forming a protective film may have only one layer (single layer), or may be a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other. Not particularly limited. In addition, in this specification, not limited to the case of the film for protective film formation, "a plurality of layers may be the same or may be different from each other" means "all layers may be the same, or all layers may be the same. are different, or only a part of the layers may be the same", and "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other".

The thickness of the film for protective film formation is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. By making the thickness of the film for protective film formation more than the said lower limit, the protective film which has higher protective ability can be formed. Furthermore, by making the thickness of the film for protective film formation below the said upper limit, it can suppress that a protective film becomes thick too much. Here, the "thickness of the film for forming a protective film" refers to the thickness of the entire film for forming a protective film. For example, the thickness of a film for forming a protective film consisting of multiple layers refers to all the layers constituting the film for forming a protective film. total thickness. In addition, "the thickness of the film for protective film formation" can be measured using the method as mentioned below. Using a contact thickness gauge, the distance between the front surface and the back surface of the film for protective film formation was measured at arbitrary 5 points of the film for protective film formation. The average value of the measured 5 points was made into the thickness of the film for protective film formation. The thicknesses of the release film, the support sheet, the adhesive layer, the semiconductor wafer, and the substrate, which will be described later, are also measured by the above-mentioned method.

The curing conditions for curing the protective film-forming film to form the protective film are not particularly limited as long as the degree of curing allows the protective film to fully perform its function, and can be appropriately selected according to the type of protective film-forming film. For example, when curing the film for forming a protective film, the illuminance of energy rays is preferably 4 to 280 mW/cm ² . Furthermore, during the aforementioned curing, the light quantity of the energy rays is preferably 3 to 1000 mJ/cm ² .

FIG. 1 is a schematic cross-sectional view of a film for forming a protective film according to an embodiment of the present invention. In addition, in the following drawings used in conjunction with the description, for the sake of easy understanding of the characteristics of the present invention and for convenience, the main parts may be enlarged and shown, and the size ratio of each component may not be the same as the actual one.

The film 13 for forming a protective film shown here is provided with a first release film 151 on one surface (sometimes referred to as "the first surface" in this specification) 13a, and is separated from the first surface 13a. The second release film 152 is provided on the surface (sometimes referred to as “the second surface” in this specification) 13 b which is the opposite side. Such a film 13 for forming a protective film is suitable for storage in a roll form, for example.

The film 13 for forming a protective film can be formed using a composition for forming a protective film described later. The film 13 for protective film formation is energy-beam curable, and satisfies the conditions of the above-mentioned adhesive force and shear strength.

Any of the first release film 151 and the second release film 152 may be known. The first peeling film 151 and the second peeling film 152 may be the same as each other, or may be different from each other, for example, the peeling force required when peeling from the film 13 for protective film formation is different.

In the film 13 for forming a protective film shown in FIG. 1, a semiconductor wafer (not shown in the drawings) is attached to the exposed surface by removing one of the first release film 151 and the second release film 152. ) of the back surface. After that, the surface exposed by removing the remaining one of the first release film 151 and the second release film 152 is used as the sticking surface of the support sheet.

＜＜Protective film forming composition＞＞ The above-mentioned film for forming a protective film can be formed using a composition for forming a protective film containing the constituent materials thereof. For example, the protective film-forming film is formed on the target position by applying the protective film-forming composition on the surface where the protective film-forming film is to be formed, and drying as necessary. In the composition for forming a protective film, the ratio of the content of each component that does not evaporate at normal temperature is usually the same as the ratio of the content of the above-mentioned components in the film for forming a protective film. In addition, in this specification, "normal temperature" means the temperature which is not particularly cold or hot, that is, the normal temperature, For example, the temperature of 15-25 degreeC etc. are mentioned.

Coating of the composition for forming a protective film can be performed by a known method, for example, use of an air knife coater (Air-knife-Coater), blade coater (Blade-Coater), bar coating Bar-Coater, Gravure-Coater, Roll-Coater, Roll-knife-Coater, Curtain-Coater Coater), die coater (Die-Coater), knife coater (Knife-Coater), screen coater (Screen-Coater), Meyer rod coater (Meyer-bar-Coater) and kiss coater ( Kiss-Coater) and other coating machine methods.

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

<Protective film forming composition (IV-1)>

As a composition for protective film formation, the composition for protective film formation (IV-1) etc. which contain the said energy-beam curable component (a) and a compound (p) are mentioned, for example. A film for forming a protective film containing the compound (p) has not been known in the prior art.

[compound (p)]

Compound (p) has a carboxyl group (-C(=O)-O-H) in one molecule or a group that forms a salt with a carboxyl group, and a polymerizable group.

Examples of the group forming a salt with a carboxyl group include a group in which a carboxylate anion (—C(=O)—O ⁻ ) generated by dissociation of a proton (H ⁺ ) from a carboxyl group forms a salt with a cation.

In the composition (IV-1) for forming a protective film and the compound (p) in the film for forming a protective film, the carboxyl group may be in a state where the proton is not dissociated (in other words, the original state of the carboxyl group is maintained), or may be in a state where the proton has been dissociated. Dissociation into carboxylate anion.

It is presumed that the compound (p) improves the interaction between the protective film forming film or protective film and the semiconductor wafer or the semiconductor wafer because it has a carboxyl group or a group that forms a salt with a carboxyl group. As a result, it is presumed that the floating of the semiconductor wafer from the protective film or the film for protective film formation can be suppressed.

Furthermore, it can be inferred that compound (p), since it has a polymerizable group, can suppress incorporation into any polymer component in the protective film (in other words, form a copolymer) and suppress the adjacency from the protective film to the protective film. The layers (membranes) move. It is presumed that since the film for forming a protective film will eventually form a protective film by curing, the copolymer derived from this compound (p) can stably exist in the protective film, so that it can stably exhibit the ability to inhibit the semiconductor wafer from falling. The effect of the protective film floating.

The compound (p) having a carboxyl salt-forming group comprises one or more anionic moieties and one or more cationic moieties. The aforementioned anion moiety has one or more carboxylate anions per one anion moiety.

That is, the number of carboxylate anions in one molecule of the compound (p) may be only one, or may be two or more. Similarly, the number of the above-mentioned anion moieties in one molecule of the compound (p) may be only one, or may be two or more, and in the case of two or more, these anion moieties may all be the same, or all different, or it may be only partly the same. That is, the anion moiety in one molecule of the compound (p) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily, and are not particularly limited. The carboxylate anion in one molecule of compound (p) may be composed of carboxyl salt-forming groups, or only a part of it may be carboxyl salt-forming groups, and usually all of them are carboxyl-forming groups. The group composition of the salt is preferred.

The valence 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 one, or two or more, and in the case of two or more, these cations may be all the same, or all may be different, or may be Yes only part is the same. That is, the cations in one molecule of the compound (p) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily, and are not particularly limited. The cations in one molecule of the compound (p) may all be composed of carboxyl salt-forming groups, or only a part of them may be carboxyl salt-forming groups, and usually all of them are carboxyl salt-forming groups. The composition of the group is better.

The group that forms a salt with a carboxyl group in one molecule of the compound (p) may be only one, or two or more, and in the case of two or more, these groups may all be the same, or all may be different , or it can be that only some of them are the same. That is, the group that forms a salt with a carboxyl group in one molecule of compound (p) may be only one type, or may be two or more types. Not particularly limited.

As a compound (p) which has a group which forms a salt with a carboxyl group, various forms corresponding to the kind and valence of a cation are mentioned. More specifically, as such a compound (p), for example, a compound composed of one anion moiety and one cation; a compound composed of two or more anion moieties and one cation; a compound composed of 1 A compound composed of two or more anion moieties and two or more cations; a compound composed of two or more anion moieties and two or more cations, etc.

Compound (p) having a carboxyl salt-forming group, the entire molecule is electrically neutral, that is, the sum of the valences of the cations in a molecule of the compound (p) is the same as the sum of the valences of the anions better.

The aforementioned cations are not particularly limited, and may be either inorganic cations or organic cations.

Examples of inorganic cations among the aforementioned cations include alkali metal ions such as lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), and potassium ions (K ⁺ ); magnesium ions (Mg ²⁺ ), Calcium ion (Ca ²⁺ ), barium ion (Ba ²⁺ ) and other alkaline earth metal ions; aluminum ion (Al ³⁺ ), zinc ion (Zn ²⁺ ), tin ion (Sn ²⁺ , Sn ⁴⁺ ), etc. Typical/main group metal ions; transition metal ions of copper ions (Cu ⁺ , Cu ²⁺ ), iron ions (Fe ²⁺ , Fe ³⁺ ), manganese ions, nickel ions, etc.; ammonium ions (NH ₄ ⁺ ), etc. non-metallic ions, etc. For example, when the cation is a sodium ion, a group that forms a salt with a carboxyl group is represented by the formula "-C(=O)-O ^- Na ⁺ ".

As the organic cation among the aforementioned cations, for example, cations derived from amine compounds, quaternary ammonium cations, and the like can be cited. As the aforementioned cation derived from an amine compound, for example, a protonated cation of a primary amine, a secondary amine, or a tertiary amine is exemplified. As the aforementioned quaternary ammonium cation, for example, a cation in which four monovalent hydrocarbon groups are bonded to one nitrogen atom can be cited.

As preferred examples of inorganic cations and organic cations that are non-metallic ions among the aforementioned cations, for example, the general formula "(Z ¹ ) ₄ N ⁺ (wherein Z ¹ is a hydrogen atom, an alkyl or an aromatic group) can be listed. , the plurality of Z ¹ may be the same as or different from each other, and when there are 2 or more Z ¹ s, these alkyl groups may be bonded to each other to form a ring.)" represents a cation. The carboxyl salt-forming group composed of such cations can be represented by the general formula "-C(=O)-O ^- N ⁺ (Z ¹ ) ₄ (wherein Z ¹ is the same as above)".

In the aforementioned general formula, all of the plural (that is, four) Z ^1s may be the same, or all may be different, or only some of them may be the same.

The above ^- mentioned alkyl group in Z1 may be any of straight chain, branched chain and cyclic, and in the case of cyclic, may be any of monocyclic and polycyclic. The aforementioned aromatic group in Z ¹ may be either monocyclic or polycyclic.

The number of carbon atoms in the straight-chain or branched alkyl group in Z1 is preferably ¹ to 10, and examples of such alkyl groups include methyl, ethyl, n-propyl, and isopropyl. , n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl , 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-ethyl-1-methyl propyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 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, iso Octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-di Methylhexyl, 5,5-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl and decyl, etc. The number of carbon atoms of the linear or branched alkyl group in Z ¹ may be, for example, any of 1 to 8, 1 to 5, and 1 to 3, but these are only examples.

The number of carbon atoms in the aforementioned cyclic alkyl group in Z1 is preferably ³ to 10. Examples of such alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo Heptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl and tricyclodecanyl, etc. The number of carbon atoms of the cyclic alkyl group in Z ¹ may be, for example, any of 3-8 and 3-6, but these are only examples.

In the case where 2 or more (that is, 2, 3 or 4) Z ¹ are the aforementioned alkyl groups, these 2 or more alkyl groups may be bonded to each other and bonded to these alkyl groups The nitrogen atoms together form a ring. In this case, the position where two or more alkyl groups are bonded to each other is not particularly limited, and the formed ring may be either monocyclic or polycyclic.

The number of carbon atoms of the aforementioned aryl group in Z1 is preferably ⁶ to 20, and examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m- Tolyl, p-tolyl, xylyl (also known as dimethylphenyl), etc., and ^one or more hydrogen atoms in these aromatic groups are further replaced by these aromatic groups, the aforementioned in Z1 Aryl groups substituted by alkyl groups etc. These aromatic groups having substituents preferably have 6-20 carbon atoms including substituents.

The compound (p) may have only a carboxyl group in one molecule, or may have only a carboxyl group that forms a salt, or may have both a carboxyl group and a carboxyl group that form a salt.

The number of the carboxyl group and the group forming a salt from the carboxyl group in one molecule of the compound (p) may be only one each, or may be two or more each. Furthermore, the total number of carboxyl groups in one molecule of compound (p) and groups that form salts from carboxyl groups is not particularly limited, but is preferably 1 to 3, and more preferably 1 to 2.

In the compound (p), the position of the carboxyl group and the group forming a salt with the carboxyl group is not particularly limited. For example, in a compound (p) having a chain structure, these groups may be bonded to the terminal portion of the main chain (or the terminal portion of the main chain), or may be bonded to a non-terminal portion. In addition, in this specification, a "main chain" means the chain skeleton which has the largest number of atoms constituting the chain skeleton among the chain skeletons.

In the compound (p), the number of the carboxyl group bonded to one atom and the group forming a salt with the carboxyl group may be only one, or may be two or more (for example, when the aforementioned atom is a carbon atom Next, it is 2~4).

As the aforementioned polymerizable group in the compound (p), for example, a group having a polymerizable unsaturated bond, a group having an ethylenically unsaturated bond (also referred to as a double bond or C=C) can be cited. Group is better.

The number of the aforementioned polymerizable groups in one molecule of the compound (p) may be only one, or may be two or more, preferably 1 to 3, and more preferably 1 to 2.

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

The compound (p) preferably has an ester bond in addition to a carboxyl group or a carboxyl group forming a salt and a polymerizable group, and preferably has a carboxylate bond (from the formula "-C(=O)-O -" represents the group, or also known as carbonyloxy) is preferred. By using such a compound (p), the effect of suppressing the floating of a semiconductor wafer from a protective film or a film for protective film formation becomes more remarkable.

The number of the aforementioned ester bonds in one molecule of the compound (p) may be only 1, or may be 2 or more, preferably 1 to 4, and more preferably 1 to 3.

As a preferable example of the compound (p), for example, aliphatic dicarboxylic acid mono(meth)acryloxyalkyl ester (that is, the hydrogen atom of one carboxyl group of the aliphatic dicarboxylic acid is replaced by ( meth)acryloxyalkyl substituted compound); aromatic dicarboxylic acid mono(meth)acryloxyalkyl ester (that is, the hydrogen atom of one carboxyl group of aromatic dicarboxylic acid is replaced by ( meth)acryloxyalkyl); a compound in which the carboxyl group of the aforementioned aliphatic dicarboxylic acid mono(meth)acryloxyalkyl ester is substituted by a salt-forming group of the aforementioned carboxyl group; and the aforementioned A compound in which the carboxyl group of the aromatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is substituted by the above-mentioned group forming a salt with the carboxyl group, etc.

The said aliphatic dicarboxylic acid is a compound which has two carboxyl groups and the part other than these carboxyl groups is a linear, branched or cyclic non-aromatic divalent hydrocarbon group. The number of carbon atoms in the aforementioned hydrocarbon group is preferably 1-10, more preferably 2-8, and particularly preferably 2-6. For example, any of 2-5 and 2-4 may be used. The aforementioned hydrocarbon group is preferably an alkylene group.

The said aromatic dicarboxylic acid means the compound which has two carboxyl groups and the part other than these carboxyl groups is a divalent aromatic hydrocarbon group (it is also called an arylene group). The aforementioned aromatic hydrocarbon group may be either monocyclic or polycyclic. Examples of the above-mentioned aromatic hydrocarbon group include divalent groups (also referred to as arylene groups) in which one hydrogen atom is removed from the above-mentioned aromatic group in Z ¹ . The number of carbon atoms in the aforementioned aromatic hydrocarbon group is preferably 6-20, particularly preferably 6-15, and more preferably 6-12.

In aliphatic dicarboxylic acid mono(meth)acryloxyalkyl esters and compounds in which the carboxyl group is replaced by the above-mentioned group that forms a salt with a carboxyl group, the alkyl group bonded to the (meth)acryloxyl group The group (in other words, the alkylene group in the (meth)acryloxyalkyl group) may be linear, branched, or cyclic, or may have both a chain structure and a cyclic structure , and preferably linear or branched.

