KR102445532B1 - Composite sheet for forming a protective film - Google Patents

Abstract

A substrate is provided, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate, and the laser printing property of the protective film formed from the film for forming a protective film is excellent, and the visibility of printing of the protective film is also excellent A composite sheet for forming a protective film is provided. The composite sheet for forming a protective film includes a substrate, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate, and the support sheet, which is a laminate of the substrate and the pressure-sensitive adhesive layer, has a haze higher than 45%, Transmission clarity of the support sheet is 100 or more.

Description

Composite sheet for forming a protective film

The present invention relates to a composite sheet for forming a protective film.

This application claims priority based on Japanese Patent Application No. 2017-068187 for which it applied to Japan on March 30, 2017, and uses the content here.

DESCRIPTION OF RELATED ART In recent years, manufacture of the semiconductor device to which the mounting method called a so-called face down method is applied is performed. In the face-down method, a semiconductor chip having electrodes such as bumps on the circuit surface is used, and the electrodes are joined to the substrate. For this reason, the back surface opposite to the circuit surface of the semiconductor chip can be exposed.

On the exposed back surface of the semiconductor chip, a resin film made of an organic material is formed as a protective film, and the protective film-formed semiconductor chip obtained by forming the protective film in this way can be introduced into a semiconductor device. The protective film is used in the process after the dicing process to prevent so-called chipping, in which cracks and defects are generated in the semiconductor chip.

For formation of such a protective film, the composite sheet for protective film formation which equips the support sheet with the film for protective film formation is used. As the support sheet, for example, a laminated sheet in which an adhesive layer or the like is laminated on a resin substrate is used. In the composite sheet for forming a protective film, in addition to the film for forming a protective film having the ability to form a protective film, the support sheet can function as a dicing sheet, and the film for forming a protective film and the dicing sheet can be integrated.

On the other hand, in the manufacturing process of a semiconductor device, printing (in this specification, it may be called "laser printing") is performed by irradiation of a laser beam to the surface of the support sheet side of the protective film affixed to a semiconductor wafer or a semiconductor chip. There are cases. At this time, the laser beam is irradiated through the support sheet from the side opposite to the side on which the protective film of the support sheet (base material) is formed. And the printing is observed through the support sheet.

Moreover, in the manufacturing process of a semiconductor device, the state of the semiconductor wafer or semiconductor chip provided with the film for forming a protective film or a protective film may be inspected by an infrared camera or the like through the support sheet and these films or protective films for forming a protective film.

Thus, in the manufacturing process of a semiconductor device, laser printing, the film for protective film formation, a protective film, a semiconductor wafer, or the observation of a semiconductor chip may be performed through a support sheet. And the structure of a support sheet has a big influence on these factors and the precision of observation.

For example, the composite sheet for protective film formation which has high light transmittance and is excellent in the visibility of the image of a semiconductor chip in the test|inspection of a semiconductor chip after a dicing process is disclosed so far (refer patent document 1). In the base material constituting the support sheet in the composite sheet for forming a protective film, when it is wound into a roll, at least one surface is usually an uneven surface in order to prevent sticking of the base materials, so-called blocking. And the presence of this uneven|corrugated surface made a support sheet cloudy, and there existed a problem that the semiconductor chip containing a protective film could not be observed clearly, and the visibility of a semiconductor chip was bad. On the other hand, in the composite sheet for resin film formation disclosed by patent document 1, by laminating|stacking an adhesive layer on the uneven|corrugated surface of a base material, and making haze of a support sheet 45 % or less, the visibility of the semiconductor chip via a support sheet. is improving

Japanese Patent No. 5432853 Publication

However, even if the visibility of the semiconductor chip via the support sheet is high, it cannot necessarily be said that the laser printing property of the protective film via the support sheet is excellent. This is because, even if the support sheet enables the improvement of the visibility of the semiconductor chip, the laser printing of the protective film through the support sheet and the visibility of printing cannot necessarily be performed satisfactorily. And it is not certain whether the composite sheet for protective film formation disclosed by patent document 1 is also excellent in laser printing property.

Accordingly, a substrate is provided, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate, and the laser printing property of the protective film formed from the film for forming a protective film is excellent, and the visibility of printing of the protective film Also provides an excellent composite sheet for forming a protective film.

That is, the composite sheet for forming a protective film according to the first aspect of the present invention includes a substrate, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate, and is a laminate of the substrate and the pressure-sensitive adhesive layer. The haze of the support sheet is higher than 45%, and the transmission clarity of the support sheet is 100 or more.

In the composite sheet for forming a protective film according to the above aspect, an adhesive layer for a jig may be provided in a region where the film for forming a protective film is not laminated among the surfaces of the pressure-sensitive adhesive layer on the side provided with the film for forming a protective film.

Energy-beam sclerosis|hardenability may be sufficient as the said film for protective film formation.

Thermosetting may be sufficient as the said film for protective film formation.

Non-hardening may be sufficient as the said film for protective film formation.

Energy ray curability or non-energy ray curability may be sufficient as the said adhesive layer.

The thickness of the said adhesive layer may be 3-20 micrometers.

The surface roughness (Ra) of one surface of the said base material is 0.11 micrometer or more, and the said adhesive layer may directly contact and laminate|stack on the surface of the said surface roughness.

(1) a substrate is provided, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate, wherein a haze of a support sheet that is a laminate of the substrate and the pressure-sensitive adhesive layer is higher than 45%, and the support sheet A composite sheet for forming a protective film with a transmittance clarity of 100 or more.

(2) The composite sheet for forming a protective film according to (1), wherein the adhesive layer for a jig is provided in a region where the film for forming a protective film is not laminated among the surfaces of the pressure-sensitive adhesive layer on the side provided with the film for forming a protective film. .

(3) The composite sheet for protective film formation as described in (1) or (2) whose said film for protective film formation is energy-beam sclerosis|hardenability.

(4) The composite sheet for protective film formation as described in (1) or (2) whose said film for protective film formation is thermosetting.

(5) The composite sheet for forming a protective film according to (1) or (2), wherein the film for forming a protective film is non-curable.

(6) The composite sheet for forming a protective film according to any one of (1) to (5), wherein the pressure-sensitive adhesive layer is energy ray-curable or non-energy-curable.

(7) The composite sheet for protective film formation in any one of (1)-(6) whose thickness of the said adhesive layer is 3-20 micrometers.

(8) Formation of a protective film according to any one of (1) to (7), wherein the surface roughness (Ra) of one surface of the substrate is 0.11 µm or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness for composite sheets.

According to the above aspect, a substrate is provided, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate, and the laser printing property to the protective film formed from the film for forming a protective film is excellent, and the A composite sheet for forming a protective film having excellent print visibility is also provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 1st Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 2nd Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 3rd Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 4th Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 5th Embodiment of this invention.

◇ Composite sheet for forming a protective film

The composite sheet for protective film formation of this embodiment is provided with a base material, and an adhesive layer and the film for protective film formation are laminated|stacked in this order on the said base material. That is, in the composite sheet for protective film formation of this embodiment, a base material, an adhesive layer, and the film for protective film formation are laminated|stacked in this order. Moreover, in the composite sheet for protective film formation of this embodiment, the haze of the support sheet which is a laminated body of the said base material and an adhesive layer is higher than 45 %, and the transmission clarity of the said support sheet is 100 or more.

In addition, in this specification, "film for forming a protective film" means that it is before pasting on the back surface of a semiconductor wafer or semiconductor chip, and "protective film" means that the film for forming a protective film is pasted on the back surface of a semiconductor wafer or semiconductor chip. it means. In addition, when the film for protective film formation has sclerosis|hardenability, what hardened the film for protective film formation is called "a protective film."

In addition, in this specification, even after the film for protective film formation is pasted on a semiconductor wafer or a semiconductor chip, as long as the laminated structure of a support sheet and the film for protective film formation is maintained, this laminated structure is called "composite sheet for protective film formation". call it

The film for forming a protective film is used as a protective film for protecting the back surface (the surface opposite to the electrode formation surface) of a semiconductor wafer or semiconductor chip. And when the haze of a support sheet is higher than 45 % and transmission clarity is 100 or more, the film for protective film formation of this embodiment can make favorable laser printing property and the visibility of printing of a protective film. More specifically, after affixing the composite sheet for forming a protective film on the back surface of a semiconductor wafer or semiconductor chip, laser printing is performed on the support sheet side surface of the protective film affixed to the semiconductor wafer or semiconductor chip. At this time, the laser beam is irradiated through the support sheet from the side opposite to the side on which the protective film of the support sheet (base material) is formed. And the printing is observed through the support sheet. At this time, when the transmission clarity of the support sheet is 100 or more, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.