The number of carbon atoms 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, 2 to 6 may also be used. ~5, and any one of 2~4. The number of carbon atoms in the cyclic alkyl group is not particularly limited, but is preferably 3-10, more preferably 4-8, and particularly preferably 5-6.

The compound (p) has a chain structure, and the carboxyl group or the group forming a salt from the carboxyl group, and the polymerizable group are all terminal parts of the main chain, and the non-terminal part of the main chain preferably has an ester bond.

As preferable examples of such compound (p), for example, aliphatic dicarboxylic acid mono(meth)acryloxyalkyl esters; and the aforementioned aliphatic dicarboxylic acid mono(meth)acryloxyalkyl esters; A compound in which the carboxyl group of an alkyl alkyl ester is substituted by the above-mentioned group forming a salt with a carboxyl group.

As a particularly good example of the compound (p), for example, 1-[2-(acryloxy)ethyl] succinate (also known as succinic acid mono(2-acryloxyethyl), CH ₂ =CH–C(=O)–O–CH ₂ CH ₂ –O–C(=O)–CH ₂ CH ₂ –C(=O)–OH); succinic acid 1-[2-(methylpropene Acyloxy)ethyl] (CH ₂ =C(–CH3)–C(=O)–O–CH ₂ CH ₂ –O–C(=O)–CH ₂ CH ₂ –C(=O)–OH ); 1-[2-(acryloyloxy)ethyl] glutarate (CH ₂ =CH–C(=O)–O–CH ₂ CH ₂ –O–C(=O)–CH _{2 CH} CH ₂ –C(=O)–OH); succinic acid 1-[2-(acryloyloxy)ethyl] carboxyl group is replaced by the above-mentioned carboxyl salt-forming group; succinic acid 1-[2 - a compound in which the carboxyl group of (methacryloxy)ethyl] is replaced by the above-mentioned group forming a salt with a carboxyl group; and the carboxyl group of glutaric acid 1-[2-(acryloxy)ethyl] is replaced by the above-mentioned A compound substituted with a carboxyl group that forms a salt.

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

The protective film-forming composition (IV-1) and the compound (p) contained in the protective film-forming film may be used alone, or two or more kinds may be used, and when two or more kinds are used, any Choose its combination and proportion.

In the composition for forming a protective film (IV-1), the ratio of the content of the compound (p) to the total content of components other than the solvent (that is, the content of the compound (p) in the film for forming a protective film, in other words , the mass of the compound (p) relative to the total mass of the film for forming a protective film) is preferably at least 0.15% by mass, more preferably at least 0.2% by mass, and particularly preferably at least 0.25% by mass. When the ratio of the said content is more than the said lower limit, the effect of suppressing the floating of a semiconductor wafer from the said protective film or the film for protective film formation becomes more remarkable.

On the other hand, the upper limit value of the ratio of the said content (content of compound (p) in the film for protective film formation) is not specifically limited. However, from the viewpoint of avoiding the influence caused by the excessive use of the compound (p), as a result, the degree of curing of the protective film is further improved and the performance of the protective film is further improved, the ratio of the aforementioned content is preferably 3% by mass or less , preferably 2% by mass or less, and particularly preferably 1% by mass or less.

The ratio of the content (the content of the compound (p) in the protective film forming film) can be appropriately adjusted within the range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, the proportion of the aforementioned content is preferably 0.15-3% by mass, more preferably 0.2-2% by mass, and particularly preferably 0.25-1% by mass, but these are just examples.

[Energy ray curable component (a)] The energy ray-curable component (a) is a component that is cured by irradiation of energy rays, that is, a component for imparting film-forming properties, flexibility, and the like to the film for forming a protective film. As the energy ray curable component (a), for example, a polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000, and a polymer (a1) having an energy ray curable group and having an absolute molecular weight or weight A compound (a2) having an average molecular weight of 100 to 80,000. At least a part of the aforementioned polymer (a1) may already be cross-linked by a cross-linking agent (f) described later, or may not be cross-linked. In addition, in this specification, the so-called weight average molecular weight is a standard polystyrene equivalent value measured by gel-permeation-chromatography (GPC) method unless otherwise specified.

(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 of another compound. Acrylic resin (a1-1 ).

Examples of the aforementioned functional groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms). Substituted group), epoxy group, etc. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor wafers, the aforementioned functional groups are preferably groups other than carboxyl groups. Among the above, the aforementioned functional group is preferably a hydroxyl group.

‧Acrylic polymer with functional groups (a11) Examples of the acrylic polymer (a11) having a functional group include polymers obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group, and may be A polymer obtained by copolymerizing with a monomer other than an acrylic monomer (non-acrylic monomer) in addition to these monomers. In addition, the aforementioned acrylic polymer (a11) may be a random (random) copolymer or a block (block) copolymer.

Examples of the acrylic monomer having the aforementioned functional groups include hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, substituted amino-containing monomers, and epoxy-containing monomers. Wait.

Examples of the aforementioned hydroxyl-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; vinyl alcohol And non-(meth)acrylic unsaturated alcohols (unsaturated alcohols without a (meth)acryl skeleton) such as acrylic alcohol.

In addition, in this specification, "(meth)acryl" means the concept including both "acryl" and "methacryl". The same applies to other terms similar to (meth)acrylic acid.

As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; Ethylenically unsaturated dicarboxylic acids (that is, dicarboxylic acids having ethylenically unsaturated bonds), such as aconic acid, maleic acid, and citraconic acid; Anhydrides; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate, etc.

The acrylic monomers having the aforementioned functional groups are preferably hydroxyl-containing monomers or carboxyl-containing monomers, and more preferably hydroxyl-containing monomers.

The acrylic monomers having the aforementioned functional groups constituting the aforementioned acrylic polymer (a11) may be used alone or in combination of two or more. .

Examples of acrylic monomers having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth) ) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, decadecyl (meth)acrylate Hexadecyl (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

Furthermore, examples of acrylic monomers that do not have the aforementioned functional groups include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxy (meth)acrylate, (meth)acrylic acid esters containing alkoxyalkyl groups such as methoxymethyl esters and ethoxyethyl (meth)acrylates; aryl (meth)acrylates containing phenyl (meth)acrylates, etc. (Meth)acrylates with aromatic groups; non-crosslinkable (meth)acrylamide and its derivatives; N,N-dimethylaminoethyl (meth)acrylate and (methyl) ) Non-crosslinkable tertiary amino (meth)acrylates such as N,N-dimethylaminopropyl acrylate, etc.

The acrylic monomers not having the aforementioned functional groups constituting the aforementioned acrylic polymer (a11) may be used alone or in combination of two or more. When using two or more types, combinations thereof and Proportion.

Examples of the non-acrylic monomers include ethylene and olefins such as norbornene; vinyl acetate; and styrene. The non-acrylic monomer constituting the acrylic polymer (a11) may be used alone or in two or more types. When two or more types are used, the combination and ratio thereof may be selected arbitrarily.

In the acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group to the total amount of structural units constituting the acrylic polymer (a11) , preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. Since the aforementioned ratio is within such a range, energy rays in the aforementioned acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray-curable compound (a12) The content of curable groups can be easily adjusted within the range where the protective film has a better degree of curing.

The above-mentioned acrylic polymer (a11) constituting the above-mentioned acrylic resin (a1-1) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily .

In the protective film forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass based on the total mass of the protective film forming composition (IV-1). , 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) has one or more kinds selected from the group consisting of isocyanate group, epoxy group, and carboxyl group as the functional A group that reacts with a group is preferable, and it is more preferable to have an isocyanate group as the aforementioned group. For example, when the energy ray-curable compound (a12) has 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 aforementioned energy ray curable compound (a12) preferably has 1 to 5 aforementioned energy ray curable groups in 1 molecule, and more preferably has 1 to 3 groups.

Examples of the aforementioned energy ray-curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacrylyl isocyanate , allyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; Acryl monoisocyanate compound obtained by reacting diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate; Acryl monoisocyanate compound obtained by reacting diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc. Among the above, the aforementioned energy ray curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be used alone or in combination of two or more. Proportion.

In the acrylic resin (a1-1), the energy derived from the energy ray-curable compound (a12) is The content of the radiation-curable group is preferably 20-120 mol%, more preferably 35-100 mol%, and particularly preferably 50-100 mol%. Since the ratio of the foregoing content is within such a range, the adhesive force of the protective film formed by curing becomes greater. In addition, when the aforementioned energy ray-curable compound (a12) is a monofunctional (having one aforementioned group in 1 molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mole %, while the aforementioned energy When the radiation curable compound (a12) is a polyfunctional (having two or more of the above-mentioned groups in one molecule) compound, the upper limit of the ratio of the above-mentioned content exceeds 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.

When at least a part of the polymer (a1) is cross-linked by the cross-linking agent (f), the polymer (a1) does not belong to the constituents of the acrylic polymer (a11) described above. Any of the above-mentioned monomers, but may be a polymer in which a monomer having a group reactive with the crosslinking agent (f) is polymerized and crosslinked at the group reactive with the crosslinking agent (f), or A polymer derived from the aforementioned energy ray curable compound (a12) and cross-linked at a group reactive with the aforementioned functional group may also be used.

The above-mentioned polymer (a1) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used alone, or may be used in two or more kinds. When two or more kinds are used, The combination and proportion thereof can be selected arbitrarily.

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

The aforementioned compound (a2) is not particularly limited as long as it satisfies the aforementioned conditions and its molecular weight is smaller than that of the aforementioned polymer (a1). Epoxy resins with groups, phenolic resins with energy ray curable groups, etc.

Among the aforementioned compounds (a2), examples of low-molecular-weight compounds having energy-ray-curable groups include polyfunctional monomers or oligomers, and acrylate-based compounds having (meth)acryl groups better. Examples of the aforementioned acrylate compounds include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethylene Oxylated bisphenol A di(meth)acrylate, 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)acryl) oxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also known as tricyclodecane dimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene Diethylene glycol (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, and 2-hydroxy - Difunctional (meth)acrylates such as 1,3-di(meth)acryloxypropane; ginseng (2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified ginseng-(2-(meth)acryloxyethyl)isocyanurate , Ethoxylated Glyceryl Tri(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Ditrimethylolpropane Tetra(meth)acrylate Acrylates, Ethoxylated Neopentylthritol Tetra(meth)acrylates, Neopentylthritol Tetra(meth)acrylates, Di-Neoerythritol Poly(meth)acrylates, and Di-Neopentylthritol Multifunctional (meth)acrylates such as hexa(meth)acrylates; Polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers, etc.

Among the aforementioned compounds (a2), as an epoxy resin having an energy ray curable group and a phenolic resin having an energy ray curable group, for example, "Japanese Patent Laid-Open No. 2013-194102" can be used. The materials described in paragraph 0043 et al. This resin also corresponds to the resin constituting the thermosetting component (h) described later, but in the present invention, it is handled as the aforementioned compound (a2).

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

The compound (IV-1) for forming a protective film and the aforementioned compound (a2) contained in the film for forming a protective film may be used alone or in combination of two or more. Any combination and proportion thereof can be selected arbitrarily.

[Polymer (b) not having an energy ray curable group] In the case where the composition for forming a protective film (IV-1) and the film for forming a protective film contain the aforementioned compound (a2) as the aforementioned energy ray-curable component (a), a compound having no energy ray-curable group is further contained. Polymer (b) is preferred. At least a part of the aforementioned polymer (b) may already be cross-linked by a cross-linking agent (f) described later, or may not be cross-linked.

Examples of the polymer (b) not having an energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and urethane acrylate resins. , polyvinyl alcohol (PVA), butyral resin, polyester urethane resin, etc. Among the above, the polymer (b) is preferably an acrylic polymer (hereinafter, sometimes simply referred to as "acrylic polymer (b-1)").

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, glycidyl group-containing ( Meth)acrylates, hydroxyl-containing (meth)acrylates, and substituted amino-containing (meth)acrylates, etc. Here, the "substituted amino group" is as described above.

Examples of the aforementioned alkyl (meth)acrylate include (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate (also known as lauryl (meth)acrylate), ( Tridecyl (meth)acrylate, Myristyl (meth)acrylate (also known as myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Hexadecyl (meth)acrylate Composition of ester (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), etc. The alkyl group of the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

Examples of the (meth)acrylate having a cyclic skeleton include isobornyl (meth)acrylate and cycloalkyl (meth)acrylate such as dicyclopentyl (meth)acrylate. ester; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylate, such as dicyclopentenyloxyethyl (meth)acrylate, etc.

As said glycidyl group containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example. Examples of the hydroxyl group-containing (meth)acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate, Base) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, etc. Examples of the substituted amino group-containing (meth)acrylate 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; and styrene.

Examples of the aforementioned polymer (b) having no energy ray-curable group that is at least partially crosslinked by the crosslinking agent (f) include reactive functional groups and crosslinking groups in the aforementioned polymer (b). The polymer after the reaction of the agent (f). The above-mentioned reactive functional group can be appropriately selected according to the type of crosslinking agent (f), 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 carboxyl group, and an amino group, among which a hydroxyl group having high reactivity with an isocyanate group is preferred. Furthermore, when the crosslinking agent (f) is an epoxy compound, examples of the reactive functional groups include carboxyl groups, amino groups, amido groups, and the like, among which those having high reactivity with epoxy groups Carboxyl is preferred. However, the aforementioned reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a semiconductor wafer, a circuit of a semiconductor wafer, or the like.

As a polymer (b) which has the said reactive functional group but does not have an energy-ray curable group, the polymer obtained by polymerizing the monomer which has the said reactive functional group at least is mentioned, for example. In the case of the acrylic polymer (b-1), any one of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) or Both, monomers having the aforementioned reactive functional groups can be used. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing a hydroxyl group-containing (meth)acrylate. In addition, the above-mentioned acrylic monomers or non-acrylic monomers exemplified by polymerizing a monomer in which one or more hydrogen atoms are replaced by the above-mentioned reactive functional groups obtained polymer.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of structural units derived from monomers having a reactive functional group relative to the total amount of structural units constituting the polymer (b) , preferably 1 to 25% by mass, and more preferably 2 to 20% by mass. With this ratio being within such a range, the degree of crosslinking in the aforementioned polymer (b) can become a more preferable range.

From the viewpoint of making the film-forming properties of the protective film-forming composition (IV-1) better, the weight average molecular weight (Mw) of the polymer (b) not having an energy ray curable group is 10000~ 2,000,000 is preferable, and 100,000 to 1,500,000 is more preferable.

The protective film-forming composition (IV-1) and the polymer (b) having no energy ray-curable group contained in the protective film-forming film may be used alone or in combination of two or more. When using 2 or more types, the combination and ratio can be chosen arbitrarily.

Examples of the protective film forming composition (IV-1) include compositions containing either or both of the aforementioned polymer (a1) and the aforementioned compound (a2) in addition to the compound (p). Furthermore, when the composition (IV-1) for protective film formation contains the said compound (a2), it is preferable to further contain the polymer (b) which does not have an energy-ray curable group, and in this case, It is also preferable to further contain the aforementioned (a1). In addition, the composition (IV-1) for protective film formation may contain the said polymer (a1) and the polymer (b) which does not have an energy-ray curable group, and may not contain the said compound (a2).

When the protective film forming composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2) and the polymer (b) having no energy ray curable group, the protective film forming composition In the substance (IV-1), the content of the aforementioned compound (a2) is 10 to 400 mass parts relative to 100 mass parts of the total content of the aforementioned polymer (a1) and the polymer (b) not having an energy ray curable group. Parts are preferable, and 30 to 350 parts by mass is more preferable.

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 with respect to the total content of components other than the solvent Content ratio (that is, the sum of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group in the protective film-forming film relative to the total mass of the protective film-forming film content), preferably 5-90% by mass, more preferably 10-80% by mass, particularly preferably 15-70% by mass, for example, any of 20-60% by mass and 25-50% by mass one. When the ratio of the said total content exists in such a range, the energy-beam curability of the film for protective film formation becomes more favorable.

In the case where the protective film forming composition (IV-1) contains the aforementioned energy ray curable component (a) and the polymer (b) not having an energy ray curable group, the protective film forming composition (IV-1) -1) and the film for forming a protective film, the content of the aforementioned polymer (b) is preferably 50 to 400 parts by mass, preferably 100 to 350 parts by mass, based on 100 parts by mass of the content of the energy ray curable component (a). It is preferable, and it is especially preferable to use 150-300 mass parts. When the said content of the said polymer (b) exists in such a range, the energy-beam curability of the film for protective film formation becomes more favorable.

The protective film-forming composition (IV-1) may contain components other than the energy ray-curable component (a), the polymer (b) having no energy ray-curable group, and the compound (p) depending on the purpose. selected from photopolymerization initiator (c), filler (d), coupling agent (coupling agent) (e), crosslinking agent (f), colorant (g), thermosetting component (h), curing accelerator (i ) and general-purpose additives (z) in the group consisting of 1 or 2 or more. For example, by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the formed protective film-forming film can be improved by heating. The adhesive strength of the adhesive can also be improved, and the strength of the protective film formed by the protective film-forming film can also be improved.

[Photopolymerization initiator (c)] As the photopolymerization initiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl acetal Benzoin compounds such as ketones; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethane- Acetophenone compounds such as 1-keto; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acyl phosphine oxide compounds such as benzyl phenyl sulfide, tetramethylthiuram monosulfide and other sulfides; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisiso Azo compounds such as butyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, and 2-(dimethylamino)-1-(4-mol Olinophenyl)-2-benzyl-1-butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- , benzophenone compounds such as 1-(O-acetyloxime); peroxides; diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; and 2-chloroanthraquinone, etc. In addition, as a photoinitiator (c), for example, a quinone compound, such as 1-chloroanthraquinone; and a photosensitizer, such as an amine, etc. can be used.

The photopolymerization initiator (c) contained in the protective film forming composition (IV-1) may be used alone, or may be used in two or more kinds, and in the case of using two or more kinds, any of them may be selected combination and proportion.

In the case of using the photopolymerization initiator (c), in the protective film forming composition (IV-1), the photopolymerization initiator ( The content of c) 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 the filler (d), it becomes easy to adjust the thermal expansion coefficient of the protective film obtained by hardening the film for protective film formation. Furthermore, by optimizing the coefficient of thermal expansion for the object on which the protective film is to be formed, the reliability of the package obtained using the protective film forming composite sheet can be further improved. Furthermore, 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 property etc. can also be improved. As the filler (d), for example, a filler made of a heat-conducting material is exemplified.

The filler (d) may be either an organic filler or an inorganic filler, and an inorganic filler is preferable. Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide, silicon carbide, and boron nitride; beads obtained by spheroidizing the above inorganic fillers grains; surface-modified products of the above-mentioned inorganic fillers; single-crystal fibers of the above-mentioned inorganic fillers; and glass fibers, etc. Among the above, silica or alumina is preferred as the inorganic filler.

The average particle size of the filler (d) is not particularly limited, but is preferably 0.01-20 μm, more preferably 0.1-15 μm, and particularly preferably 0.3-10 μm. When the average particle size of the filler (d) is in such a range, the adhesiveness of the protective film to the object on which the protective film is to be formed can be maintained, and at the same time, the decrease in light transmittance of the protective film can be suppressed. In addition, in this specification, "average particle diameter" means the particle diameter (D50) value of 50% of cumulative values in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified.

The filler (d) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by one type, or two or more types may be used, and when two or more types are used, any Choose its combination and proportion.

In the case of using the filler (d), in the composition for forming a protective film (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the protective film forming The content of the filler (d) in the film) is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass, for example, 40 to 70% by mass and Either of 45 to 65% by mass. When the content of the filler (d) is within such a range, the adjustment of the coefficient of thermal expansion becomes easier.

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

The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group contained in the energy ray curable component (a), the polymer (b) having no energy ray curable group, etc., and is Silane coupling agent is preferred. As a preferred example of the aforementioned silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-Mercaptopropylmethyldimethoxysilane, Bis(3-triethoxysilylpropyl)tetrasulfane, Methyltrimethoxysilane, Methyltriethoxysilane , Vinyl trimethoxysilane, vinyl triacetoxysilane and imidazole silane, etc.

The coupling agent (e) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used alone, or may be used in two or more kinds, and when two or more kinds are used, it may be Any combination and proportion thereof can be selected arbitrarily.

In the case of using the coupling agent (e), in the composition for forming a protective film (IV-1) and the film for forming a protective film, relative to the energy ray-curable component (a) and the energy ray-curable group The total content of the polymer (b) is 100 parts by mass, and the content of the coupling agent (e) is preferably 0.03-20 parts by mass, more preferably 0.05-10 parts by mass, and particularly preferably 0.1-5 parts by mass . When the above-mentioned content of the coupling agent (e) is more than the above-mentioned lower limit, the dispersibility of the filler (d) in the resin can be improved, and the adhesiveness of the film for forming a protective film to the adherend can be improved, so that the The effect brought about by using the coupling agent (e) is obtained. Furthermore, since the said content of a coupling agent (e) is below the said upper limit, the generation|occurrence|production of outgassing (outgas) is suppressed further.

[Crosslinking agent (f)] By crosslinking the energy ray-curable component (a), the polymer (b) having no energy ray-curable group, etc., using the crosslinking agent (f), it is possible to adjust the initial adhesive force and the cohesion.

Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine type Crosslinking agent (crosslinking agent having an aziridine group), etc.

Examples of the aforementioned organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc." ); trimers of the aforementioned aromatic polyvalent isocyanate compounds, etc.; isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds Wait. The aforementioned "adduct" refers to aromatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, or alicyclic polyvalent isocyanate compounds with ethylene glycol, propylene glycol, neopentyl glycol, trimethylol Reaction products of low-molecular-weight active hydrogen-containing compounds such as propane or castor oil. As an example of the aforementioned adduct, a xylylene diisocyanate adduct of trimethylolpropane as described later, etc. are mentioned. Furthermore, the term "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; Isocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; polyols such as trimethylolpropane added toluene di Any one or two or more compounds of isocyanate, hexamethylene diisocyanate and xylylene diisocyanate; and lysine diisocyanate, etc.

Examples of the aforementioned organic polyvalent imine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β -Aziridinylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, and N,N'-toluene-2,4-bis(1-aziridinylamide) Three extended melamine and so on.

In the case of using an organic polyvalent isocyanate compound as the crosslinking agent (f), a hydroxyl-containing polymer is used as the energy ray-curable component (a) or a polymer (b) having no energy ray-curable group is good. When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, by the crosslinking agent (f) and energy The reaction between the radiation-curable component (a) and the polymer (b) not having an energy-beam-curable group can easily introduce a crosslinked structure into the film for forming a protective film.

The crosslinking agent (f) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by 1 type, or may use 2 or more types, and when 2 or more types are used, The combination and proportion thereof can be selected arbitrarily.

In the case of using the crosslinking agent (f), in the composition for forming a protective film (IV-1), relative to the energy ray curable compound (a) and the polymer (b) not having an energy ray curable group ) in a total content of 100 parts by mass, the content of the crosslinking agent (f) is preferably 0.01-20 parts by mass, more preferably 0.1-10 parts by mass, and particularly preferably 0.5-5 parts by mass. Since the said content of a crosslinking agent (f) is more than the said lower limit, the effect by using a crosslinking agent (f) can be acquired more notably. Furthermore, when the said content of a crosslinking agent (f) is below the said upper limit, excessive use of a crosslinking agent (f) can be suppressed.

[Coloring agent (g)] Examples of the colorant (g) include known colorants such as inorganic pigments, organic pigments, and organic dyes.

Examples of the aforementioned organic pigments and organic dyes include ammonium (Aminium) pigments, cyanine (Cyanine) pigments, merocyanine (Merocyanine) pigments, Croconium (Croconium) pigments, Squarylium pigments, Azulenium pigments, Polymethine pigments, Naphthoquinone pigments, Pyrylium pigments, Phthalocyanine pigments, Naphthalocyanine pigments, Naphthalactam pigments, Azo pigments, condensed azo pigments, Indigo pigments, Perinone pigments, Perylene pigments ) pigments, Dioxazine pigments, Quinacridone pigments, Isoindolinone pigments, Quinophthalone pigments, Pyrrole pigments, Thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indole phenol pigments, triallyl methane ) pigments, Anthraquinone pigments, Naphthol pigments, Azomethine pigments, Benzimidazolone pigments, Pyranthrone pigments and Shilin (Threne) pigments, etc.

Examples of the aforementioned inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, and ruthenium-based pigments. , platinum pigments, ITO (indium tin oxide) pigments, and ATO (antimony tin oxide) pigments, etc.

The coloring agent (g) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, you may use Any combination and proportion thereof can be selected arbitrarily.

When using a coloring agent (g), content of the coloring agent (g) in the protective film forming composition (IV-1) and the protective film forming film can be adjusted suitably according to the objective. For example, in the case of adjusting the printing visibility by adjusting the content of the colorant (g) and adjusting the light transmittance of the protective film, in the protective film forming composition (IV-1), relative to all the solvents The ratio of the total content of the components to the content of the colorant (g) (that is, the content of the colorant (g) in the protective film forming film) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass , and preferably 0.8 to 5% by mass. When the said content of a coloring agent (g) is more than the said lower limit, the effect by using a coloring agent (g) can be acquired more notably. Furthermore, when the said content of a coloring agent (g) is below the said upper limit, excessive use of a coloring agent (g) can be suppressed.

[Thermosetting composition (h)] The thermosetting component (h) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used alone, or may be used in two or more kinds, and in the case of using two or more kinds, it may be Any combination and proportion thereof can be selected arbitrarily.

Examples of the thermosetting component (h) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferred.

(epoxy thermosetting resin) Epoxy thermosetting resin is composed of epoxy resin (h1) and thermosetting agent (h2). The epoxy-based thermosetting resins contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be used only by one type, or two or more types may be used, and when two or more types are used, it may be Any combination and proportion thereof can be selected arbitrarily.

‧Epoxy resin (h1) Examples of the epoxy resin (h1) include known epoxy resins such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydride, o-cresol novolak epoxy resin Dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin, etc. Oxygen compounds.

An epoxy resin having an unsaturated hydrocarbon group can also be used as the epoxy resin (h1). An epoxy resin having an unsaturated hydrocarbon group has higher miscibility with an acrylic resin than an epoxy resin not having an unsaturated hydrocarbon group. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the composite sheet for protective film formation can be improved.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound obtained by converting a part of the epoxy group of a 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 an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group. In addition, as an epoxy resin which has an unsaturated hydrocarbon group, the compound which the group which has an unsaturated hydrocarbon group and the aromatic ring etc. which comprise an epoxy resin are directly bonded is mentioned, for example. The unsaturated hydrocarbon group is a polymerizable unsaturated group. As its specific example, vinyl (ethenyl, also known as vinyl), 2-propenyl (2-propenyl, also known as allyl), (formyl base) acryl group, and (meth)acrylamide group, etc., preferably acryl group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30,000, and preferably 400 to 10,000 from the viewpoint of the curability of the protective film forming film, and the strength and heat resistance of the protective film. Preferably, 500-3000 is particularly preferred. In this specification, unless otherwise specified, the "number average molecular weight" means the number average molecular weight represented by a value in terms of standard polystyrene measured by gel permeation chromatography (GPC). The epoxy equivalent of the epoxy resin (h1) is preferably 100-1000 g/eq, more preferably 150-800 g/eq. In this specification, "epoxy equivalent" refers to the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.

One type of epoxy resin (h1) may be used alone, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

‧Heat curing agent (h2) The thermal 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 functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional groups, for example, phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid groups are functional groups of acid anhydrides, etc., wherein the functional groups of phenolic hydroxyl groups, amino groups, and acid groups as acid anhydrides are preferred, and A phenolic hydroxyl group or an amino group is preferred.

Among the thermosetting agents (h2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, and aromatic resins. Alkylphenol resins, etc. Among the thermosetting agents (h2), examples of the amine curing agent having an amine group include dicyandiamide and the like.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl groups of a phenolic resin is substituted by a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the phenolic resin. Compounds on the aromatic ring, etc. The aforementioned 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.

In the case of using a phenolic curing agent as the thermal curing agent (h2), from the viewpoint of improving the peelability of the protective film from the support sheet, the thermal curing agent (h2) should have a high softening point or a high glass transition temperature. good. In this specification, the term "glass transition temperature" is measured by measuring the DSC curve of a sample using a differential scanning calorimeter, and is expressed as the temperature at the inflection point of the obtained DSC curve.

In the thermosetting agent (h2), for example, the number average molecular weight of resin components such as polyfunctional phenolic resin, novolac type phenolic resin, dicyclopentadiene type phenolic resin, and aralkylphenol resin is 300 to 30,000. Preferably, 400-10000 is more preferable, and 500-3000 is especially preferable. The molecular weight of non-resin components such as bisphenol and dicyandiamide in the thermosetting agent (h2) is not particularly limited, and is preferably 60-500, for example.

The thermosetting agent (h2) can be used individually by 1 type, or 2 or more types can also be used, and when using 2 or more types, the combination and ratio can be chosen arbitrarily.

In the case of using a thermosetting component (h), in the composition for forming a protective film (IV-1) and the film for forming a protective film, the thermosetting agent (h2 ) content is preferably 0.01 to 20 parts by mass.

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

[Curing Accelerator (i)] The curing accelerator (i) is a component for adjusting the curing rate of the film for protective film formation. Preferred examples of the curing accelerator (i) include triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and ginseng (dimethylaminomethyl)phenol. Class amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4- Imidazoles such as methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylphosphonium tetraphenylborate and triphenylphosphine Tetraphenylboron salts such as tetraphenylborate and the like.

The curing accelerator (i) may be used alone or in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the case of using the curing accelerator (i), the content of the curing accelerator (i) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited, and can be determined according to the content of the curing accelerator (i) used together. The ingredients are properly selected.

[General Additive (z)] The general-purpose additive (z) can be a known additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. For example, plasticizers, antistatic agents, antioxidants, and gettering agents can be listed as preferred ones. example.

The general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be used only by one type, or two or more types may be used, and when two or more types are used, it may be Any combination and proportion thereof can be selected arbitrarily. In the case of using the general-purpose additive (z), the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited, and can be appropriately selected according to the purpose.

[solvent] The protective film forming composition (IV-1) preferably further contains a solvent. The protective film-forming composition (IV-1) containing a solvent has good handling properties. The aforementioned solvents are not particularly limited, and examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butanol Alcohols such as ethyl acetate; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides such as dimethylformamide and N-methylpyrrolidone Species (compounds having an amide bond) and the like are preferred examples. The solvent contained in the protective film forming composition (IV-1) may be used alone or in two or more kinds. When two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

From the viewpoint that the components contained in the composition for forming a protective film (IV-1) can be mixed more uniformly, the solvent contained in the composition for forming a protective film (IV-1) is based on methyl ethyl ketone, toluene , ethyl acetate, etc. are preferred.