In addition, in the prior art, in order to thicken laser printing, it is necessary to perform laser printing with high power, and there has been a problem that manufacturing cost is high. Moreover, when printing with high output, there existed a possibility that gas accumulation|storage may generate|occur|produce between a protective film and a support sheet when irradiated through a support sheet. Moreover, although generation|occurrence|production of gas accumulation|storage was avoidable by raising the adhesive force of a support sheet, on the other hand, there existed a subject that pickup aptitude was impaired. For this reason, it was necessary to laser-print a support sheet directly on a protective film after peeling. On the other hand, in the composite sheet for protective film formation of this embodiment, when a haze is higher than 45 %, in the inside of a support sheet, a laser beam is scattered moderately. For this reason, laser printing can be made thick effectively, and the visibility of laser printing can be improved. In addition, since it is not necessary to increase the laser output, generation of gas accumulation can be suppressed, and laser printing can be performed while the support sheet and the protective film are adhered. Moreover, since the adhesive force of a support sheet is also moderate, pick-up aptitude is also favorable.

Further, in the case of a composite sheet for forming a protective film in which the pressure-sensitive adhesive layer for a jig is colorless and transparent in the prior art, or a composite sheet for forming a protective film having a configuration that does not include an adhesive layer for a jig, the composite sheet for forming a protective film on the back surface of a semiconductor wafer or semiconductor chip When affixed with a mounter, the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as "adjustment of the position of the tape tip") was not possible. On the other hand, in the composite sheet for protective film formation of this embodiment, when a haze is higher than 45 %, it detects by the optical sensor mounted on the mounter, and can position a tape front-end|tip.

Although the thickness of the semiconductor wafer or semiconductor chip which is the object of use of the composite sheet for protective film formation of this embodiment is not specifically limited, It is preferable that it is 30 micrometers or more and 1000 micrometers or less from the point which the effect in this embodiment is obtained more remarkably, 100 It is more preferable that they are micrometer or more and 300 micrometers or less.

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

◎ Support sheet

The said support sheet is provided with a base material, is provided with an adhesive layer on the said base material, and consists of multiple layers of two or more layers. The constituent material and thickness of these multiple layers may be mutually the same or different, and the combination of these multiple layers is not specifically limited unless the effect in this embodiment is impaired.

In addition, in this specification, it is not limited to the case of a support sheet, "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, and only some layers may be 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."

Preferred support sheets include, for example, those in which the pressure-sensitive adhesive layer is laminated in direct contact with the substrate, and those in which the pressure-sensitive adhesive layer is laminated on the substrate with an intermediate layer interposed therebetween. As a more preferable support sheet, what is laminated|stacked in direct contact with an adhesive layer on a base material is mentioned.

An example of the composite sheet for protective film formation of this embodiment is demonstrated for each type of such a support sheet, referring drawings below. On the other hand, the drawings used in the following description may enlarge and show the main part for convenience in order to make the characteristics of the present embodiment easy to understand, and the dimensional ratio of each component is not limited to the same as in reality.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 1st Embodiment of this invention.

The composite sheet 1A for protective film formation shown here equips the adhesive layer 12 on the base material 11, and equips the adhesive layer 12 with the film 13 for protective film formation. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 . In other words, the composite sheet 1A for forming a protective film has a structure in which the film 13 for forming a protective film is laminated on one surface 10a of the support sheet 10 . In addition, the composite sheet 1A for forming a protective film further includes a release film 15 on the entire surface (upper surface and side surface) of the surface 13a of the film 13 for forming a protective film and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. This is stacked.

On the other hand, in the present specification, the "release film" is a film having a peeling function, specifically, in order to protect the film for forming a protective film before sticking to a semiconductor wafer, the film affixed on the surface of the film for forming a protective film. That is, it is used by peeling it during operation.

In the composite sheet 1A for forming a protective film, the haze of the support sheet 10, which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more. .

The composite sheet 1A for protective film formation shown in FIG. 1 is a semiconductor wafer (not shown) in the central side partial area|region among the surface 13a of the film 13 for protective film formation in the state from which the peeling film 15 was removed. is pasted on the other side of Moreover, the area|region near the periphery of the film 13 for protective film formation is affixed to jigs, such as a ring frame, and is used.

It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 2nd Embodiment of this invention. In addition, in the drawings after FIG. 2, the same code|symbol as the case of the case of the illustrated figure is attached|subjected to the same component as that shown in the figure already demonstrated, and the detailed description is abbreviate|omitted.

The composite sheet 1B for protective film formation shown here is the same thing as 1 A of composite sheets for protective film formation shown in FIG. 1 except the point provided with the adhesive bond layer 16 for jig|tools. That is, in the composite sheet 1B for protective film formation, the adhesive layer 12 is laminated|stacked on the one surface 11a of the base material 11. The film 13 for protective film formation is laminated|stacked on the partial area|region of the central side of the surface 12a of the adhesive layer 12, ie, a semiconductor wafer pasting area. The adhesive layer 16 for a jig|tool is laminated|stacked on the part of the surface 12a of the adhesive layer 12, ie, in the area|region near the periphery. The release film 15 is laminated|stacked on the surface 13a (upper surface) of the film 13 for protective film formation, and the surface 16a (upper surface) of the adhesive bond layer 16 for jig|tools.

In the composite sheet for forming a protective film 1B, the haze of the support sheet 10, which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more. .

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

As for the composite sheet 1B for protective film formation shown in FIG. 2, the back surface of a semiconductor wafer (not shown) is affixed to the surface 13a of the film 13 for protective film formation in the state from which the peeling film 15 was removed. In addition, the upper surface of the surface 16a of the adhesive bond layer 16 for jigs is affixed to jigs, such as a ring frame, and is used.

It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 3rd Embodiment of this invention.

The composite sheet 1A for protective film formation shown here 1 C of composite sheets for protective film formation shown here except the point provided with the intermediate|middle layer 17 between the adhesive layer 12 and the film 13 for protective film formation 1A for protective film formation shown in FIG. ) is the same as In 1 C of composite sheets for protective film formation, the support sheet 10 is the laminated body of the base material 11, the adhesive layer 12, and the intermediate|middle layer 17. As shown in FIG. In other words, 1 C of composite sheets for protective film formation have the structure in which the film 13 for protective film formation was laminated|stacked on one surface 10a (17a) of the support sheet 10. In addition, the composite sheet 1C for forming a protective film further comprises the entire surface (top and side) of the surface 13a of the film 13 for forming a protective film, the surface (side) of the intermediate layer 17a, and the surface 12a of the pressure-sensitive adhesive layer. ) (upper surface), a release film 15 is laminated.

In the composite sheet 1C for forming a protective film, the haze of the support sheet 10, which is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17, is higher than 45%, and the penetration of the support sheet 10 is higher than 45%. Sharpness is greater than 100.

The composite sheet 1C for protective film formation shown in FIG. 3 is a semiconductor wafer (not shown) in the central side partial area|region among the surface 13a of the film 13 for protective film formation in the state from which the peeling film 15 was removed. is pasted on the other side of Moreover, the area|region near the periphery of the film 13 for protective film formation is affixed to jigs, such as a ring frame, and is used.

It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 4th Embodiment of this invention.

The composite sheet 1D for forming a protective film shown here is the same as that of the composite sheet 1A for forming a protective film shown in Fig. 1 , except that the intermediate layer 17 is provided between the base 11 and the pressure-sensitive adhesive layer 12 . will be. In the composite sheet 1D for forming a protective film, the support sheet 10 is a laminate of the base material 11 , the intermediate layer 17 , and the pressure-sensitive adhesive layer 12 . In other words, the composite sheet 1D for forming a protective film has a structure in which the film 13 for forming a protective film is laminated on one surface 10a ( 12a ) of the support sheet 10 . Further, the composite sheet 1D for forming a protective film is further provided with a release film 15 on the entire surface (upper surface and side surface) of the surface 13a of the film 13 for forming a protective film and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. ) are stacked.

In the composite sheet 1D for forming a protective film, the haze of the support sheet 10, which is a laminate of the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12, is higher than 45%, and the penetration of the support sheet 10 is higher than 45%. Sharpness is greater than 100.

The composite sheet 1D for protective film formation shown in FIG. 4 is a semiconductor wafer (not shown) in the central side partial area|region among the surface 13a of the film 13 for protective film formation in the state from which the peeling film 15 was removed. is pasted on the other side of Moreover, the area|region near the periphery of the film 13 for protective film formation is affixed to jigs, such as a ring frame, and is used.