＜<Manufacturing method of protective film forming composition>> A composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by preparing each component for constituting the composition for forming a protective film. The order of addition when preparing each component is not specifically limited, You may add 2 or more types of components at the same time. In the case of using a solvent, it can be used by mixing the solvent with any of the formulation components other than the solvent and diluting the formulation components in advance, or by not mixing any of the formulation components other than the solvent. It is used by mixing the solvent and this preparation component as it is diluted beforehand. The mixing method of the components is not particularly limited at the time of preparation, and can be appropriately selected from known methods such as mixing by rotating a stirrer or stirring blade, mixing by using a mixer, and mixing by applying ultrasonic waves. The temperature and time during the addition and mixing of each component are not particularly limited as long as they do not cause deterioration of each compounded component, and can be appropriately adjusted, but the temperature is preferably 15-30°C.

◇Manufacturing method of protective film forming film The film for protective film formation can be manufactured by apply|coating the composition for protective film formation on a peeling film (preferably the peeling-treated surface), and drying as needed. The production method at this time is as described above. Moreover, for example, as shown in FIG. 1, the film for protective film formation is stored normally with the peeling film bonded to the both surfaces. Therefore, on the exposed surface (the surface opposite to the side provided with the release film) of the protective film forming film formed on the release film as described above, a release film (with its release-treated surface) can be further bonded. preferably).

◇How to use the film for protective film formation As mentioned above, the composite sheet for protective film formation can be comprised by providing the said film for protective film formation on a support sheet. The composite sheet for protective film formation is attached to the back surface (surface on the opposite side to the electrode formation surface) of a semiconductor wafer through the film for protective film formation among them. After that, starting from this state, the target semiconductor wafer and semiconductor device can be manufactured by the manufacturing method described later.

On the other hand, the film for forming a protective film may not be provided on the support sheet, but may be provided on the back surface of the semiconductor wafer first. For example, first, a film for forming a protective film is attached to the back surface of the semiconductor wafer, and a support sheet is attached to the exposed surface of the film for forming a protective film (the side opposite to the side attached to the semiconductor wafer). surface), or by irradiating the film for forming a protective film in this attached state with energy rays and curing it into a protective film, and then attaching the supporting sheet to the exposed surface of the protective film (and the surface attached to the semiconductor wafer) The side is the surface on the opposite side), and then a composite sheet for forming a protective film is formed. After that, starting from this state, the target semiconductor wafer and semiconductor device can be manufactured by the manufacturing method described later.

◇Composite sheets for protective film formation The composite sheet for protective film formation according to one embodiment of the present invention includes a support sheet, and includes the film for protective film formation on the support sheet.

In the present invention, as long as it is a laminated structure that maintains the cured product of the support sheet and the protective film forming film (in other words, the support sheet and the protective film) even after the protective film forming film is cured, the laminated structure is called "" Composite sheet for protective film formation".

The thickness of the semiconductor wafer to be used as the protective film forming composite sheet of the present invention is not particularly limited, but it is preferably 30 to 1000 μm, and 100 to 100 μm from the viewpoint of easy division into semiconductor wafers described later. 400 μm is preferred. Hereinafter, the structure of the composite sheet for protective film formation will be explained in detail.

◎Support piece The aforementioned support sheet may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers. When the support sheet is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.

As a preferable support sheet, for example, a support sheet provided with a base material and an adhesive layer layered on the base material in direct contact with the base material (the base material and the adhesive agent are laminated in direct contact in this order) support sheet); a support sheet obtained by directly contacting the substrate, an intermediate layer, and an adhesive in this order in the thickness direction of these film layers; a support sheet composed of only the substrate, etc. Hereinafter, an example of the composite sheet for protective film formation of the present invention will be described for each type of support sheet as described above with reference to the drawings.

Fig. 2 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. In addition, in the drawings after FIG. 2 , the same constituent elements as those shown in the already described drawings are assigned the same reference numerals as those shown in the already described drawings, and 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 agent layer 12 is provided on the base material 11, and the film 13 for protective film formation is provided on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the composite sheet 1A for forming a protective film has a surface (referred to as "the first surface" in this specification) 10a on one side of the support sheet 10. The film 13 for protective film formation is laminated|stacked. In addition, 1 A of composite sheets for protective film formation are equipped with the peeling film 15 further on the film 13 for protective film formation.

In the protective film forming composite sheet 1A, the adhesive layer 12 is laminated on one surface (in this specification, sometimes referred to as "the first surface") 11a of the substrate 11, and the protective film forming film 13 is laminated. On the entire surface (in this specification, sometimes referred to as "the first surface") 12a of one side of the adhesive layer 12, the adhesive layer 16 for jigs is laminated on the first surface of the film 13 for forming a protective film. On a part of the surface 13a (that is, the region near the edge), the release film 15 is laminated on the first surface 13a of the protective film forming film 13 on the surface where the adhesive layer 16 for the jig is not laminated and the jig. on the surface 16 a (upper surface and side surface) of the adhesive layer 16 .

In the composite sheet 1A for protective film formation, the film 13 for protective film formation is energy-beam curable, and satisfies the conditions of the said adhesive force and shear strength.

The adhesive layer 16 for jigs may be, for example, a single-layer structure containing an adhesive component, or may be a multi-layer structure in which film layers containing an adhesive component are laminated on both surfaces of a core sheet. .

In the composite sheet 1A for forming a protective film shown in FIG. 2 , the back surface of a semiconductor wafer (not shown) is attached to the first surface 13 a of the film 13 for forming a protective film with the release film 15 removed, and The upper side of the surface 16 a of the jig adhesive layer 16 is attached to a jig such as a ring-frame for use.

3 is a schematic cross-sectional view of a composite sheet for forming a protective film 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 not having the adhesive agent layer 16 for jigs. That is, in the protective film forming composite sheet 1B, the 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 adhesive layer 12. , and the release film 15 is laminated on the entire surface of the first surface 13a of the film 13 for protective film formation.

In the composite sheet 1B for protective film formation, the film 13 for protective film formation is energy-beam curable, and satisfies the conditions of the said adhesive force and shear strength.

In the protective film forming composite sheet 1B shown in FIG. 3 , the back surface of a semiconductor wafer (not shown) is attached to the center of the first surface 13 a of the protective film forming film 13 in the state where the peeling film 15 is removed. Part of the area on the side, and the area near the edge portion is attached to a jig such as a ring frame for use.

4 is a schematic cross-sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention. 1 C of composite sheets for protective film formation shown here are the same as 1 A of composite sheets for protective film formation shown in FIG. 2 except not having the adhesive agent layer 12. That is, in 1 C of composite sheets for protective film formation, the support sheet 10 is comprised only from the base material 11. Furthermore, the film 13 for forming a protective film is laminated on the first surface 11a of the substrate 11 (the first surface 10a of the support sheet 10 ), and the adhesive layer 16 for jigs is laminated on the first surface 13a of the film 13 for forming a protective film. part (that is, the area near the edge), and the release film 15 is laminated on the first surface 13a of the protective film forming film 13 in the area where the jig adhesive layer 16 and the jig adhesive are not laminated. On the surface 16a (upper surface and side surface) of the layer 16.

In 1 C of composite sheets for protective film formation, the film 13 for protective film formation is energy-beam curable, and satisfies the conditions of the said adhesive force and shear strength.

The composite sheet 1C for forming a protective film shown in FIG. 4 is the same as the composite sheet 1A for forming a protective film shown in FIG. It is attached to the first surface 13a of the film 13 for protective film formation, and the upper side of the surface 16a of the adhesive agent layer 16 for jigs is attached to jigs, such as a ring frame, for use.

5 is a schematic cross-sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 1D for protective film formation shown here is the same as the composite sheet 1C for protective film formation shown in FIG. 4 except not having the adhesive agent layer 16 for jigs. That is, in the composite sheet 1D for protective film formation, the film 13 for protective film formation is laminated|stacked on the 1st surface 11a of the base material 11, and the peeling film 15 is laminated|stacked on the whole of the 1st surface 13a of the film 13 for protective film formation. On the surface.

In the composite sheet 1D for protective film formation, the film 13 for protective film formation is energy-beam curable, and satisfies the conditions of the said adhesive force and shear strength.

The composite sheet 1D for forming a protective film shown in FIG. 5 is the same as the composite sheet 1B for forming a protective film shown in FIG. It is attached to a part of the central region of the first surface 13 a of the protective film forming film 13 , and the region near the edge is attached to a jig such as a ring frame for use.

6 is a schematic cross-sectional view of a composite sheet for forming a protective film according to 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 the shape of the film for protective film formation being different. That is, the composite sheet 1E for protective film formation is provided with the base material 11, the adhesive agent layer 12 is provided on the base material 11, and the film 23 for protective film formation is provided on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12 , in other words, the protective film forming composite sheet 1E has a structure in which the protective film forming film 23 is laminated on the first surface 10 a of the support sheet 10 . In addition, the composite sheet 1E for protective film formation is equipped with the peeling film 15 on the film 23 for protective film formation further.

In the protective film forming composite sheet 1E, the adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film forming film 23 is laminated on a part of the first surface 12a of the adhesive layer 12 (that is, area on the central side). And the peeling film 15 is laminated|stacked on the area|region which does not have the film 23 for laminated|stacked protective film formations among the 1st surface 12a of the adhesive layer 12, and the surface 23a (upper surface and side surface) of the film 23 for protective film formations.

When the composite sheet 1E for protective film formation is seen planarly from above, the surface area of the film 23 for protective film formation is smaller than the surface area of the adhesive agent layer 12, and it has a circular shape, for example.

In the composite sheet 1E for protective film formation, the film 23 for protective film formation is energy-beam curable, and satisfies the conditions of the said adhesive force and shear strength.

In the protective film-forming composite sheet 1E shown in FIG. 6 , the back surface of a semiconductor wafer (not shown) is attached to the surface 23a of the protective film-forming film 23 with the release film 15 removed, and the adhesive In the first surface 12a of the layer 12, the region where the film 23 for forming a laminated protective film is not present is attached to a jig such as a ring frame for use.

In addition, in the composite sheet 1E for forming a protective film shown in FIG. 6, in the first surface 12a of the adhesive layer 12, the area where the film 23 for forming a protective film is not laminated may be laminated as shown in FIGS. 2 and 4. The adhesive layer (not shown) for the jig shown. The protective film forming composite sheet 1E having the jig adhesive layer as described above is the same as the protective film forming composite sheet shown in Fig. 2 and Fig. 4, and the surface of the jig adhesive layer is attached to the annular Fixtures such as frames are available for use.

As mentioned above, in the composite sheet for protective film formation, the support sheet and the film for protective film formation may have any form, and may be equipped with the adhesive agent layer for jigs. However, as shown in FIGS. 2 and 4 , as a composite sheet for forming a protective film provided with an adhesive layer for jigs, it is generally preferable to have an adhesive layer for jigs on the film for forming a protective film.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. Part of the structure of the composite sheet for forming a protective film shown in FIGS. 2 to 6 may be changed or deleted, or other structures may be added to the structures described so far.

For example, in the composite sheet for protective film formation shown in FIG. 4 and FIG. 5, an intermediate layer may be provided between the base material 11 and the film 13 for protective film formation. As the intermediate layer, any one can be selected according to the purpose. In addition, in the composite sheet for protective film formation shown in FIG. 2, FIG. 3, and FIG. 6, you may provide an intermediate|middle layer between the base material 11 and the adhesive agent layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be a support sheet obtained by laminating a substrate, an intermediate layer, and an adhesive layer in this order in the thickness direction of these film layers. Here, the intermediate layer is the same as the intermediate layer that can also be provided in the composite sheet for protective film formation shown in FIG. 4 and FIG. 5 . In addition, in the composite sheet for protective film formation shown in FIGS. 2-6, the film layer other than the said intermediate|middle layer may be provided in arbitrary positions. In addition, in the composite sheet for protective film formation, some gaps may be formed between the peeling film and the film layer directly contacting this peeling film. In addition, in the composite sheet for protective film formation, the size, shape, etc. of each layer can be adjusted arbitrarily according to the purpose.

In the composite sheet for forming a protective film of the present invention, as will be described later, the film layers such as the adhesive layer and the like that are in direct contact with the film for forming a protective film of the support sheet are preferably non-energy ray curable. Such a composite sheet for forming a protective film can more easily pick up (pick-up) a semiconductor wafer with a protective film attached thereto.

The support sheet may be transparent or opaque, or may be colored according to the purpose. Among them, in the present invention in which the film for protective film formation has energy ray curability, it is preferable that the support sheet allows energy ray transmission.

For example, in the support sheet, the light transmittance for light having a wavelength of 375 nm is preferably 30% or higher, more preferably 50% or higher, and particularly preferably 70% or higher. When the light transmittance of the above-mentioned light is in such a range, when the film for protective film formation is irradiated with energy rays (ultraviolet rays) via a support sheet, the degree of hardening of the film for protective film formation can be further raised. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 375 nm is not particularly limited. For example, the light transmittance of the aforementioned light may be 95% or less.

Furthermore, in the support sheet, the transmittance of light with a wavelength of 532 nm is preferably at least 30%, more preferably at least 50%, and particularly preferably at least 70%. Since the light transmittance of the above-mentioned light exists in such a range, when irradiating laser light to the film for protective film formation or a protective film via a support sheet, and marking on these films, marking can be made more clearly. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 532 nm is not particularly limited. For example, the light transmittance of the aforementioned light may be 95% or less.

Furthermore, in the support sheet, the light transmittance for light with a wavelength of 1064 nm is preferably at least 30%, more preferably at least 50%, and particularly preferably at least 70%. Since the light transmittance of the above-mentioned light exists in such a range, when irradiating laser light to the film for protective film formation or a protective film via a support sheet, and marking on these films, marking can be made more clearly. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, the light transmittance of the aforementioned light may be 95% or less.

Furthermore, in the support sheet, the light transmittance for light with a wavelength of 1342 nm is preferably at least 30%, more preferably at least 50%, and particularly preferably at least 70%. Since the light transmittance of the aforementioned light is within such a range, when the semiconductor wafer is irradiated with laser light through the supporting sheet and the film for forming a protective film or the protective film, it is possible to more easily form a modification on the semiconductor wafer. sex layer. On the other hand, in the support sheet, the upper limit value of the light transmittance of light having a wavelength of 1342 nm is not particularly limited. For example, the light transmittance of the aforementioned light may be 95% or less. Next, each layer constituting the support sheet will be described in more detail.

○ Substrate The aforementioned base material is in the form of a sheet or a film, and various resins are exemplified as its constituent material. Examples of the above-mentioned resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene , polymethylpentene, and polyolefins other than polyethylene such as norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, and ethylene-based copolymers such as ethylene-norbornene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (obtained by using vinyl chloride as a monomer) resins); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate , polyethylene 2,6-naphthalate, and polyesters in which all structural units are wholly aromatic polyesters with aromatic cyclic groups; copolymers of two or more of the aforementioned polyesters; poly( Meth)acrylates; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene ethers; polyphenylene sulfides; Wait. In addition, as said resin, the polymer alloy (polymer-alloy) of the mixture of the said polyester and another resin etc. is mentioned, for example. In the aforementioned polymer blend such as a mixture of polyester and other resins, it is preferable that the amount of resin other than polyester is relatively small. Furthermore, as the above-mentioned resin, for example, a cross-linked resin obtained by cross-linking one or two or more of the aforementioned resins listed above; using one or more of the aforementioned resins listed above Modified resins such as two or more ionomers.

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

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

The thickness of the substrate is preferably 50-300 μm, more preferably 60-100 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer can be further improved. Here, the "thickness of the substrate" refers to the thickness of the entire substrate, for example, the thickness of a substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the substrate.

It is preferable that the thickness of the base material has high accuracy, that is, it is preferable that the thickness variation in any part can be suppressed. Among the above-mentioned constituent materials, examples of materials that can be used to form such a base material having a high-precision thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, Ethylene-vinyl acetate copolymer, etc.

In addition to the above-mentioned main constituent materials such as resins, the substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

It is preferable that the optical properties of the substrate satisfy the optical properties of the support sheet described above. For example, the substrate can be transparent or opaque, or it can also be colored according to the purpose, or other layers can also be deposited. Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the substrate allows energy ray transmission.

In order to improve the adhesion between the base material and other layers such as an adhesive layer provided on the base material, roughening treatment by sand blasting (sand blast) treatment, solvent treatment, etc., may be applied to the surface of the base material. , Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone‧ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and oxidation treatment such as hot air treatment, etc. In addition, the base material may be a base material treated with a primer (primer) on the surface. Furthermore, the base material may also have an antistatic coating; it is used to prevent the base material from sticking to other sheets or the base material to the film layer of the adsorption table when the protective film forming composite sheets are stacked for storage.

The substrate can be produced by a known method. For example, the resin-containing substrate can be produced by molding a resin composition containing the aforementioned resin.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains an adhesive. Examples of the aforementioned adhesive include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonate, ester resins, etc. Resins, preferably acrylic resins.

In addition, in the present invention, the term "adhesive resin" is a concept that includes both adhesive resins and adhesive resins. A resin that exhibits adhesiveness due to other ingredients, a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water, etc.

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

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

It is preferable that the optical properties of the adhesive layer satisfy the optical properties of the support sheet described above. The adhesive layer may be transparent or opaque, or may be colored according to the purpose. Furthermore, in the present invention in which the film for protective film formation has energy ray curability, it is preferable that the pressure-sensitive adhesive layer is permeable to energy ray.

The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. An adhesive layer formed using an energy ray-curable adhesive can easily adjust physical properties before and after curing.

＜＜Adhesive composition＞＞ The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer is formed on the target position by applying the adhesive composition on the surface where the adhesive layer is to be formed, and drying it as necessary. The more specific method for forming the adhesive layer will be described in detail later together with the methods for forming other layers. In the adhesive composition, the content ratio of the components that do not evaporate at normal temperature is usually the same as the content ratio of the aforementioned components in the adhesive layer.

The application of the adhesive composition can be performed by a known method, for example, use of an air knife coater, a knife coater, a rod coater, a gravure coater, a roll coater, a roll coater, etc. Type knife coater, shower curtain coater, die coater, knife coater, screen coater, Mailer rod coater, and kiss coater and other coating machine methods.

The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferable to heat and dry it. It is preferable to dry the solvent-containing adhesive composition at 70-130° C. for 10 seconds to 5 minutes.

In the case where the adhesive layer has energy ray curability, as an adhesive composition containing an energy ray curable adhesive, that is, as an energy ray curable adhesive composition, for example, non-energy ray curable Adhesive composition (I-1) consisting of an adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)") and an energy ray-curable compound; Adhesives for energy ray-curable adhesive resin (I-2a) in which unsaturated groups are introduced into side chains of permanent adhesive resin (I-1a) Composition (I-2); Adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray-curable compound, and the like.

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

[Adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin. As said acrylic resin, the acrylic polymer which has the structural unit derived from an alkyl (meth)acrylate at least is mentioned, for example. The structural unit of the said acrylic resin may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be chosen arbitrarily.

As the above-mentioned alkyl (meth)acrylate, for example, an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester can be mentioned, and the above-mentioned alkyl group is a straight chain or Branched chains are preferred. Examples of the alkyl (meth)acrylate include, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-(meth)acrylate Nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (also known as lauryl (meth)acrylate ), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth) Cetyl acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate) , nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

From the viewpoint of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms. Furthermore, from the viewpoint of further improving the adhesive force of the adhesive layer, the number of carbon atoms in the alkyl group is preferably 4-12, and more preferably 4-8. Furthermore, the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably an alkyl methacrylate.

The aforementioned acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. As the aforementioned functional group-containing monomer, for example, the reaction of the aforementioned functional group with the later-described crosslinking agent as the starting point of crosslinking, the reaction of the aforementioned functional group with the later-described unsaturated group-containing compound A monomer that can introduce unsaturated groups into the side chains of acrylic polymers by reacting with unsaturated groups, etc.

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxyl 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 carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

Examples of the aforementioned hydroxyl-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; and vinyl Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols without a (meth)acryl skeleton) such as alcohol and acrylic alcohol.

Examples of the aforementioned carboxyl group-containing monomers include (meth)acrylic acid, ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid, and crotonic acid; Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds), such as acid, itaconic acid, maleic acid, and citraconic acid; of the aforementioned ethylenically unsaturated dicarboxylic acids Anhydrides; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate, etc.

The functional group-containing monomers are preferably hydroxyl-containing monomers and carboxyl-containing monomers, and more preferably hydroxyl-containing monomers.

The functional group-containing monomer constituting the acrylic polymer may be used alone, or two or more of them may be used, and when two or more are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned acrylic polymer, the content of structural units derived from functional group-containing monomers relative to the total amount of structural units is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, Moreover, 3-30 mass % is especially preferable.

In addition to the structural units derived from alkyl (meth)acrylates and the structural units derived from functional group-containing monomers, the aforementioned acrylic polymer may further have structural units derived from other monomers. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with an alkyl (meth)acrylate or the like. Examples of other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The aforementioned other monomers constituting the aforementioned acrylic polymer may be used alone, or may be used in combination of two or more, and when using two or more, combinations and ratios thereof may be selected arbitrarily.

The aforementioned acrylic polymer can be used as the aforementioned non-energy ray curable adhesive resin (I-1a). On the other hand, a product obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the aforementioned energy ray polymer. Curable adhesive resin (I-2a) is used.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be used only by one type, or two or more types may be used, and when two or more types are used, any combination thereof may be selected and Proportion.

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, based on the total content of components other than the solvent. Better, and especially preferably 15-90% by mass.

[Energy ray curable compound] Examples of the aforementioned energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers (oligomers) that have an energy ray polymerizable unsaturated group and are curable by energy ray irradiation. . In energy ray curable compounds, as monomers, for example, trimethylolpropane tri(meth)acrylate, neopentylthritol (meth)acrylate, neopentylthritol tetra(meth)acrylate, di Polyvalent (meth)acrylic acid such as neopentylitol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol (meth)acrylate esters; urethane (meth)acrylates; polyester (meth)acrylates; polyether (meth)acrylates; and epoxy (meth)acrylates, etc. Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers listed above, and the like. From the point of view that the molecular weight is relatively large and the storage modulus of the adhesive layer hardly decreases, the energy ray-curable compound is urethane (meth)acrylate, and urethane (meth)acrylate Oligomers of esters are preferred.

The aforementioned energy ray-curable compounds contained in the adhesive composition (I-1) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the adhesive composition (I-1), the content of the energy ray-curable compound is 1 to 95% by mass relative to the total content of components other than the solvent in the adhesive composition (I-1). Preferably, 5-90 mass % is more preferable, and 10-85 mass % is especially preferable.

[Crosslinking agent] In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a) In this case, the adhesive composition (I-1) preferably further contains a crosslinking agent.

The aforementioned crosslinking agent is, for example, a crosslinking agent capable of reacting with the aforementioned functional group to crosslink the adhesive resins (I-1a) to each other. Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of the above-mentioned diisocyanates. ); Epoxy cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents with glycidyl groups); Hexa[1-(2-methyl)-aziridyl]triphosphatriazine, etc. Aziridine crosslinking agent (crosslinking agent with aziridine group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanuric acid Ester crosslinking agent (crosslinking agent with isocyanuric acid skeleton), etc. From the standpoint of improving the cohesive force of the adhesive to increase the adhesive force of the adhesive layer and being easy to obtain, the crosslinking agent is preferably an isocyanate crosslinking agent.

The crosslinking agent contained in the adhesive composition (I-1) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1a). It is preferable, and it is especially preferable to use 0.3-15 mass parts.

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

Examples of the aforementioned photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1- Acetophenone compounds such as ketones; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acyl phosphine oxide compounds; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyronitrile, etc. azo compounds; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxides; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone ; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; and 2 - Chloranthraquinone etc. In addition, as said photoinitiator, the quinone compound, such as 1-chloroanthraquinone, the photosensitizer, such as an amine, etc. can be used, for example.

The photopolymerization initiator contained in the adhesive composition (I-1) may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be selected arbitrarily.

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

[Other additives] The adhesive composition (I-1) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, Known additives such as reaction inhibitors and crosslinking accelerators (catalysts). In addition, as a reaction inhibitor, for example, an unexpected crosslinking reaction of the adhesive composition (I-1) in storage due to the action of the catalyst mixed in the adhesive composition (I-1) can be suppressed. As a reaction inhibitor, for example, a reaction inhibitor of a chelate complex formed by chelating with a catalyst, and more specifically, a reaction inhibitor having two or more carbonyl groups (—C( =O)–) reaction inhibitor.

The other additives contained in the adhesive composition (I-1) may be used only by one type, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

In the adhesive composition (I-1), the content of other additives is not particularly limited, and can be appropriately selected according to the type.

[solvent] The adhesive composition (I-1) may also contain a solvent. Since the adhesive composition (I-1) contains a solvent, the coatability to the surface to be coated can be improved.

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

As the aforementioned solvent, for example, the solvent used when preparing the adhesive resin (I-1a) may not be removed from the adhesive resin (I-1a) and directly used in the adhesive composition (I-1), Alternatively, when preparing the adhesive composition (I-1), the same or different solvent as that used for the preparation of the adhesive resin (I-1a) may be added separately.

The solvent contained in the adhesive composition (I-1) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

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

＜Adhesive composition (I-2)＞ As described above, the aforementioned adhesive composition (I-2) contains the energy ray-curable adhesive resin (I- 2a).

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

The aforementioned unsaturated group-containing compound reacts with the functional group in the adhesive resin (I-1a) in addition to the aforementioned energy ray polymerizable unsaturated group, so the aforementioned unsaturated group-containing compound has the ability to be compatible with the adhesive The compound of the group to which the resin (I-1a) is bonded. As the aforementioned energy ray polymerizable unsaturated group, for example, (meth)acryl, vinyl (ethenyl, also called vinyl), and allyl (allyl, also called 2-propenyl (2 -propenyl)), etc., preferably (meth)acryl. As the group that can be bonded to the functional group in the adhesive resin (I-1a), for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and an isocyanate group that can be bonded to a hydroxyl group or an epoxy group Bonded hydroxyl and amine groups, etc.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be used only by one type, or two or more types may be used, and when two or more types are used, any combination thereof may be selected and Proportion.

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, based on the total mass of components other than the solvent. Good, and 10-90% by mass is especially good.

[Crosslinking agent] In the case of using, for example, the same adhesive resin (I-1a) as the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer as the adhesive resin (I-2a), the adhesive composition (I-2) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-2) include the same crosslinking agents as in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2a). It is preferable, and it is especially preferable to use 0.3-15 mass parts.

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

Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same photopolymerization initiators as in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2a). 1 part is preferred, and 0.05 to 5 parts by mass is particularly preferred.

[Other additives] The adhesive composition (I-2) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of other additives in the adhesive composition (I-2) include the same ones as those in the adhesive composition (I-1). As for other additives contained in the adhesive composition (I-2), only one type may be used, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be selected arbitrarily.

In the adhesive composition (I-2), the content of other additives is not particularly limited, and can be appropriately selected according to the type.

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

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

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, based on the total mass of components other than the solvent. Better, and especially preferably 15-90% by mass.

[Energy ray curable compound] Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and are curable by irradiation with energy rays, and can be The same energy ray-curable compounds contained in the adhesive composition (I-1) are listed. The aforementioned energy ray-curable compounds contained in the adhesive composition (I-3) may be used alone, or may be used in two or more kinds. When two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-3), the content of the aforementioned energy ray-curable compound is preferably 0.01 to 300 parts by mass, preferably 0.03 to 300 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2a). 200 mass parts is preferable, and 0.05-100 mass parts is especially preferable.

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

Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same photopolymerization initiators as in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, the combination and ratio can be selected arbitrarily.

In the adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray-curable compound. More preferably, it is preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives] The adhesive composition (I-3) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include the same ones as in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-3) may be used only by 1 type, or 2 or more types may be used, and when 2 or more types are used, the combination and ratio can be chosen arbitrarily.

In the adhesive composition (I-3), the content of other additives is not particularly limited, and can be appropriately selected according to the type.

[solvent] The adhesive composition (I-3) may contain a solvent for the same purpose as that of the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-3) include the same solvents as in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-3) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the adhesive composition (I-3), the content of the solvent is not particularly limited, and can be appropriately adjusted.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)> So far, the adhesive composition (I-1), adhesive composition (I-2) and adhesive composition (I-3) have been mainly described, and the components contained in these adhesive compositions have been described, It is also possible to use general adhesive compositions other than these three adhesive compositions (referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)" in this specification. ").

Adhesive compositions other than the adhesive compositions (I-1) to (I-3) include non-energy ray curable adhesive compositions in addition to energy ray curable adhesive compositions. thing. Examples of non-energy ray-curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, The adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an ester resin preferably contains an acrylic resin.

Adhesive compositions other than adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content of the cross-linking agent can be the same as that of the above-mentioned adhesives. In the case of agent composition (I-1) and the like.

＜Adhesive composition (I-4)＞ As a preferable example of an adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same adhesive resin (I-1a) as in the adhesive composition (I-1). The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be used only by one type, or two or more types may be used, and when two or more types are used, any combination thereof may be selected and Proportion.

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, based on the total mass of components other than the solvent. Better, and especially preferably 15-90% by mass.

[Crosslinking agent] In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a) In this case, the adhesive composition (I-4) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-4) include the same crosslinking agents as in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-4) may be used alone, or may be used in two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily.

In the aforementioned adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1a). It is preferable, and it is especially preferable to use 0.3-15 mass parts.

[Other additives] The adhesive composition (I-4) may contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include the same ones as in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-4) may be used only by 1 type, or 2 or more types may be used, and when 2 or more types are used, the combination and ratio can be chosen arbitrarily.

In the adhesive composition (I-4), the content of other additives is not particularly limited, and can be appropriately selected according to the type.

[solvent] The adhesive composition (I-4) may contain a solvent for the same purpose as that of the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-4) may be used alone, or two or more kinds may be used, and when two or more kinds are used, the combination and ratio thereof may be selected arbitrarily. In the adhesive composition (I-4), the content of the solvent is not particularly limited, and can be appropriately adjusted.

In the above composite sheet for forming a protective film, the adhesive layer is preferably non-energy ray curable. This is because if the adhesive layer has energy ray curability, when the film for protective film formation is hardened by the irradiation of an energy ray, it cannot suppress that an adhesive layer also hardens|cures simultaneously. When the adhesive layer and the film for protective film formation are hardened simultaneously, the film for protective film formation after hardening, and an adhesive layer may adhere mutually at the interface between them so that they cannot be peeled off. In this case, the semiconductor wafer (semiconductor wafer with a protective film) provided with a cured protective film-forming film (that is, protective film) on the back surface becomes difficult to change from the cured adhesive layer The support sheet peels off, and then it becomes impossible to pick up the semiconductor wafer with the protective film normally. By making the adhesive layer in the support sheet non-energy ray curable, such a problem can be reliably avoided, and the semiconductor wafer with the protective film can be picked up more easily.

Here, the effect in the case where the adhesive layer is non-energy ray curable has been described, but even if the film layer directly in contact with the protective film forming film of the support sheet is a film layer other than the adhesive layer, The same effect can be exhibited as long as this film layer is non-energy ray curable.