It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 5th Embodiment of this invention.

The composite sheet 1E for protective film formation shown here is the same thing as the composite sheet 1B for protective film formation shown in FIG. 2 except the point in which the film for protective film formation is laminated|stacked on the whole surface of the surface of an adhesive layer. That is, in the composite sheet 1E for protective film formation, the adhesive layer 12 is laminated|stacked on the one surface 11a of the base material 11. As shown in FIG. The film 13 for forming a protective film is laminated|stacked on the whole surface of the surface 12a of the adhesive layer 12. As shown in FIG. The adhesive bond layer 16 for jig|tools is laminated|stacked on a part of the surface 13a of the film 13 for protective film formation, ie, the area|region in the vicinity of a periphery. The release film 15 is laminated|stacked on the surface 13a (upper surface) of the film 13 for protective film formation, and the surface 16a (upper surface and side surface) of the adhesive bond layer 16 for jig|tools.

In the composite sheet 1E for forming a protective film, the haze of the support sheet 10, which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more. .

As for the composite sheet 1E for protective film formation shown in FIG. 5, the back surface of a semiconductor wafer (not shown) is affixed to the surface 13a of the film 13 for protective film formation in the state from which the peeling film 15 was removed. In addition, the upper surface of the surface 16a of the adhesive bond layer 16 for jigs is affixed to jigs, such as a ring frame, and is used.

Thus, the composite sheet for protective film formation of this embodiment may be equipped with the adhesive bond layer for jigs, no matter what form the support sheet and the film for protective film formation are. However, normally, as shown in FIGS. 2 and 5, in the composite sheet for protective film formation of this embodiment provided with the adhesive bond layer for jigs, the adhesive bond layer for jigs on the support sheet 10 or the film 13 for protective film formation. (16) is preferably provided.

The composite sheet for forming a protective film of the present embodiment is not limited to that shown in Figs. 1 to 5, and within a range that does not impair the effect in the present embodiment, some configurations of those shown in Figs. 1 to 5 are changed or deleted, Another configuration may be added to what has been described so far.

For example, in the composite sheet for protective film formation shown in FIG.2 and FIG.5, the intermediate|middle layer 17 may be formed between the adhesive layer 12 and the film 13 for protective film formation. That is, in the composite sheet for protective film formation of this embodiment, as for the support sheet 10, the base material 11, the adhesive layer 12, and the intermediate|middle layer 17 may be laminated|stacked in this order. Here, the intermediate|middle layer 17 is the same as the intermediate|middle layer 17 which may be formed in the composite sheet for protective film formation shown in FIGS. As the intermediate layer 17, any one can be selected according to the purpose.

In addition, in the composite sheet for protective film formation shown in FIG. 2 and FIG. 5, the intermediate|middle layer 17 may be formed between the base material 11 and the adhesive layer 12, for example. That is, in the composite sheet for protective film formation of this embodiment, as for the support sheet 10, the base material 11, the intermediate|middle layer 17, and the adhesive layer 12 may be laminated|stacked in this order. Here, the intermediate|middle layer 17 is the same as the intermediate|middle layer 17 which may be formed in the composite sheet for protective film formation shown in FIGS. As the intermediate layer 17, any one can be selected according to the purpose.

In addition, in the composite sheet for protective film formation shown in FIGS. 1-5, the intermediate|middle layer 17 may be formed in the location other than the location shown in FIGS.

In addition, layers other than the said intermediate|middle layer 17 may be formed in arbitrary locations in the composite sheet for protective film formation shown to FIGS.

In addition, in the composite sheet for protective film formation shown in FIGS. 3 and 4, the adhesive bond layer 16 for jigs may be formed.

In addition, in the composite sheet for protective film formation of this embodiment, a part of clearance gap may arise between the peeling film 15 and this peeling film 15 and the layer in direct contact.

In addition, in the composite sheet for protective film formation of this embodiment, the magnitude|size and shape of each layer can be adjusted arbitrarily according to the objective.

In the composite sheet for protective film formation of this embodiment, the support sheet may be opaque and may be colored according to the objective.

Specifically, the transmission clarity of the supporting sheet is 100 or more, preferably 150 or more, more preferably 200 or more and 450 or less, and still more preferably 300 or more and 430 or less.

When the transmission clarity of a support sheet is the said range, the light scattering in the outer surface of a support sheet can be suppressed and the visibility of laser printing can be improved.

In addition, the transparency of transmission of a support sheet can be measured based on JISK7374-2007 using the image-measuring machine "ICM-10P" manufactured by Suga Test Co., Ltd. or the like.

Moreover, in order to make the transmission clarity of a support sheet into the said range, what is necessary is just to adjust the surface roughness of the outer surface of a support sheet, for example.

Moreover, the haze of a support sheet is higher than 45 %, Preferably they are 46 % or more, More preferably, they are 47 % or more and 90 % or less, More preferably, they are 50 % or more and 85 % or less.

Conventionally, it is necessary to increase the laser output in order to increase the thickness of the laser printing, and when irradiated through the support sheet, gas accumulation occurs between the protective film and the support sheet. For this reason, it was necessary to laser-print a support sheet directly on a protective film after peeling. On the other hand, in the composite sheet for protective film formation of this embodiment, when the haze of a support sheet is the said range, a laser beam is scattered moderately in a support sheet inside. For this reason, laser printing can be made thick effectively, and the visibility of laser printing can be improved. Also, it is not necessary to increase the laser output. For this reason, generation|occurrence|production of gas accumulation|storage can be suppressed and laser printing can be performed with the support sheet and the state in which the protective film adhere|attached.

Further, in the case of a composite sheet for forming a protective film in which the pressure-sensitive adhesive layer for a jig is colorless and transparent in the prior art, or a composite sheet for forming a protective film having a configuration that does not include an adhesive layer for a jig, the composite sheet for forming a protective film on the back surface of a semiconductor wafer or semiconductor chip When affixed with a mounter, the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as "adjustment of the position of the tape tip") was not possible. On the other hand, in the composite sheet for protective film formation of this embodiment, when the haze of a support sheet is the said range, it is detected by the optical sensor mounted on the mounter, and the position of a tape front-end|tip can be adjusted.

In addition, the haze of a support sheet can be measured based on JISK7136-2000 using NDH-5000 etc. by the Nippon Denshoku Industries Co., Ltd. product. Moreover, in order to make the haze of a support sheet into the said range, what is necessary is just to make a base material or an intermediate|middle layer contain a filler or a coloring agent, and to adjust, for example. Or, for example, what is necessary is just to change the firmness of an adhesive layer, to form a space|interval between a base material or an intermediate|middle layer, and an adhesive layer, and to adjust.

Moreover, when the film for protective film formation has energy-beam sclerosis|hardenability, it is preferable for a support sheet to permeate|transmit an energy-beam.

For example, in the support sheet, the transmittance measured using an integrating sphere of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance|permeability of the said light is such a range and an energy ray (ultraviolet ray) is irradiated to the film for protective film formation through a support sheet, the hardening degree of the film for protective film formation improves more.

On the other hand, the upper limit of the transmittance|permeability of the light whose wavelength is 375 nm in a support sheet is although it does not specifically limit, For example, it is possible to set it as 95 %.

In addition, in this specification, "energy-beam sclerosis|hardenability" means the property to harden|cure by irradiating an energy-beam. "Non-energy-ray-curable" means the property which does not harden even if it irradiates an energy-beam, and thermosetting and non-hardening are included. "Thermosetting" means the property to harden|cure by heating. "Non-hardening" means the property which does not harden|cure by heating, irradiation of an energy ray, etc.

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

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

Next, each layer constituting the support sheet will be described in more detail.

○ Description

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

Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer (copolymer obtained using ethylene as a monomer) ; vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyester in which all structural units have aromatic cyclic groups; a copolymer of two or more of the above polyesters; poly(meth)acrylic acid ester; Polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; Polyether ketone etc. are mentioned.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are also mentioned, for example. In the polymer alloy of the polyester and other resins, it is preferable that the amount of the resin other than the polyester is relatively small.

Moreover, as said resin, For example, 1 type(s) or 2 or more types of the said resin exemplified so far are crosslinked; Modified resins, such as an ionomer using 1 type(s) or 2 or more types of the said resin illustrated so far, are also mentioned.

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

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

The base material may consist of one layer (single layer), may be composed of two or more layers, and when composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited. does not

It is preferable that they are 40 micrometers or more and 300 micrometers or less, and, as for the thickness of a base material, it is more preferable that they are 60 micrometers or more and 150 micrometers or less. When the thickness of a base material is such a range, the flexibility of the said composite sheet for protective film formation, and the sticking property with respect to a semiconductor wafer or a semiconductor chip improve more.