＜＜Manufacturing method of adhesive composition＞＞ Adhesive compositions (I-1) to (I-3) can be obtained by preparing the above-mentioned adhesive and, if necessary, components other than the above-mentioned adhesive, etc., which are used to constitute the adhesive composition. Adhesive compositions other than the adhesive compositions (I-1) to (I-3) such as the , adhesive composition (I-4), and the like. The order of addition when preparing each component is not specifically limited, You may add 2 or more types of components at the same time. In the case of using a solvent, it can be used by mixing the solvent with any of the formulation components other than the solvent and diluting the formulation components in advance, or by not mixing any of the formulation components other than the solvent. It is used by mixing the solvent and this preparation component as it is diluted beforehand. The mixing method of each component is not particularly limited at the time of preparation, and can be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, and a method of mixing using ultrasonic waves. The temperature and time during the addition and mixing of each component are not particularly limited as long as they do not cause deterioration of each compounded component, and can be appropriately adjusted, but the temperature is preferably 15-30°C.

◇Manufacturing method of composite sheet for protective film formation The aforementioned composite sheet for protective film formation can be produced by laminating each of the above-mentioned layers in a corresponding positional relationship. The method of forming each layer is as described above. For example, in the case of laminating an adhesive layer on a substrate when producing a support sheet, the above-mentioned adhesive composition can be applied to the substrate and dried if necessary.

On the other hand, for example, when a film for forming a protective film is further laminated on an adhesive layer already laminated on a substrate, the composition for forming a protective film can be applied on the adhesive layer to form a protective film directly. Form a film. The film layer other than the film for protective film formation can be laminated|stacked on the adhesive layer by the same method using the composition for forming this film layer. As described above, when using any one of the compositions to form a continuous two-layer laminated structure, the composition may be further coated on the film layer formed from the aforementioned composition to form a new layer. However, the film layer laminated later among these two layers is formed in advance on the other release film using the aforementioned composition, and the exposed surface of the formed film layer on the side opposite to the side contacting the aforementioned release film and the It is preferable that the exposed surfaces of another film layer that has been formed in advance are attached to each other to form a continuous two-layer laminated structure. In this case, the composition is preferably applied to the release-treated surface of the release film. After forming the laminated structure, the release film can be removed as required.

For example, in the production of a composite sheet for forming a protective film formed by laminating an adhesive layer on a substrate and laminating a film for forming a protective film on the adhesive layer (the support sheet is a laminate of the substrate and the adhesive layer) In the case of a composite sheet for forming a protective film), the adhesive composition is applied to the base material and dried as required, and the adhesive layer is laminated on the base material first, and then a protective film is additionally coated on the release film. The composition is used and dried as necessary, and the film for protective film formation is formed on the peeling film first. Next, the exposed surface of the film for forming a protective film and the exposed surface of the adhesive layer laminated on the substrate are attached to each other, so that the film for forming a protective film is laminated on the adhesive layer, and a composite sheet for forming a protective film is obtained. .

In addition, in the case of laminating the adhesive layer on the substrate, instead of applying the adhesive composition on the substrate as described above, the adhesive composition may be applied on the release film and dried as required. , and then firstly form the adhesive layer on the release film, and then attach the exposed surface of this layer to the surface of the substrate side to laminate the adhesive layer on the substrate. In either method, the release film can be removed at any time after forming the desired laminated structure.

As described above, since any layer other than the base material constituting the protective film forming composite sheet can be formed in advance on the release film and bonded to the surface of the target layer, it can be laminated according to needs. By selecting a film layer that can be used in this way, a composite sheet for forming a protective film can be manufactured.

In addition, the protective film forming composite sheet is usually stored in a state where a release film is bonded to the surface of the outermost layer (eg, protective film forming film) opposite to the support sheet of the protective film forming composite sheet. Therefore, it is also possible to apply a composition for forming the outermost layer constituting a composition for forming a protective film, etc. on the release film (preferably a release-treated surface of the release film), and dry it as required, and then Firstly, the outermost film layer is formed on the release film, and then on the exposed surface on the opposite side to the release film contacting this layer, other layers are laminated by any of the above methods, and the release film is not removed. In the directly bonded state, a composite sheet for protective film formation is further obtained.

◇Manufacturing method of semiconductor wafer The film for protective film formation and the composite sheet for protective film formation mentioned above can be applied to manufacture of a semiconductor wafer. As the manufacturing method of the semiconductor wafer at this time, for example, a manufacturing method including the following steps can be cited: a film for forming a protective film that has not yet constituted the composite sheet for forming a protective film, or a protective film in the composite sheet for forming a protective film. A step of attaching a film-forming film to a semiconductor wafer (hereinafter sometimes simply referred to as "attaching step"); a step of irradiating energy rays to the protective film-forming film attached to the semiconductor wafer to form a protective film Step (hereinafter sometimes simply referred to as "protective film forming step"): irradiating laser light through the aforementioned protective film or protective film forming film in such a manner as to focus on a focal point set inside the aforementioned semiconductor wafer, to form a laser beam on the aforementioned semiconductor wafer. forming a modified layer inside the wafer (hereinafter sometimes simply referred to as "modified layer forming step"); the aforementioned semiconductor wafer on which the aforementioned modified layer is formed is placed on the aforementioned protective film together with the aforementioned protective film or film for protective film film or protective film forming film in the surface direction (direction parallel to the surface) to cut the protective film or protective film forming film and at the same time divide the aforementioned semiconductor wafer at the position of the modified layer, and then A plurality of semiconductor wafers are obtained (hereinafter sometimes simply referred to as "dividing step").

Here, the expanding direction of the semiconductor wafer is specifically set to be the surface direction of the protective film or the film for forming a protective film, which is usually the same as the surface direction of the semiconductor wafer (for example, the direction of the aforementioned back surface).

Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. 7 to 9 are schematic cross-sectional views for explaining one embodiment of a method for manufacturing a semiconductor wafer when using a film for forming a protective film that does not yet constitute a composite sheet for forming a protective film. In addition, FIGS. 10 to 12 are cross-sections illustrating an embodiment of a method for manufacturing a semiconductor wafer in the case of using a composite sheet for forming a protective film formed by integrating a film for forming a protective film with a support sheet in advance. schematic diagram.

<<Manufacturing method of semiconductor wafer in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film>> First, an embodiment of the production method in the case of using a film for forming a protective film that does not yet constitute a composite sheet for forming a protective film will be described by taking the case of the film for forming a protective film as shown in FIG. 1 as an example (this embodiment Sometimes referred to as "Manufacturing method (1)-1").

In the aforementioned attaching step of manufacturing method (1)-1, as shown in FIG. surface) 9b. Here, the first release film 151 is removed from the protective film forming film 13 and the first surface 13 a of the protective film forming film 13 is bonded to the back surface 9 b of the semiconductor wafer 9 . In addition, here, the illustration of the bump etc. on the surface of a circuit in the semiconductor wafer 9 is abbreviate|omitted.

After the attaching step of manufacturing method (1)-1, in the aforementioned protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with an energy ray, and further on the semiconductor wafer 9 A protective film 13' is formed, as shown in (b) of FIG. 7 . The energy ray irradiation may be performed after removing the second release film 152 from the film 13 for protective film formation.

Furthermore, after the attaching step of the manufacturing method (1)-1, in the above-mentioned modifying layer forming step, by adopting a method of focusing on the focal point set inside the semiconductor wafer 9, through the protective film 13 'Irradiating laser light to form a modified layer 91 inside the semiconductor wafer 9, as shown in (c) of FIG. 7 . The irradiation of laser light may be performed after removing the second release film 152 from the protective film 13'.

After the modified layer forming step of the manufacturing method (1)-1, before the aforementioned dividing step, as shown in (d) of FIG. A surface (sometimes referred to as a "first surface" in this specification) 13a' on the side of the wafer 9 is a surface (sometimes called a "second surface" in this specification) 13b' on the opposite side. The support sheet 10 is a support sheet as shown in FIG. 2 and so on, and is attached to the protective film 13' through the adhesive layer 12 of the support sheet.

Next, in the aforementioned dividing step of manufacturing method (1)-1, the semiconductor wafer 9 on which the modified layer 91 is formed is placed on the surface of the protective film 13' (the first surface 13a' or the second surface 13a' together with the protective film 13'). The surface 13b') extends in the direction to cut the protective film 13' and at the same time divide the semiconductor wafer 9 at the position of the modified layer 91 to obtain a plurality of semiconductor wafers 9', as shown in (e) of FIG. 7 . At this time, the protective film 13' is cut (divided) at a position along the edge portion of the semiconductor wafer 9'. The cut protection film 13' is denoted by reference numeral 130'.

In the dividing step, by expanding (expanding) the semiconductor wafer 9 and the protective film 13' in the direction indicated by the arrow I in (d) of FIG. ) The semiconductor wafer 9 and the protective film 13' are divided.

In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

In addition, FIG. 7 depicts the situation where the support sheet 10 is attached to the protective film 13' after the protective film forming step and the modified layer forming step are performed. However, in the production method (1)-1, the protective film forming step and the modified layer forming step may be performed after the support sheet 10 is attached to the protective film forming film 13, or the protective film forming step may be performed after the protective film forming step. After the support sheet 10 is attached to the protective film 13', the modified layer forming step is performed.

In the manufacturing method (1)-1, since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into the semiconductor wafers 9 ′ in the aforementioned dividing step, it is possible to suppress the semiconductor wafer 9 ′ from forming the protective film 13 ′. Or the cut protective film 130' floats.

In the manufacturing method (1)-1, the modified layer forming step is performed after the protective film forming step, but in the semiconductor wafer manufacturing method according to this embodiment, the protective film may be formed after the modified layer forming step. Formation step (this embodiment may be referred to as "manufacturing method (1)-2"). FIG. 8 is a schematic cross-sectional view illustrating an embodiment of such a method of manufacturing a semiconductor wafer.

As in the case of manufacturing method (1)-1, in the aforementioned attaching step of manufacturing method (1)-2, as shown in FIG. 8( a ), the protective film forming film 13 is attached to the semiconductor wafer. 9 back surface 9b.

After the attaching step of the manufacturing method (1)-2, in the above modified layer forming step, by adopting a method of focusing on the focal point set inside the semiconductor wafer 9, the protective film forming film 13 Laser light is irradiated to form modified layer 91 inside semiconductor wafer 9 , as shown in FIG. 8( b ). Irradiation with laser light may be performed after removing the 2nd release film 152 from the film 13 for protective film formation.

Furthermore, after the attaching step of the manufacturing method (1)-2, in the aforementioned protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with an energy ray, and the semiconductor wafer 9 is further formed. A protective film 13' is formed on the circle 9, as shown in (c) of FIG. 8 . By performing this step, a semiconductor wafer with a protective film can be obtained in the same state as after completion of the modified layer forming step of the manufacturing method (1)-1 (ie, FIG. 7( c )).

Afterwards, as in the case of manufacturing method (1)-1 (as shown in FIG. 7(d) to FIG. 7(e)), the support sheet 10 is attached to the second surface 13b' of the protective film 13', Next, by performing the aforementioned dividing step, the protective film 13' is cut and the semiconductor wafer 9 is divided at the position of the modified layer 91 at the same time, thereby obtaining a plurality of semiconductor wafers 9', as shown in (d)-figure 8 8(e). In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

In addition, FIG. 8 depicts a situation where the support sheet 10 is attached to the protective film 13' after the modified layer forming step and the protective film forming step are performed. However, in the production method (1)-2, the modified layer forming step and the protective film forming step may be performed after the support sheet 10 is attached to the protective film forming film 13, or may be performed after the modified layer forming step. The protective film forming step is performed after the support sheet 10 is attached to the film 13 for protective film formation.

In the manufacturing method (1)-2, since the film 13 for forming a protective film is used, when the semiconductor wafer 9 is divided into the semiconductor wafers 9 ′ in the aforementioned dividing step, it is also possible to suppress the semiconductor wafer 9 ′ from forming from the protective film 13 . ' or the cut protective film 130' floats.

In the manufacturing methods (1)-1 and (1)-2, the dividing step is performed after the protective film forming step, but in the semiconductor wafer manufacturing method according to this embodiment, the protective film forming step may not be performed In this case, a dividing step is performed, and a protective film forming step is performed after the dividing step (the present embodiment may be referred to as "manufacturing method (1)-3"). FIG. 9 is a schematic cross-sectional view illustrating an embodiment of such a method of manufacturing a semiconductor wafer.

Manufacturing method (1)-3 can be carried out in the same manner as the attachment step and modified layer forming step of manufacturing method (1)-2 (as shown in Figure 8(a) to Figure 8(b)). The aforementioned attaching step and modified layer forming step are shown in (a) to (b) of FIG. 9 .

After the modified layer forming step of the production method (1)-3, before the aforementioned dividing step, as shown in FIG. 9( c ), the support sheet 10 is attached to the second surface of the protective film forming film 13 13b.

Next, in the aforementioned dividing step of manufacturing method (1)-3, the semiconductor wafer 9 on which the reformed layer 91 was formed is placed on the surface of the protective film forming film 13 (first surface 13 a ) together with the protective film forming film 13 . Or expand in the direction of the second surface 13b) to cut the protective film forming film 13 and at the same time divide the semiconductor wafer 9 at the position of the modified layer 91, and then obtain a plurality of semiconductor wafers 9', as shown in Figure 9 (d ) shown. At this time, the film 13 for protective film formation is cut|disconnected (segmented) at the position along the edge part of the semiconductor wafer 9'. The film 13 for forming a protective film after dicing is denoted by reference numeral 130 . In the dividing step, by expanding (expanding) the semiconductor wafer 9 and the protective film forming film 13 in the direction indicated by the arrow I in FIG. 9(c), a force (tension) is applied in this direction. The semiconductor wafer 9 and the film 13 for forming a protective film are divided. By the above method, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a film for protective film formation.

In addition, FIG. 9 has shown the case where the support sheet 10 is attached to the film 13 for protective film formation after performing a modified layer formation process. However, in manufacturing method (1)-3, you may perform a modified layer formation process after attaching the support sheet 10 to the film 13 for protective film formation.

In the manufacturing method (1)-3, since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into the semiconductor wafers 9 ′ in the aforementioned dividing step, it is possible to suppress the semiconductor wafer 9 ′ from forming the protective film 9 ′. The film 13 or the cut protective film forming film 130 floats.

In the manufacturing method (1)-3, after the aforementioned dividing step, by irradiating the protective film forming film 130 with energy rays through the supporting sheet 10, as shown in FIG. A protective film 130' is formed thereon.

In (e) of FIG. 9 , the situation in which the protective film 130' is formed before picking up the semiconductor wafer 9' is shown, but the protective film 130' can also be formed at any time after the division step such as picking up the semiconductor wafer 9'. 'Formation.

<<Manufacturing method of semiconductor wafer in the case of using a protective film forming composite sheet in which a protective film forming film and a support sheet are integrated in advance>>

Next, regarding one embodiment of the production method in the case of using a composite sheet for protective film formation in which the film for protective film formation and the support sheet are integrated in advance, the composite sheet for protective film formation as shown in FIG. An example will be described (this embodiment may be referred to as "manufacturing method (2)-1").

In the aforementioned attaching step of manufacturing method (2)-1, as shown in FIG. Surface 9b. The protective film forming composite sheet 1A is used after removing the peeling film 15 .

After the attaching step of manufacturing method (2)-1, in the aforementioned protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with an energy ray, and further on the semiconductor wafer 9 A protective film 13' is formed as shown in (b) of FIG. 10 . At this time, energy rays are irradiated to the film 13 for protective film formation via the support sheet 10 .

In addition, here, the composite sheet for protective film formation after the film 13 for protective film formation becomes the protective film 13' is shown by the code|symbol 1A'. This also applies to the subsequent schemas.

Furthermore, after the attaching step of the manufacturing method (2)-1, in the above-mentioned modified layer forming step, by adopting a method of focusing on the focal point set inside the semiconductor wafer 9, the protective film 13 '(Composite sheet 1A' for protective film formation') is irradiated with laser light to form modified layer 91 inside semiconductor wafer 9, as shown in (c) of FIG. 10 .

Next, in the aforementioned dividing step of the manufacturing method (2)-1, the semiconductor wafer 9 on which the modified layer 91 is formed and the protective film 13 ′ are placed on the surface of the protective film 13 ′ (the first surface 13 a ′ or the second surface 13 a ′). The surface 13b') is extended in the direction to cut the protective film 13' and at the same time divide the semiconductor wafer 9 at the position of the modified layer 91, and then obtain a plurality of semiconductor wafers 9', as shown in (d) of Figure 10 . At this time, the protective film 13' is cut (divided) at a position along the edge portion of the semiconductor wafer 9', and becomes the protective film 130'. In the dividing step, by expanding (expanding) the semiconductor wafer 9 and the protective film 13' in the direction indicated by the arrow I in (c) of FIG. ) of the semiconductor wafer 9 and the protective film 13' are divided. In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

In the manufacturing method (2)-1, since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into the semiconductor wafers 9 ′ in the aforementioned dividing step, it is possible to suppress the Or the cut protective film 130' floats.

In the manufacturing method (2)-1, the modified layer forming step is performed after the protective film forming step, but in the semiconductor wafer manufacturing method according to this embodiment, the protective film may be formed after the modified layer forming step. Formation step (this embodiment may be referred to as "manufacturing method (2)-2"). FIG. 11 is a schematic cross-sectional view illustrating an embodiment of such a method of manufacturing a semiconductor wafer.

As in the case of manufacturing method (2)-1, in manufacturing method (2)-2, as shown in FIG. 11( a ), the protective film forming film 13 in the protective film forming composite sheet 1A is attached on the back surface 9 b of the semiconductor wafer 9 .

After the attaching step of manufacturing method (2)-2, in the above-mentioned modified layer forming step, by adopting a method of focusing on the focal point set inside the semiconductor wafer 9 , the protective film forming film 13 (Composite sheet for forming a protective film 1A) is irradiated with laser light to form a reformed layer 91 inside the semiconductor wafer 9, as shown in FIG. 11( b ).

Furthermore, after the attaching step of the manufacturing method (2)-2, in the protective film forming step described above, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with energy rays, and the semiconductor wafer 9 is further formed. A protective film 13' is formed on the circle 9, as shown in (c) of FIG. 11 . By performing this step, a semiconductor wafer with a protective film can be obtained in the same state as after completion of the modified layer forming step of the manufacturing method (2)-1 (ie, (c) of FIG. 10 ).

Afterwards, similar to the case of manufacturing method (2)-1 (as shown in (d) of FIG. 10 ), by performing the aforementioned dividing step, the protective film 13 ′ is cut and at the same time, the semiconductor Wafer 9 is divided to obtain a plurality of semiconductor wafers 9 ′, as shown in (d) of FIG. 11 . In the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

In the manufacturing method (2)-2, since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into the semiconductor wafers 9 ′ in the aforementioned dividing step, it is possible to suppress the semiconductor wafer 9 ′ from forming the protective film 13 ′ Or the cut protective film 130' floats.

In the manufacturing methods (2)-1 and (2)-2, the dividing step is performed after the protective film forming step, but in the semiconductor wafer manufacturing method according to this embodiment, the protective film forming step may not be performed In this case, a dividing step is performed, and a protective film forming step is performed after the dividing step (the present embodiment may be referred to as "manufacturing method (2)-3"). FIG. 12 is a schematic cross-sectional view illustrating an embodiment of such a method of manufacturing a semiconductor wafer.

The manufacturing method (2)-3 can be carried out in the same way as the attaching step and the modified layer forming step of the manufacturing method (2)-2 (as shown in FIG. 11(a) to FIG. 11(b)). The aforementioned attaching step and modified layer forming step are shown in (a) to (b) of FIG. 12 .

Next, in the aforementioned dividing step of manufacturing method (2)-3, the semiconductor wafer 9 on which the reformed layer 91 is formed is placed on the surface of the film 13 for protective film formation (first surface 13 a ) together with the film 13 for forming a protective film. Or expand in the direction of the second surface 13b) to cut the protective film forming film 13 and at the same time divide the semiconductor wafer 9 at the position of the modified layer 91, and then obtain a plurality of semiconductor wafers 9', as shown in Figure 12 (c ) shown. At this time, the film 13 for protective film formation is cut|disconnected (segmented) at the position along the edge part of the semiconductor wafer 9'. In the dividing step, by expanding (expanding) the semiconductor wafer 9 and the protective film forming film 13 in the direction indicated by the arrow I in FIG. 12(b), a force (tension) is applied in this direction The semiconductor wafer 9 and the film 13 for forming a protective film are divided. By the above method, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a film for protective film formation.

In the manufacturing method (2)-3, since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into the semiconductor wafers 9 ′ in the aforementioned dividing step, it is possible to suppress the semiconductor wafer 9 ′ from forming the protective film. The film 13 or the cut protective film forming film 130 floats.

In the manufacturing method (2)-3, after the aforementioned division step, the protective film 130 is irradiated with energy rays to form the protective film 130 on the semiconductor wafer 9 , as shown in (d) of FIG. 12 . Show. In (d) of FIG. 12 , the case where the protective film 130' is formed before picking up the semiconductor wafer 9' is shown, however, the protective film 130 may be formed at any time after the division step such as picking up the semiconductor wafer 9'. 'Formation.

So far, the method of manufacturing a semiconductor wafer in the case of 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. For the sake of explanation, however, the method for manufacturing a semiconductor wafer of the present invention is not limited thereto. For example, in the case of using a composite sheet for forming a protective film, it is also possible to use the composite sheets for forming a protective film shown in FIGS. A semiconductor wafer was produced in the same manner as the composite sheet for forming a protective film other than the composite sheet for forming a protective film shown in 2 . Moreover, it is also possible to use a support sheet other than the support sheet 10 shown in FIG. Semiconductor wafers are manufactured in the same manner. As described above, in the case of using the protective film-forming composite sheet, support sheet, etc. of other embodiments, steps may be appropriately added, changed, or deleted in the above-mentioned production method based on structural differences of these sheets. , to produce semiconductor wafers.

◇Manufacturing method of semiconductor device After the semiconductor wafer is obtained by the above-mentioned manufacturing method, the semiconductor wafer is directly peeled off from the support sheet and picked up in the state where the divided protective film is attached (that is, as a semiconductor wafer with a protective film) (not shown). drawn). Afterwards, by the same method as the prior art, the obtained semiconductor chip with protective film is flip-chip connected to the circuit surface of the substrate to form a semiconductor package. Then, by using the semiconductor package, a target semiconductor device (not shown) can be manufactured.

The film for forming a protective film in one aspect of the present invention is an energy ray curable film for forming a protective film, and the film for forming a protective film has a gap between the film for forming a protective film and a silicon wafer when measured by the following method: The adhesive force is 3.6N/25mm or more and 8N/25mm or less. The film for forming a protective film has the shear of the protective film when the protective film is formed by irradiating ultraviolet rays to the film for forming a protective film. The cut strength is 11 N/3 mm□ or more and 13 N/3 mm□ or less, and the film for forming a protective film includes a compound having a carboxyl group or a group that forms a salt with a carboxyl group, and a polymerizable group. Adhesion between the film for forming a protective film and the silicon wafer: After attaching the film for forming a protective film with a thickness of 25 μm on the silicon wafer, the method was used to bring the film for forming a protective film and the silicon wafer into contact with each other. The surfaces of the surfaces form an angle of 180° with each other, and the film for forming a protective film is peeled away from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time is measured, and This measured value was taken as the adhesive force between the film for protective film formation and the silicon wafer. ^Shear strength of the protective film: After attaching the protective film forming film with a thickness of ²⁵ μm to the silicon wafer, the protective film was The film for forming was irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film, and the obtained silicon wafer with a protective film was diced into silicon wafers with a protective film with a size of 3mm×3mm, and only the The protective film in the obtained silicon wafer with protective film is applied to the surface direction of the protective film at a speed of 200 μm/s, and the maximum value of the force applied until the protective film is destroyed (N/3mm □) As the shear strength of the protective film.

The aforementioned compound may be an aliphatic dicarboxylic acid mono(meth)acryloxyalkyl ester.

The aforementioned compound may also be succinic acid mono(2-acryloyloxyethyl).

A film for forming a protective film according to another aspect of the present invention is an energy ray-curable film for forming a protective film, and the film for forming a protective film contains: ε-caprolactone-modified ginseng-(2-acryloyloxy ethyl) isocyanurate (content: 5 to 15% by mass relative to the total mass of solids in the protective film forming composition (IV-1)) as the energy ray curable component (a2); acrylic acid Acrylic polymer obtained by copolymerization of methyl ester (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (content: relative to the total mass of solids in the protective film forming composition (IV-1) 25 to 30% by mass) as a polymer (b) without an energy ray curable group; 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl- 1-butanone (content: 0.3 to 1% by mass relative to the total mass of solids in the composition for forming a protective film (IV-1)) as a photopolymerization initiator (c); silica filler (content: 50 to 65% by mass relative to the total mass of solids in the composition for forming a protective film (IV-1)) as a filler (d); 3-methacryloxypropyltrimethoxysilane (content: relative The total mass of solids in the composition for forming a protective film (IV-1) is 0.2 to 0.6% by mass) as a coupling agent (e); containing a phthalocyanine-based blue dye, an isoindolinone-based yellow dye, and anthracene A quinoid red pigment and a styrene acrylic resin pigment (content: 2 to 6% by mass relative to the total mass of solids in the composition for forming a protective film (IV-1)) as a colorant (g); having a carboxyl group or a compound that forms a salt with a carboxyl group, and a polymerizable group (content: 0.15 to 3% by mass relative to the total mass of solids in the composition for forming a protective film (IV-1), and 0.25 to 1% by mass % is preferable) as the compound (p) (however, the total content of each component does not exceed 100% by mass based on the total mass of solid components in the composition for forming a protective film (IV-1)).

The film for forming a protective film has a property that the adhesive force between the film for forming a protective film and a silicon wafer is 3.6 N/25 mm or more and 8 N/25 mm or less when measured by the following method. When the film for forming a protective film is irradiated with ultraviolet rays to form a protective film, the shear strength of the protective film when measured by the following method is 11N/3mm□ or more and 13N/3mm□ or less, and the film for forming a protective film contains A carboxyl group, a group that forms a salt with a carboxyl group, and a compound of a polymerizable group. Adhesion between the film for forming a protective film and the silicon wafer: After attaching the film for forming a protective film with a thickness of 25 μm on the silicon wafer, the method was used to bring the film for forming a protective film and the silicon wafer into contact with each other. The surfaces of the surfaces form an angle of 180° with each other, and the film for forming a protective film is peeled away from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time is measured, and This measured value was taken as the adhesive force between the film for protective film formation and the silicon wafer. ^Shear strength of the protective film: After attaching the protective film forming film with a thickness of ²⁵ μm to the silicon wafer, the protective film was The film for forming was irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film, and the obtained silicon wafer with a protective film was diced into silicon wafers with a protective film with a size of 3mm×3mm, and only the The protective film in the obtained silicon wafer with protective film is applied to the surface direction of the protective film at a speed of 200 μm/s, and the maximum value of the force applied until the protective film is destroyed (N/3mm □) As the shear strength of the protective film.

The aforementioned compound may be an aliphatic dicarboxylic acid mono(meth)acryloxyalkyl ester.

The aforementioned compound may also be succinic acid mono(2-acryloyloxyethyl).

A silicon wafer with a protective film as another aspect of the present invention includes a protective film that is a cured product of an energy ray curable protective film forming film, and a silicon wafer on which the aforementioned protective film forming film is attached. A cut-off silicon wafer, wherein the adhesive force between the film for forming a protective film before curing and the aforementioned silicon wafer is 3.6 N/25 mm or more and 8 N/25 mm or less when measured by the following method, and the following method The shear strength of the protective film at the time of measurement is 11N/3mm□ or more and 13N/3mm□ or less. Adhesion between the film for forming a protective film and the silicon wafer: After attaching the film for forming a protective film with a thickness of 25 μm on the silicon wafer, the method was used to bring the film for forming a protective film and the silicon wafer into contact with each other. The surfaces of the surfaces form an angle of 180° with each other, and the film for forming a protective film is peeled away from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time is measured, and This measured value was taken as the adhesive force between the film for protective film formation and the silicon wafer. ^Shear strength of the protective film: After attaching the protective film forming film with a thickness of ²⁵ μm to the silicon wafer, the protective film was The film for forming was irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film, and the obtained silicon wafer with a protective film was diced into silicon wafers with a protective film with a size of 3mm×3mm, and only the The protective film in the obtained silicon wafer with protective film is applied to the surface direction of the protective film at a speed of 200 μm/s, and the maximum value of the force applied until the protective film is destroyed (N/3mm □) As the shear strength of the protective film.

The said film for protective film formation contains the compound which has a carboxyl group or a group which forms a salt with a carboxyl group, and a polymeric group.

The aforementioned compound may be an aliphatic dicarboxylic acid mono(meth)acryloxyalkyl ester.

The aforementioned compound may also be succinic acid mono(2-acryloyloxyethyl).

A silicon wafer with a film for forming a protective film as another aspect of the present invention includes an energy ray curable film for forming a protective film, and a silicon wafer on which the film for forming a protective film is attached, wherein the protective film The film for forming has an adhesive force between the film for forming a protective film and a silicon wafer of 3.6 N/25 mm or more and 8 N/25 mm or less when measured by the following method, and when the film for forming a protective film is irradiated with ultraviolet rays to form a protective film In the case of a film, the shear strength of the protective film when measured by the following method is 11N/3mm□ or more and 13N/3mm□ or less. Adhesion between the film for forming a protective film and the silicon wafer: After attaching the film for forming a protective film with a thickness of 25 μm on the silicon wafer, the method was used to bring the film for forming a protective film and the silicon wafer into contact with each other. The surfaces of the surfaces form an angle of 180° with each other, and the film for forming a protective film is peeled away from the silicon wafer at a peeling speed of 300mm/min, and the peeling force (N/25mm) at this time is measured, and This measured value was taken as the adhesive force between the film for protective film formation and the silicon wafer. ^Shear strength of the protective film: After attaching the protective film forming film with a thickness of ²⁵ μm to the silicon wafer, the protective film was The film for forming was irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film, and the obtained silicon wafer with a protective film was diced into silicon wafers with a protective film with a size of 3mm×3mm, and only the The protective film in the obtained silicon wafer with protective film is applied to the surface direction of the protective film at a speed of 200 μm/s, and the maximum value of the force applied until the protective film is destroyed (N/3mm □) As the shear strength of the protective film.

The said film for protective film formation contains the compound which has a carboxyl group or a group which forms a salt with a carboxyl group, and a polymeric group.

The aforementioned compound may be an aliphatic dicarboxylic acid mono(meth)acryloxyalkyl ester.