Here, the "thickness of a base material" means the thickness of the whole base material, for example, the thickness of the base material which consists of multiple layers means the total thickness of all the layers which comprise a base material. In addition, as a measuring method of the thickness of a base material, the method of measuring thickness using a contact thickness meter in arbitrary five places, and calculating the average of the measured values etc. are mentioned, for example.

It is preferable that a base material has high thickness precision, ie, that the nonuniformity of thickness was suppressed irrespective of a site|part. Among the constituent materials described above, examples of the material usable for constituting the substrate having such high thickness precision include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts and softeners (plasticizers) in addition to the main constituent materials such as the resin.

For example, since the haze of a support sheet can be made into the said range when a base material contains a filler or a coloring agent, the visibility of laser printing can be made favorable.

The optical properties of the substrate may satisfy the optical properties of the support sheet described above. That is, the base material may be transparent, may be opaque, may be colorless according to the objective, may be colored, and another layer may be processed (for example, vapor deposition).

And when the film for protective film formation has energy-beam sclerosis|hardenability, it is preferable for a base material to permeate|transmit an energy-beam.

In order to improve the adhesion of the substrate to other layers such as the pressure-sensitive adhesive layer formed thereon, concavo-convex treatment by sandblasting, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame A treatment, chromic acid treatment, or oxidation treatment such as hot air treatment may be applied to the surface.

In addition, as for a base material, the thing to which the primer process was given may be sufficient as the surface.

In addition, the base material may have an antistatic coating layer and a layer that prevents the base material from adhering to another sheet or from adhering the base material to the adsorption table when the composite sheet for forming a protective film is stacked and stored.

Among these, it is preferable that the surface of the substrate has been subjected to electron beam irradiation treatment in particular from the viewpoint that generation of fragments of the substrate due to the friction of the blades during dicing is suppressed.

Further, in the surface-treated substrate, the upper limit of the surface roughness (Ra) of the surface exposed as the outer surface of the support sheet among the substrate is 0.60 µm or less, preferably 0.50 µm or less, more preferably 0.40 µm or less, still more preferably is 0.30 μm or less. When the surface roughness of the substrate is equal to or less than the upper limit, light scattering on the outer surface of the substrate can be reduced and the transmission clarity of the support sheet can be within the above range, so that the visibility of laser printing can be improved.

In addition, the lower limit of surface roughness Ra is not specifically limited, For example, 0.005 micrometer or more may be sufficient, 0.01 micrometer or more may be sufficient, 0.03 micrometer or more may be sufficient, and 0.05 micrometer or more may be sufficient as it.

In addition, when the surface of the substrate has a surface having a surface roughness equal to or less than the upper limit and a surface having a surface roughness of 0.11 µm or more, it is preferable to laminate another layer such as an adhesive layer on the surface having a surface roughness of 0.11 µm or more. Thereby, the surface roughness exposed as the outer surface of the support sheet among the base materials is equal to or less than the upper limit, light scattering on the outer surface of the base material can be reduced, and the transmission clarity of the support sheet can be made within the above range. Visibility can be made favorable.

In addition, when the surface roughness of the substrate is equal to or less than the upper limit on both surfaces, another layer such as an adhesive layer is laminated on the surface having the larger surface roughness, and the surface having the smaller surface roughness is exposed as the outer surface.

In addition, in this specification, unless otherwise indicated, "surface roughness" means so-called arithmetic mean roughness calculated based on JIS B0601:2001, and may be abbreviated as "Ra".

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

○ Adhesive layer

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

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferable.

In addition, in this embodiment, "adhesive resin" is a concept including both the resin which has adhesiveness and the resin which has adhesiveness, For example, the resin itself not only has adhesiveness, but also other components, such as an additive, and Also includes resins exhibiting adhesiveness when combined with resins, resins exhibiting adhesiveness by the presence of triggers such as heat or water.

An adhesive layer may consist of one layer (single layer), may consist of two or more layers, and may consist of multiple layers. doesn't happen

It is preferable that they are 3 micrometers or more and 20 micrometers or less, as for the thickness of an adhesive layer, it is more preferable that they are 5 micrometers or more and 20 micrometers or less, It is especially preferable that they are 5 micrometers or more and 17 micrometers or less.

When the thickness of an adhesive layer is more than the said lower limit, adhesive force can be improved. Moreover, when the surface roughness is 0.11 micrometer or more of a base material, it can be set as the laminated body which has a smooth surface in which the surface of a base material is buried and the light scattering of the base material outer surface was reduced. On the other hand, when the thickness of an adhesive layer is below the said upper limit, blade dicing aptitude and pick-up aptitude can be made favorable.

Here, the "thickness of an adhesive layer" means the thickness of the whole adhesive layer, for example, the thickness of the adhesive layer which consists of multiple layers means the total thickness of all the layers which comprise an adhesive layer. On the other hand, as a measuring method of the thickness of an adhesive layer, the method of measuring thickness using a contact-type thickness meter in arbitrary 5 places, and calculating the average of a measured value etc. are mentioned, for example.

By appropriately adjusting the hardness of the pressure-sensitive adhesive layer, a gap can be formed between the pressure-sensitive adhesive layer and the base material or the intermediate layer, so that the haze of the support sheet can be adjusted within the above range.

The optical properties of the pressure-sensitive adhesive layer should just satisfy the optical properties of the support sheet described above. That is, the adhesive layer may be opaque and may be colored according to the objective.

And when the film for protective film formation has energy-beam sclerosis|hardenability, it is preferable that an adhesive layer permeate|transmits an energy-beam.

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

<<Adhesive composition>>

The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site|part by coating an adhesive composition on the formation target surface of an adhesive layer, and drying it as needed. A more specific method of forming the pressure-sensitive adhesive layer will be described later in detail along with a method of forming other layers. The ratio of content of components which do not vaporize at normal temperature in an adhesive composition becomes the same as the ratio of content of the said components of an adhesive layer normally. In addition, in this specification, "room temperature" means the temperature which is not specifically cooled or heated, ie, normal temperature, For example, the temperature of 15 degreeC or more and 25 degrees C or less is mentioned.

The pressure-sensitive adhesive composition may be coated by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, and a Meyer bar. The method using various coaters, such as a coater and a kiss coater, is mentioned.

The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent to be described later, it is preferably heat-dried, and in this case, for example, at 70°C or more and 130°C or less for 10 seconds or more and 5 minutes or less It is preferable to dry under the conditions of

When the pressure-sensitive adhesive layer is energy-ray-curable, the pressure-sensitive adhesive composition containing the energy-ray-curable pressure-sensitive adhesive, that is, the energy-ray-curable pressure-sensitive adhesive composition, includes, for example, a non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter referred to as "adhesive resin ( I-1a)") and a pressure-sensitive adhesive composition (I-1) containing an energy ray-curable compound; Energy ray-curable pressure-sensitive adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)") containing pressure-sensitive adhesive composition (I-2); The adhesive composition (I-3) containing the said adhesive resin (I-2a) and an energy-beam curable compound, etc. are mentioned.

<Adhesive composition (I-1)>

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

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) is preferably an acrylic resin.

As said acrylic resin, the acrylic polymer which has a structural unit derived from (meth)acrylic-acid alkylester at least is mentioned, for example.

The number of structural units which the said acrylic resin has may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

As said (meth)acrylic acid alkylester, C1-C20 of the alkyl group which comprises an alkylester is mentioned, for example, It is preferable that the said alkyl group is linear or branched.

More specifically, as (meth)acrylic acid alkylester, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) Isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Isooctyl acrylate, (meth)acrylic acid n-octyl, (meth)acrylic acid n-nonyl, (meth)acrylic acid isononyl, (meth)acrylic acid decyl, (meth)acrylic acid undecyl, (meth)acrylic acid dodecyl ((meth)acrylate ) acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl ((meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)acrylic acid palmityl), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl), (meth)acrylic acid nonadecyl, (meth)acrylic acid icosyl, etc. are mentioned.

It is preferable that the said acrylic polymer has the structural unit derived from the C2 or more (meth)acrylic-acid alkylester of the said alkyl group from the point which the adhesive force of an adhesive layer improves. And it is preferable that carbon number of the said alkyl group is 2 or more and 12 or less, and, as for the point which the adhesive force of an adhesive layer improves more, it is more preferable that it is 4 or more and 8 or less. Moreover, it is preferable that carbon number of the said alkyl group is 4 or more (meth)acrylic-acid alkylesters are acrylic acid alkylesters.

It is preferable that the said acrylic polymer has the structural unit derived from a functional group containing monomer further in addition to the structural unit derived from the (meth)acrylic-acid alkylester.

As the functional group-containing monomer, for example, when the functional group reacts with a crosslinking agent described later, it becomes a starting point of crosslinking, or when the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later, introduction of an unsaturated group into the side chain of the acrylic polymer. what makes it possible is

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

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

As the hydroxyl group-containing monomer, for example, (meth) acrylate hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) ) hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic-type unsaturated alcohols (unsaturated alcohol which does not have a (meth)acryloyl skeleton), such as vinyl alcohol and allyl alcohol, etc. are mentioned.

Examples of the carboxyl group-containing monomer include 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 an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

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

The number of functional group-containing monomers constituting the acrylic polymer may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1% by mass or more and 29% by mass or less with respect to the total amount of the structural unit, more preferably 2% by mass or more and 25% by mass or less, 3% by mass It is especially preferable that it is more than 23 mass %.

The said acrylic polymer may have the structural unit derived from another monomer other than the structural unit derived from the structural unit derived from (meth)acrylic-acid alkylester, and a functional group containing monomer further.

The said other monomer will not be specifically limited if it is a monomer copolymerizable with (meth)acrylic-acid alkylester etc.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

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

The acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1a).

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

The number of adhesive resins (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

It is preferable that content of the adhesive resin (I-1a) with respect to the total content of all components other than a solvent in an adhesive composition (I-1) is 5 mass % or more and 99 mass % or less, It is 10 mass % or more and 95 mass % or less It is more preferable, and it is especially preferable that they are 15 mass % or more and 90 mass % or less.

[Energy-ray-curable compound]

As said energy-beam-curable compound which an adhesive composition (I-1) contains, it has an energy-beam polymerizable unsaturated group, and the monomer or oligomer which can be hardened by irradiation of an energy-beam is mentioned.

As a monomer among the energy ray-curable compounds, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1 polyvalent (meth)acrylates such as ,4-butylene glycol di(meth)acrylate and 1,6-hexanediol (meth)acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; Epoxy (meth)acrylate etc. are mentioned.

As an oligomer among energy-beam-curable compounds, the oligomer etc. which form by superposition|polymerization of the monomer illustrated above are mentioned, for example.

The energy-beam-curable compound has a relatively large molecular weight, and a urethane (meth)acrylate or urethane (meth)acrylate oligomer is preferable in terms of difficulty in reducing the storage elastic modulus of the pressure-sensitive adhesive layer.

The number of said energy-beam curable compounds contained in an adhesive composition (I-1) may be one, and two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound relative to the total content of all components other than the solvent is preferably 1% by mass or more and 95% by mass or less, more preferably 2% by mass or more and 90% by mass or less It is preferable, and it is especially preferable that they are 3 mass % or more and 85 mass % or less. For example, any of 3 mass % or more and 80 mass % or less, 3 mass % or more and 65 mass % or less, 3 mass % or more and 50 mass % or less, and 3 mass % or more and 35 mass % or less may be sufficient.

[crosslinking agent]

When using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkylester as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I-1) is additionally a crosslinking agent It is preferable to contain

The crosslinking agent reacts with the functional group to crosslink the adhesive resins (I-1a).

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; metal chelate-based crosslinking agents such as aluminum chelates (crosslinking agents having a metal chelate structure); isocyanurate-based crosslinking agent (crosslinking agent having isocyanuric acid skeleton); and the like.

The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoint of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive strength of the pressure-sensitive adhesive layer and the ease of availability.

The number of crosslinking agents contained in the adhesive composition (I-1) may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The content of the crosslinking agent in the pressure-sensitive adhesive composition (I-1) is preferably 0.01 parts by mass or more and 50 parts by mass or less, and 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the content of the adhesive resin (I-1a). It is preferable, and it is especially preferable that they are 0.3 mass part or more and 23 mass parts or less.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photoinitiator. The adhesive composition (I-1) containing a photoinitiator fully advances hardening reaction even if it irradiates comparatively low energy energy rays, such as an ultraviolet-ray.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, etc. phosphorus compounds; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone etc. are mentioned.

Moreover, as said photoinitiator, For example, Quinone compounds, such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. can also be used.

The number of photoinitiators contained in the pressure-sensitive adhesive composition (I-1) may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

The content of the photoinitiator in the pressure-sensitive adhesive composition (I-1) is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.03 parts by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the content of the energy ray-curable compound. , It is especially preferable that they are 0.05 mass part or more and 5 mass parts or less.

[Other additives]

The adhesive composition (I-1) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect in this embodiment.

Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders, crosslinking accelerators (catalysts) ) and other known additives.

On the other hand, a reaction retarder suppresses that the crosslinking reaction not intended in the adhesive composition (I-1) during storage advances by the action|action of the catalyst mixed in the adhesive composition (I-1), for example. . Examples of the reaction retardant include those that form a chelate complex by chelating with a catalyst, and more specifically, those having two or more carbonyl groups (-C(=O)-) in one molecule. have.

One type may be sufficient as the other additive which adhesive composition (I-1) contains, and 2 or more types may be sufficient as it, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Content of another additive in adhesive composition (I-1) is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-1) may contain a solvent. By containing the solvent, the adhesive composition (I-1) improves the coating aptitude with respect to the coating object surface.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; Esters, such as ethyl acetate (carboxylate ester); ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; Alcohol, such as 1-propanol and 2-propanol, etc. are mentioned.

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

The number of solvents contained in the pressure-sensitive adhesive composition (I-1) may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

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

<Adhesive composition (I-2)>

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

[Adhesive resin (I-2a)]

The adhesive resin (I-2a) is 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 unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.

As said energy-beam polymerizable unsaturated group, a (meth)acryloyl group, a vinyl group (ethenyl group), an allyl group (2-propenyl group) etc. are mentioned, for example, A (meth)acryloyl group is preferable.

Examples of the group capable of bonding with a functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding with a carboxy group or an epoxy group.

As said unsaturated group containing compound, (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, etc. are mentioned, for example.

The number of adhesive resins (I-2a) which the adhesive composition (I-2) contains may be one, and two or more types may be sufficient as them, and in the case of two or more types, these combinations and a ratio can be selected arbitrarily.

It is preferable that content of the adhesive resin (I-2a) with respect to the total content of all components other than a solvent in an adhesive composition (I-2) is 5 mass % or more and 99 mass % or less, It is 10 mass % or more and 95 mass % or less It is more preferable, and it is especially preferable that they are 10 mass % or more and 90 mass % or less.

[crosslinking agent]

When using the acrylic polymer having a structural unit derived from the same functional group-containing monomer as in the adhesive resin (I-1a), for example, as the pressure-sensitive adhesive resin (I-2a), the pressure-sensitive adhesive composition (I-2) is additionally and may contain a crosslinking agent.

As said crosslinking agent in an adhesive composition (I-2), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The number of crosslinking agents contained in the pressure-sensitive adhesive composition (I-2) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The content of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) is preferably 0.01 parts by mass or more and 25 parts by mass or less, and 0.05 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the content of the adhesive resin (I-2a). It is preferable, and it is especially preferable that they are 0.1 mass part or more and 15 mass parts or less.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-2) may further contain a photoinitiator. The adhesive composition (I-2) containing a photoinitiator fully advances hardening reaction even if it irradiates comparatively low energy energy rays, such as an ultraviolet-ray.

As said photoinitiator in adhesive composition (I-2), the thing similar to the photoinitiator in adhesive composition (I-1) is mentioned.

One type may be sufficient as the photoinitiator which adhesive composition (I-2) contains, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The content of the photoinitiator in the pressure-sensitive adhesive composition (I-2) is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.03 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the content of the adhesive resin (I-2a). It is preferable, and it is especially preferable that they are 0.05 mass part or more and 5 mass parts or less.

[Other additives]

The adhesive composition (I-2) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect in this embodiment.

As said other additive in an adhesive composition (I-2), the thing similar to the other additive in an adhesive composition (I-1) is mentioned.

One type may be sufficient as the other additive which adhesive composition (I-2) contains, and 2 or more types may be sufficient as it, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Content of another additive in adhesive composition (I-2) is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in adhesive composition (I-2), the thing similar to the solvent in adhesive composition (I-1) is mentioned.

The number of solvents which the pressure-sensitive adhesive composition (I-2) contains may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

The content of the solvent in the pressure-sensitive adhesive composition (I-2) is not particularly limited, and may be appropriately adjusted.