The aforementioned compound may also be succinic acid mono(2-acryloyloxyethyl). [Example]

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

<Materials for the preparation of protective film-forming composition> The raw materials used to prepare the composition for protective film formation are as follows. [Energy ray curable component (a2)] (a2)-1: ε-caprolactone-modified ginseng-(2-acryloxyethyl)isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional based UV-curable compounds). [Polymer (b) not having an energy ray curable group] (b)-1: Acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) (weight average molecular weight: 300,000 , with a glass transition temperature of 6 °C). [Photopolymerization initiator (c)] (c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone ("Irgacure (registered trademark) 369 manufactured by BASF Corporation) "). [Filler (d)] (d)-1: Silica filler (fused silica filler, average particle size: 8 μm). [Coupling agent (e)] (e)-1: 3-methacryloxypropyltrimethoxysilane ("KBM-503" by Shin-Etsu Chemical Co., Ltd., silane coupling agent). [Coloring agent (g)] (g)-1: 32 parts by mass of a phthalocyanine-based blue pigment (blue pigment 15:3), 18 parts by mass of an isoindolinone-based yellow pigment (yellow pigment 139), and 50 parts by mass of anthraquinone A type of red pigment (red pigment 177) is mixed so that the total amount of the above three pigments/the amount of styrene acrylic resin=1/3 (mass ratio). [compound (p)] (P)-1: Succinic acid mono(2-acryloyloxyethyl)

[Example 1] ＜Manufacture of composite sheet for protective film formation＞ (Preparation of protective film-forming composition (IV-1)) Energy ray curable component (a2)-1, polymer (b)-1, photopolymerization initiator (c)-1, filler (d)-1, coupling agent (e)-1, colorant (g )-1 and compound (p)-1 were dissolved or dispersed in methyl ethyl ketone so that the contents of the above components (solid content, parts by mass) became the values shown in Table 1, and stirred at 23°C to A protective film forming composition (IV-1) having a solid content concentration of 50% by mass was prepared. In addition, "-" described in the column of the component contained in Table 1 means that the composition for protective film formation (IV-1) does not contain this component.

(Preparation of Adhesive Composition (I-4)) A non-energy ray-curable adhesive composition (I-4) with a solid content concentration of 30% by mass was prepared, which contained an acrylic polymer (100 parts by mass, solid content) and an isocyanate crosslinking agent (Nippon Polyurethane Co., Ltd. "Coronate L" manufactured by (Nippon Polyurethane Industry Co., Ltd.), a toluene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content), and also contains methyl ethyl Ketones as solvents. The aforementioned acrylic polymer is obtained by copolymerizing 2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass), and has a weight average molecular weight of 600,000.

(Manufacture of support sheet) A peeling film ("SP-PET 381031" manufactured by Lintec Co., Ltd., 38 μm thick) obtained by peeling one surface of a polyethylene terephthalate film with silicone treatment ), the adhesive composition (I-4) obtained above was coated, and dried by heating at 120°C for 2 minutes to form a non-energy ray-curable adhesive with a thickness of 10 μm. Adhesive layer. Next, a polypropylene-based film (80 μm in thickness) as a base material was attached to the exposed surface of the adhesive layer to obtain a base material, an adhesive layer, and a release film in this order in the thickness direction of these film layers. A support sheet composed of laminated layers.

(Manufacture of composite sheets for protective film formation) A peeling film obtained by peeling one surface of a polyethylene terephthalate film with silicone treatment (the second peeling film, "SP-PET" manufactured by Lintec Corporation) 382150", a thickness of 38 μm), the protective film-forming composition (IV-1) obtained above was coated, and heated at 100°C for 2 minutes and dried to produce a thickness of 25μm energy ray curable protective film forming film. Next, the peeling-treated surface of the peeling film (the first peeling film, "SP-PET 381031" manufactured by Lintec Co., Ltd., 38 μm in thickness) was attached to the obtained film for forming a protective film without the second peeling film. 2 On the exposed surface on the side of the release film, a laminated film having a first release film on one surface of the film for forming a protective film and a second release film on the other surface is obtained.

Next, the release film was removed from the adhesive layer of the support sheet obtained above. In addition, the first release film was removed from the laminated film obtained above. Thereafter, the surface exposed by removing the above-mentioned release film in the adhesive layer and the surface exposed by removing the above-mentioned first release film in the film for forming a protective film are bonded to each other to manufacture a substrate, an adhesive The agent layer, the film for protective film formation, and the 2nd release film were laminated|stacked in this order in the thickness direction of these film layers, and the composite sheet for protective film formation obtained was laminated|stacked.

<Evaluation of film for protective film formation> (Adhesion force between protective film forming film and silicon wafer) The surface exposed by removing the first release film from the above-obtained laminated film in the film for forming a protective film was attached to an adhesive tape ("D-841" manufactured by Lintec Corporation). After that, a test piece was produced by cutting the obtained structure into a size of 25 mm×140 mm. Next, the second peeling film was removed from the film for forming a protective film in the obtained test piece, and the exposed surface of the film for forming a protective film was attached to the surface of a 6-inch silicon wafer (thickness: 300 μm). #2000 abrasive surface and let stand for 30 minutes.

Next, using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation) at a temperature of 23°C at a peeling speed of 300 mm/min, the laminate of the film for forming a protective film and the adhesive tape was separated from the silicon The wafer is pulled apart in such a way that the protective film forming film and the surfaces of the silicon wafer that are in contact with each other form an angle of 180° with each other, that is, so-called 180° peeling is performed. And, the peeling force (load, N/25mm) at this time was measured, and this measured value was defined as the adhesive force between the film for protective film formation and a silicon wafer. The results are shown in Table 1.

＜Evaluation of protective film＞ (Inhibition of floating of semiconductor wafers) The surface of the film for forming a protective film exposed by removing the first release film from the above-obtained laminated film was attached to the #2000 polished surface of an 8-inch silicon wafer (thickness: 300 μm). Next, the 2nd peeling film is removed from this film for protective film formation, and the film for protective film formation is exposed. Furthermore, the release film was removed from the adhesive layer of the support sheet obtained above to expose the adhesive layer. After that, by attaching the exposed surface of the adhesive layer and the exposed surface of the film for forming a protective film to each other and attaching them to the ring frame at the same time, the substrate, the adhesive layer, the film for forming a protective film, and the silicon wafer are attached to each other. A laminate obtained by laminating these film layers in the thickness direction in this order was fixed to a ring frame and left to stand for 30 minutes.

After that, by using an ultraviolet irradiation device ("RAD-2000m/8" manufactured by Lintec Corporation), under the conditions of illuminance of 195mW/cm ² and light intensity of 170mJ/cm ² , through the above-mentioned substrate and adhesion The agent layer irradiates the film for protective film formation with ultraviolet rays, and hardens the film for protective film formation into a protective film. Hereinafter, the structure thus obtained (that is, the structure in which the film for forming a protective film in the above-mentioned laminate has become a protective film) is referred to as "a laminate after curing". Next, in order to irradiate the silicon wafer with laser light through the protective film, the above-mentioned cured laminate and ring frame are set on a laser saw ("DFL7361" manufactured by Disco Corporation) while adjusting their positions. )superior.

Next, laser light having a wavelength of 1342 nm was irradiated through the support sheet and the protective film so as to focus on the focal point set inside the semiconductor wafer, thereby forming a modified layer inside the semiconductor wafer. Next, set the above-mentioned cured laminate and the ring frame on a grain separator (Die Separator) ("DDS2300" manufactured by Disco Company), and under the condition of 0°C, place the above-mentioned cured laminate on the aforementioned protection The surface direction of the film (along the direction of the surface) is extended to cut the protective film and at the same time divide the silicon wafer at the position of the aforementioned modified layer to obtain a plurality of silicon wafers with a size of 3mm×3mm.

Next, visually observe the obtained split state of the silicon wafer on the protective film, it is judged as "A" that the silicon wafer does not float from the protective film at all, and there is one or more silicon wafers that are lifted from the protective film. If it floats, it is judged as "B". The results are shown in Table 1.

(shear strength of protective film) Except for using a 6-inch silicon wafer (300 μm thick) instead of an 8-inch silicon wafer (300 μm thick), the base , the adhesive layer, the film for forming a protective film, and the silicon wafer were laminated in this order in the thickness direction of these film layers, and the laminate obtained was fixed on a ring frame and left to stand for 30 minutes. Also, a protective film forming film was attached to the #2000 polished surface of a 6-inch silicon wafer.

After that, by using an ultraviolet irradiation device ("RAD 2000m/8" manufactured by Lintec Corporation), under the conditions of illuminance of 195mW/cm ² and light intensity of 170mJ/cm ² , through the above-mentioned substrate and adhesion The agent layer irradiates ultraviolet rays to the film for forming a protective film to cure the film for forming a protective film into a protective film, thereby obtaining a silicon wafer with a protective film. After that, use a dicing tool to cut the silicon wafer and the protective film together (cut the silicon wafer with the protective film) and singulate it, and then obtain a plurality of silicon wafers with a protective film with a size of 3mm×3mm (that is, , silicon wafer with a protective film).

Next, using a universal push-pull tester ("DAGE 4000" manufactured by Nordson Advanced Technology Co., Ltd.), at 23°C, using a shear tool (share tool) at a speed of 200 μm/s, only the attached The protective film in the silicon wafer with the protective film exerts force in the direction of the surface of the protective film. After that, the maximum value of the force applied until the protective film was broken was confirmed, and it was set as the shear strength (N/3mm□). The results are shown in Table 1.

<Manufacture of protective film forming composite sheet, evaluation of protective film forming film and protective film> [Example 2, Comparative Example 1] Except that the amounts of the ingredients required for the preparation of the protective film-forming composition (IV-1) were changed to those shown in Table 1, the protective film-forming film and A composite sheet for forming a protective film, and evaluation of the film for forming a protective film and the protective film. The results are shown in Table 1.

[Table 1]

As can be clearly seen from the above results, in Examples 1 and 2, when the silicon wafer with the protective film is expanded, and then the protective film is cut and the silicon wafer is divided into silicon wafers at the same time, the silicon wafer is suppressed. The wafer floats from the protective film. In Examples 1 and 2, the adhesive force 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 high as 11.3 N/3 mm□ or more (11.3 to 11.4 N/3 mm□).

On the other hand, in Comparative Example 1, the lifting of the silicon wafer from the protective film was not suppressed. In Comparative Example 1, the adhesive force between the film for forming a protective film and the silicon wafer was 2.6 N/25 mm, which was lower than that of Examples 1-2. Furthermore, in Comparative Example 1, the shear strength of the protective film was 10.1 N/3mm□, which was lower than that of Examples 1-2.

From the results of these examples and comparative examples, it can be clearly confirmed that whether or not the silicon wafer is lifted will be affected by the above-mentioned adhesive force and shear strength. [industrial availability]

The present invention can be applied to the manufacture of semiconductor devices.

1A, 1A', 1B, 1C, 1D, 1E‧‧‧composite sheet for protective film formation 9‧‧‧semiconductor wafer 9b‧‧‧The back surface of the semiconductor wafer 9'‧‧‧semiconductor chip 10‧‧‧Support piece 10a‧‧‧The surface of the support sheet (1st surface) 11‧‧‧Substrate 11a‧‧‧The surface of the substrate (1st surface) 12‧‧‧adhesive layer 12a‧‧‧The surface of the adhesive layer (1st surface) 13.23‧‧‧Film for protective film formation 13a, 23a‧‧‧The surface of the protective film forming film (1st surface) 13b‧‧‧The surface of the protective film forming film (second surface) 13'‧‧‧Protective film 15‧‧‧Peeling film 16‧‧‧adhesive layer for jig 16a‧‧‧The surface of the adhesive layer for jigs 91‧‧‧Modified layer of semiconductor wafer 130‧‧‧cut protective film forming film 130'‧‧‧cut protective film 151‧‧‧The first release film 152‧‧‧Second release film

[ Fig. 1 ] is a schematic cross-sectional view of a film for forming a protective film according to an embodiment of the present invention. [ Fig. 2] Fig. 2 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 3 ] is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 4] Fig. 4 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 5] Fig. 5 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 6] Fig. 6 is a schematic cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. [ Fig. 7] Fig. 7 is a schematic cross-sectional view for explaining one embodiment of a method of manufacturing a semiconductor wafer in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film. [ Fig. 8] Fig. 8 is a schematic cross-sectional view for explaining one embodiment of a method of manufacturing a semiconductor wafer in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film. [ Fig. 9] Fig. 9 is a schematic cross-sectional view for explaining one embodiment of a method of manufacturing a semiconductor wafer in the case of using a film for forming a protective film that does not yet constitute a composite sheet for forming a protective film. [ Fig. 10] Fig. 10 is a schematic cross-sectional view illustrating an embodiment of a semiconductor wafer manufacturing method using a protective film forming composite sheet in which a protective film forming film and a support sheet are previously integrated. [ Fig. 11] Fig. 11 is a schematic cross-sectional view illustrating an embodiment of a semiconductor wafer manufacturing method using a protective film-forming composite sheet in which a protective film-forming film and a support sheet are previously integrated. [ Fig. 12] Fig. 12 is a schematic cross-sectional view illustrating an embodiment of a semiconductor wafer manufacturing method using a protective film forming composite sheet in which a protective film forming film and a support sheet are previously integrated.

1A‧‧‧Composite sheet for protective film formation

10‧‧‧Support piece

10a‧‧‧The surface of the supporting sheet (the first surface)

11‧‧‧Substrate

11a‧‧‧The surface of the substrate (the first surface)

12‧‧‧adhesive layer

12a‧‧‧The surface of the adhesive layer (the first surface)

13‧‧‧Film for protective film formation

13a‧‧‧The surface of the film for protective film formation (1st surface)

15‧‧‧Peeling film

16‧‧‧adhesive layer for jig

16a‧‧‧The surface of the adhesive layer for jigs

Claims (3)

A film for forming a protective film, which is an energy-ray-curable protective film-forming film containing a curable component, wherein the curable component is composed only of an energy-ray-curable component, and the protective film measured by the following method The adhesive force between the film for formation and the silicon wafer is 3N/25mm or more, and when the film for forming a protective film is irradiated with ultraviolet rays to form a protective film, the shear strength of the protective film measured by the following method is 10.5N/3mm□ or more, Adhesion between the protective film forming film and the silicon wafer: After attaching the aforementioned protective film forming film with a thickness of 25 μm to the silicon wafer, the aforementioned protective film forming film In the case where the surfaces of the silicon wafers originally in contact with each other form an angle of 180°, the film for forming a protective film was pulled away from the silicon wafer at a peeling speed of 300 mm/min, and the peeling force at this time was measured ( N/25mm), and this measured value is taken as the adhesive force between the protective film forming film and the silicon wafer, and the shear strength of the protective film: when the aforementioned protective film forming film with a thickness of 25 μm is attached to the silicon wafer After rounding, under the conditions of an illuminance of 195 mW/cm ² and a light intensity of 170 mJ/cm ² , the film for forming a protective film was cured into a protective film by irradiating ultraviolet rays to the film for forming a protective film, and the obtained attached The silicon wafer with protective film is cut into silicon wafer with protective film with a size of 3mm×3mm, and only the protective film in the obtained silicon wafer with protective film is protected at a speed of 200μm/s. A force was applied in the surface direction of the film, and the maximum value (N/3mm□) of the force applied until the protective film was broken was defined as the shear strength of the protective film. A composite sheet for forming a protective film, comprising a support sheet, and the film for forming a protective film as described in item 1 of the patent scope of the application is included on the support sheet. A method for manufacturing a semiconductor wafer, comprising: applying the film for forming a protective film as described in item 1 of the patent application, or the film for forming a protective film in the composite sheet for forming a protective film as described in item 2 of the scope of application attached to a semiconductor wafer; irradiating energy rays to the film for forming a protective film after being attached to the semiconductor wafer to form a protective film; irradiating laser light onto the protective film or film for forming a protective film to form a modified layer inside the semiconductor wafer; film together in the surface direction of the aforementioned protective film or protective film forming film to cut the aforementioned protective film or protective film forming film and at the same time divide the aforementioned semiconductor wafer at the position of the aforementioned modified layer, thereby obtaining a plurality of semiconductor wafers. wafer.

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