<Adhesive composition (I-3)>

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

It is preferable that content of the adhesive resin (I-2a) with respect to the total content of all components other than a solvent in an adhesive composition (I-3) is 5 mass % or more and 99 mass % or less, It is 10 mass % or more and 95 mass % or less It is more preferable, and it is especially preferable that they are 15 mass % or more and 90 mass % or less.

[Energy-ray-curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy-beam polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition (I-1) contains The same thing as an energy-ray-curable compound is mentioned.

The number of said energy-beam curable compounds contained in an adhesive composition (I-3) may be one, and two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

It is preferable that content of the said energy-beam curable compound in the said adhesive composition (I-3) is 0.01 mass part or more and 300 mass parts or less with respect to content 100 mass parts of adhesive resin (I-2a), 0.03 mass part or more and 200 mass parts It is more preferable that they are parts or less, and it is especially preferable that they are 0.05 mass part or more and 100 mass parts or less.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-3) may further contain a photoinitiator. The adhesive composition (I-3) containing a photoinitiator fully advances hardening reaction even if it irradiates comparatively low energy energy rays, such as an ultraviolet-ray.

As said photoinitiator in an adhesive composition (I-3), the thing similar to the photoinitiator in an adhesive composition (I-1) is mentioned.

The number of photoinitiators which the pressure-sensitive adhesive composition (I-3) contains may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the photoinitiator is preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.03 parts by mass with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. It is more preferable that they are 10 mass parts or more, and it is especially preferable that they are 0.05 mass parts or more and 5 mass parts or less.

[Other additives]

The adhesive composition (I-3) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect in this embodiment.

As said other additive, the thing similar to the other additive in adhesive composition (I-1) is mentioned.

One type may be sufficient as the other additive which adhesive composition (I-3) contains, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Content of another additive in adhesive composition (I-3) is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in an adhesive composition (I-3), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

The number of solvents which the pressure-sensitive adhesive composition (I-3) contains may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

In the adhesive composition (I-3), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<Adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3)>

So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described, but what has been described as the components contained therein is an overall pressure-sensitive adhesive composition ( In this specification, it can also be used similarly to "a pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3)”).

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

Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy-ray-curable pressure-sensitive adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins (I-1a). ) containing the adhesive composition (I-4) is mentioned, and it is preferable to contain an acrylic resin.

It is preferable that the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) contain one or more crosslinking agents, and the content thereof is the same as that of the pressure-sensitive adhesive composition (I-1) or the like described above. can do.

<Adhesive composition (I-4)>

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

[Adhesive resin (I-1a)]

As adhesive resin (I-1a) in adhesive composition (I-4), the thing similar to adhesive resin (I-1a) in adhesive composition (I-1) is mentioned.

The number of adhesive resins (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

It is preferable that content of the adhesive resin (I-1a) with respect to the total content of all components other than a solvent in an adhesive composition (I-4) is 5 mass % or more and 99 mass % or less, It is 10 mass % or more and 95 mass % or less It is more preferable, and it is especially preferable that they are 15 mass % or more and 90 mass % or less. For example, any, such as 3 mass % or more and 85 mass % or less, 40 mass % or more and 85 mass % or less, and 50 mass % or more and 85 mass % or less, may be sufficient.

[crosslinking agent]

When using the above acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkylester as the adhesive resin (I-1a), the adhesive composition (I-4) is additionally a crosslinking agent It is preferable to contain

As a crosslinking agent in an adhesive composition (I-4), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The number of crosslinking agents contained in the adhesive composition (I-4) may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The content of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) is preferably 0.01 parts by mass or more and 50 parts by mass or less, and more preferably 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the content of the adhesive resin (I-1a). It is preferable, and it is especially preferable that they are 1 mass part or more and 50 mass parts or less.

[Other additives]

The adhesive composition (I-4) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect in this embodiment.

As said other additive, the thing similar to the other additive in adhesive composition (I-1) is mentioned.

One type may be sufficient as the other additive which adhesive composition (I-4) contains, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Content of other additives in an adhesive composition (I-4) is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in an adhesive composition (I-4), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

The number of solvents which the pressure-sensitive adhesive composition (I-4) contains may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

The content of the solvent in the pressure-sensitive adhesive composition (I-4) is not particularly limited, and may be appropriately adjusted.

<<The manufacturing method of an adhesive composition>>

The pressure-sensitive adhesive composition (I-1) to (I-3) or the pressure-sensitive adhesive composition (I-4) other than the pressure-sensitive adhesive composition (I-1) to (I-3), such as the pressure-sensitive adhesive composition (I-4), the above-mentioned pressure-sensitive adhesive and if necessary It is obtained by mix|blending each component for comprising adhesive compositions, such as a component other than it.

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

When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and this compounding component may be used by diluting in advance, and the solvent may be mixed with these compounding components without diluting any compounding component other than the solvent in advance. You may use it by

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

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

○ middle floor

The intermediate layer is in the form of a sheet or a film, and the constituent material thereof may be appropriately selected according to the purpose, and is not particularly limited.

Moreover, the haze of the composite sheet for protective film formation can be adjusted to the said range by adjusting the haze of an intermediate|middle layer suitably.

An intermediate layer may have sclerosis|hardenability and may have non-hardening property. Moreover, when an intermediate|middle layer has sclerosis|hardenability, any one of thermosetting and energy-beam sclerosis|hardenability may be sufficient.

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

The thickness of the intermediate layer may be, for example, 0.1 µm or more and 200 µm or less, 1 µm or more and 150 µm or less, and may be 3 µm or more and 120 µm or less.

Here, the "thickness of an intermediate|middle layer" means the thickness of the whole intermediate|middle layer, and means the thickness of the sum total of all the layers which comprise an intermediate|middle layer. On the other hand, as a measuring method of the thickness of an intermediate|middle layer, the method of measuring thickness using a contact thickness meter in arbitrary five places, and calculating the average of the measured values etc. are mentioned, for example.

<<Composition for Interlayer Formation>>

An intermediate|middle layer can be formed using the composition for intermediate|middle layer formation containing the constituent material.

For example, an intermediate|middle layer can be formed in the target site|part by coating the composition for intermediate|middle layer formation on the formation target surface of an intermediate|middle layer, drying as needed, or hardening by irradiation of an energy-beam.

Coating of the composition for intermediate|middle layer formation may just be performed by a well-known method, For example, it can perform by the method similar to the case of coating of the above-mentioned adhesive composition.

The drying conditions of the composition for intermediate|middle layer formation are not specifically limited. For example, it is preferable to heat-dry the composition for intermediate|middle layer formation containing a solvent, and in this case, it is preferable to dry under conditions for 10 second - 5 minutes at 70-130 degreeC, for example.

When the composition for intermediate|middle layer formation has energy-beam sclerosis|hardenability, it is preferable to harden by irradiation of an energy-beam after drying.

There is no limitation in particular as a composition for intermediate|middle layer formation, For example, the thing similar to what was illustrated in the above-mentioned adhesive composition, etc. are mentioned.

The composition for intermediate|middle layer formation may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect of invention.

As said other additive, the thing similar to the other additive in adhesive composition (I-1) is mentioned, for example.

For example, when the composition for intermediate|middle layer formation contains a filler or a coloring agent, the haze of the composite sheet for protective film formation can be adjusted to the said range.

◎ Film for forming protective film

The film for protective film formation may have sclerosis|hardenability and may have non-hardening property.

Moreover, when the film for protective film formation has sclerosis|hardenability, either thermosetting and energy-beam sclerosis|hardenability may be sufficient.

○ Film for thermosetting protective film formation

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

The film for thermosetting protective film formation may consist of one layer (single layer), and may consist of multiple layers of two or more layers. When the film for thermosetting protective film formation consists of multiple layers, these multiple layers may mutually be same or different. Here, "a plurality of layers may be the same or different from each other" means the same as in the case of the above description. In addition, when multiple layers differ from each other, the combination of these multiple layers is not specifically limited.

It is preferable that they are 1 micrometer or more and 100 micrometers or less, as for the thickness of the film for thermosetting protective film formation, it is more preferable that they are 5 micrometers or more and 75 micrometers or less, It is especially preferable that they are 5 micrometers or more and 50 micrometers or less. When the thickness of the film for thermosetting protective film formation is more than the said lower limit, a protective film with a higher protective ability can be formed. Moreover, becoming excessive thickness is suppressed because the thickness of the film for thermosetting protective film formation is below the said upper limit.

Here, the "thickness of the film for forming a thermosetting protective film" means the thickness of the entire film for forming a thermosetting protective film, for example, the thickness of the film for forming a thermosetting protective film comprising a plurality of layers, constituting the film for forming a thermosetting protective film Means the thickness of the sum of all layers. In addition, as a measuring method of the thickness of the film for thermosetting protective film formation, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.

The curing conditions when the film for forming a thermosetting protective film is affixed to the back surface of the semiconductor wafer and cured is not particularly limited as long as the degree of curing is such that the protective film sufficiently exhibits its function. Depending on the type of the film for forming a thermosetting protective film, Just choose appropriately.

For example, the heating temperature at the time of curing the film for forming a thermosetting protective film is preferably 100°C or more and 200°C or less, more preferably 110°C or more and 180°C or less, and particularly preferably 120°C or more and 170°C or less. And, the heating time during curing is preferably 0.5 hours or more and 5 hours or less, more preferably 0.5 hours or more and 3 hours or less, and particularly preferably 1 hour or more and 2 hours or less.

<<The composition for forming a thermosetting protective film>>

The film for thermosetting protective film formation can be formed using the composition for thermosetting protective film formation containing the constituent material. For example, the film for thermosetting protective film formation can be formed in the target site|part by coating the composition for thermosetting protective film formation on the formation target surface of the film for thermosetting protective film formation, and drying as needed. The ratio of content of components which do not vaporize at normal temperature in the composition for thermosetting protective film formation becomes the same as the ratio of content of the said components of the film for thermosetting protective film formation normally. Here, "room temperature" is as described above.

Coating of the composition for thermosetting protective film formation can be performed by the method similar to the case of coating of the above-mentioned adhesive composition, for example.

Although the drying conditions of the composition for forming a thermosetting protective film are not particularly limited, the composition for forming a thermosetting protective film is preferably heat-dried when it contains a solvent to be described later. In this case, for example, at 70°C or more and 130°C or less. It is preferable to dry under the conditions of 10 second or more and 5 minutes or less.

<Composition for thermosetting protective film formation (III-1)>

As the composition for forming a thermosetting protective film, for example, a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification, simply “composition (III-1)” may be abbreviated as ) and the like.

[Polymer component (A)]

A polymer component (A) is a polymer compound for providing film formability, flexibility, etc. to the film for thermosetting protective film formation.

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

As the polymer component (A), for example, an acrylic resin (resin having a (meth)acryloyl group), polyester, a urethane resin (resin having a urethane bond), an acrylic urethane resin, a silicone resin (resin having a siloxane bond) ), a rubber-based resin (resin having a rubber structure), a phenoxy resin, and a thermosetting polyimide, and an acrylic resin is preferable.

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

It is preferable that they are 10000 or more and 2000000 or less, and, as for the weight average molecular weight (Mw) of acrylic resin, it is more preferable that they are 100000 or more and 1500000 or less. When the weight average molecular weight of acrylic resin is more than the said lower limit, the shape stability (temporal stability at the time of storage) of the film for thermosetting protective film formation improves. In addition, when the weight average molecular weight of the acrylic resin is below the above upper limit, the film for forming a thermosetting protective film on the uneven surface of the adherend easily follows, and the occurrence of voids between the adherend and the film for forming a thermosetting protective film is more suppressed. .

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

It is preferable that they are -60 degreeC or more and 70 degrees C or less, and, as for the glass transition temperature (Tg) of acrylic resin, it is more preferable that they are -30 degreeC or more and 50 degrees C or less. When Tg of acrylic resin is more than the said lower limit, the adhesive force of a protective film and a support sheet (adhesive layer) is suppressed, and the peelability of a support sheet improves. Moreover, when Tg of acrylic resin is below the said upper limit, the adhesive force of a protective film with a to-be-adhered body improves.

In addition, in this specification, a glass transition temperature (Tg) is represented by the value measured with "differential scanning calorimetry (DSC) measuring device" based on JISK7121.

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

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

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

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

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

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

(meth)acrylic acid imide;

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

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

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

The acrylic resin is, for example, in addition to the (meth)acrylic acid ester, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide one or more monomers selected from the copolymer copolymer It may be done by

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

Acrylic resin may have a functional group which can be couple|bonded with other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The said functional group of an acrylic resin may couple|bond with another compound through the crosslinking agent (F) mentioned later, and may couple|bond directly with another compound without interposing a crosslinking agent (F). When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the composite sheet for forming a protective film tends to improve.

In the present specification, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter, it may simply be abbreviated as “thermoplastic resin”) may be used alone without using the acrylic resin, or may be used in combination with the acrylic resin. do. By using the above-mentioned thermoplastic resin, the peelability of the protective film from the supporting sheet is improved, or the film for forming a thermosetting protective film on the uneven surface of the adherend is easily followed, and the occurrence of voids between the adherend and the film for forming a thermosetting protective film is reduced. It may be more restrained.

It is preferable that they are 1000 or more and 100000 or less, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that they are 3000 or more and 80000 or less. Here, "weight average molecular weight" is as having demonstrated previously.

It is preferable that they are -30 or more and 150 degrees C or less, and, as for the glass transition temperature (Tg) of the said thermoplastic resin, it is more preferable that they are -20 or more and 120 degrees C or less.

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

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

The ratio of the content of the polymer component (A) to the total content of all components other than the solvent in the composition (III-1) (that is, the content of the polymer component (A) in the film for forming a thermosetting protective film) is the polymer component (A) Regardless of the kind of , it is preferable that they are 5 mass % or more and 85 mass % or less, and it is more preferable that they are 5 mass % or more and 80 mass % or less. For example, any of 5 mass % or more and 65 mass % or less, 5 mass % or more and 50 mass % or less, and 10 mass % or more and 35 mass % or less may be sufficient.

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

[thermosetting component (B)]

A thermosetting component (B) is a component for hardening the film for thermosetting protective film formation, and forming a hard protective film.

The number of thermosetting components (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

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

(epoxy thermosetting resin)

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

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

・Epoxy resin (B1)

A well-known thing is mentioned as an epoxy resin (B1), For example, polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, ortho cresol novolac epoxy resin, dicyclopentadiene. Bifunctional or more than bifunctional epoxy compounds, such as a type|mold epoxy resin, a biphenyl type epoxy resin, a bisphenol A type|mold epoxy resin, a bisphenol F type|mold epoxy resin, and a phenylene skeleton type|mold epoxy resin, are mentioned.

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

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

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

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

Although the number average molecular weight of the epoxy resin (B1) is not particularly limited, it is preferably 300 or more and 30000 or less, more preferably 300 or more and 10000 or less, from the viewpoint of curability of the film for forming a thermosetting protective film and the strength and heat resistance of the protective film after curing, It is especially preferable that they are 300 or more and 3000 or less.

In this specification, the "number average molecular weight" means the number average molecular weight represented by the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method, unless otherwise indicated.

It is preferable that they are 100 g/eq or more and 1000 g/eq or less, and, as for the epoxy equivalent of an epoxy resin (B1), it is more preferable that they are 150 g/eq or more and 950 g/eq or less.

In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing an epoxy group of 1 gram equivalent, and can be measured according to the method of JISK7236:2001.

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

· Thermosetting agent (B2)

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

As a thermosetting agent (B2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydrideized, and a phenolic hydroxyl group, an amino group or an acid group is preferably a group obtained by anhydride, and a phenolic hydroxyl group Or it is more preferable that it is an amino group.

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

Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter, sometimes abbreviated as “DICY”).

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

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

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

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

Among the thermosetting agents (B2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolak type phenol resin, a dicyclopentadiene type phenol resin, and an aralkyl type phenol resin is preferably 300 or more and 30000 or less. , more preferably 400 or more and 10000 or less, and particularly preferably 500 or more and 3000 or less.

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

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

Composition (III-1) and the film for forming a thermosetting protective film WHEREIN: It is preferable that content of thermosetting agent (B2) is 0.1 mass part or more and 500 mass parts or less with respect to content 100 mass parts of epoxy resin (B1), 1 mass part It is more preferable that it is more than 200 mass parts. For example, any, such as 1 mass part or more and 100 mass parts or less, 1 mass part or more and 50 mass parts or less, and 1 mass part or more and 10 mass parts or less, may be sufficient. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of the film for thermosetting protective film formation advances more easily. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption of the film for thermosetting protective film formation is reduced, and the reliability of the package obtained using the composite sheet for protective film formation improves more.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is the content of the polymer component (A) It is preferable that they are 20 mass parts or more and 500 mass parts or less with respect to 100 mass parts, It is more preferable that they are 30 mass parts or more and 300 mass parts or less, It is especially preferable that they are 40 mass parts or more and 150 mass parts or less. When the said content of a thermosetting component (B) is such a range, the adhesive force of a protective film and a support sheet is suppressed, and the peelability of a support sheet improves.

[curing accelerator (C)]

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

Preferable examples of the curing accelerator (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -imidazoles such as hydroxymethylimidazole (imidazole in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines (phosphines in which one or more hydrogen atoms are substituted with organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. are mentioned.

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

When using a hardening accelerator (C), composition (III-1) and the film for thermosetting protective film formation WHEREIN: Content of a hardening accelerator (C) is 0.01 mass part or more with respect to content of 100 mass parts of thermosetting component (B) 10 It is preferable that it is a mass part or less, and it is more preferable that they are 0.1 mass part or more and 7 mass parts or less. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) is acquired more remarkably. In addition, since the content of the curing accelerator (C) is below the upper limit, for example, the high polar curing accelerator (C) moves to the adhesive interface side with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions and segregates The effect which suppresses doing becomes high, and the reliability of the semiconductor chip with a protective film obtained using the composite sheet for protective film formation improves more.

[Filling material (D)]

The composition (III-1) and the film for thermosetting protective film formation may contain the filler (D). When the film for forming a thermosetting protective film contains the filler (D), the protective film obtained by curing the film for forming a thermosetting protective film is easy to adjust the thermal expansion coefficient, and by optimizing this coefficient of thermal expansion for the object to be formed of the protective film, the composite for forming a protective film The reliability of the semiconductor chip with the protective film obtained using the sheet|seat improves more. Moreover, when the film for thermosetting protective film formation contains a filler (D), the moisture absorption of a protective film can also be reduced or heat dissipation property can also be improved.

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

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

Among these, the inorganic filler is preferably silica or alumina.

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

When a filler (D) is used, the ratio of the content of the filler (D) to the total content of all components other than the solvent in the composition (III-1) (that is, the content of the filler (D) in the film for forming a thermosetting protective film) It is preferable that they are 5 mass % or more and 80 mass % or less, and, as for ), it is more preferable that they are 7 mass % or more and 60 mass % or less. When content of a filler (D) is such a range, adjustment of the said thermal expansion coefficient becomes easier.

[Coupling agent (E)]

The composition (III-1) and the film for thermosetting protective film formation may contain the coupling agent (E). By using what has a functional group which can react with an inorganic compound or an organic compound as a coupling agent (E), the adhesiveness and adhesiveness with respect to the to-be-adhered body of the film for thermosetting protective film formation can be improved. Moreover, water resistance improves the film|membrane obtained by hardening|curing the film for thermosetting protective film formation by using a coupling agent (E), without impairing heat resistance.

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

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltriethoxysilane. Cydyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-( 2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltri Ethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

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

When using a coupling agent (E), composition (III-1) and the film for thermosetting protective film formation WHEREIN: Content of a coupling agent (E) is 100 mass parts of total content of a polymer component (A) and a thermosetting component (B) It is preferable that they are 0.03 mass parts or more and 20 mass parts or less with respect to it, It is more preferable that they are 0.05 mass parts or more and 10 mass parts or less, It is especially preferable that they are 0.1 mass parts or more and 5 mass parts or less. When the said content of a coupling agent (E) is more than the said lower limit, the improvement of the dispersibility with respect to resin of a filler (D), improvement of adhesiveness with the to-be-adhered body of the film for thermosetting protective film formation, etc. By using the coupling agent (E) The effect is obtained more conspicuously. Moreover, generation|occurrence|production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]

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

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

As said organic polyhydric isocyanate compound, For example, an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (Hereinafter, these compounds are collectively abbreviated as "aromatic polyvalent isocyanate compound etc."); a trimer, an isocyanurate body, and an adduct body, such as the said aromatic polyhydric isocyanate compound; The terminal isocyanate urethane prepolymer etc. which are obtained by making the said aromatic polyhydric isocyanate compound etc. react with a polyol compound are mentioned. The "adduct body" is a reaction product of the aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound, or alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. means, and examples thereof include xylylene diisocyanate adducts of trimethylolpropane which will be described later. In addition, "terminal isocyanate urethane prepolymer" is as having demonstrated previously.

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

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

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

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

When using a crosslinking agent (F), it is preferable that content of a crosslinking agent (F) in composition (III-1) is 0.01 mass part or more and 20 mass parts or less with respect to content 100 mass parts of a polymer component (A), 0.1 mass It is more preferable that they are a part or more and 10 mass parts or less, and it is especially preferable that they are 0.5 mass part or more and 5 mass parts or less. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is acquired more remarkably. Moreover, excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.

[Energy-ray-curable resin (G)]

Composition (III-1) may contain energy-beam curable resin (G). Since the film for thermosetting protective film formation contains energy-beam curable resin (G), a characteristic can be changed by irradiation of an energy-beam.

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

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

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

It is preferable that they are 100 or more and 30000 or less, and, as for the weight average molecular weight of the said energy ray-curable compound, it is more preferable that they are 300 or more and 10000 or less. Here, "weight average molecular weight" is as having demonstrated previously.

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

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

In composition (III-1), it is preferable that content of energy-beam-curable resin (G) is 1 mass % or more and 95 mass % or less, It is more preferable that they are 5 mass % or more and 90 mass % or less, 10 mass % or more and 85 mass % or less It is especially preferable that it is the following.

[Photoinitiator (H)]

When composition (III-1) contains energy-beam curable resin (G), in order to advance the polymerization reaction of energy-beam curable resin (G) efficiently, you may contain the photoinitiator (H).

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

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

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

In the composition (III-1), the content of the photoinitiator (H) is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the energy ray-curable resin (G) content. It is more preferable, and it is especially preferable that they are 2 mass parts or more and 5 mass parts or less.

[Colorant (I)]

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

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

The organic pigments and organic dyes include, for example, aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squarylium pigments, azrenium pigments, polymethine pigments, and naphthoquinone pigments. , pyrylium pigment, phthalocyanine pigment, naphthalocyanine pigment, naphtholactam pigment, azo pigment, condensed azo pigment, indigo pigment, perinone pigment, perylene pigment, dioxazine pigment, quinacridone pigment, Isoindolinone pigment, quinophthalone pigment, pyrrole pigment, thioindigo pigment, metal complex pigment (metal complex dye), dithiol metal complex pigment, indole phenol pigment, triarylmethane pigment, anthra A quinone type pigment|dye, a naphthol type pigment|dye, an azomethine type pigment|dye, a benzimidazolone type pigment|dye, a pyranthrone type pigment|dye, a srene type pigment|dye, etc. are mentioned.

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

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

When using a coloring agent (I), what is necessary is just to adjust content of the coloring agent (I) of the film for thermosetting protective film formation suitably according to the objective. For example, by adjusting content of the coloring agent (I) of the film for thermosetting protective film formation and adjusting the light transmittance of a protective film, printing visibility at the time of laser printing with respect to a protective film can be adjusted. Moreover, by adjusting content of the coloring agent (I) of the film for thermosetting protective film formation, the designability of a protective film can be improved, or it can also make it difficult to show the grinding traces on the back surface of a semiconductor wafer. In consideration of this point, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, the content of the colorant (I) in the film for forming a thermosetting protective film) is 0.1 It is preferable that they are mass % or more and 10 mass % or less, It is more preferable that they are 0.1 mass % or more and 7.5 mass % or less, It is especially preferable that they are 0.1 mass % or more and 5 mass % or less. When the said content of a coloring agent (I) is more than the said lower limit, the effect by using a coloring agent (I) is acquired more remarkably. Moreover, when the said content of a coloring agent (I) is below the said upper limit, the excessive fall of the light transmittance of the film for thermosetting protective film formation is suppressed.

[Universal Additive (J)]

Composition (III-1) and the film for thermosetting protective film formation may contain the general-purpose additive (J) within the range which does not impair the effect in this embodiment.

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

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

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

[menstruum]

It is preferable that the composition (III-1) further contains a solvent. The composition (III-1) containing a solvent becomes favorable in handling property.

Although the said solvent is not specifically limited, As a preferable thing, For example, Hydrocarbons, such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

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

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

<<The manufacturing method of the composition for thermosetting protective film formation>>

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

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

When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and this compounding component may be used by diluting in advance, and the solvent may be mixed with these compounding components without diluting any compounding component other than the solvent in advance. You may use it by

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

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15°C or more and 30°C or less.

○ Film for forming energy ray-curable protective film

The film for energy ray-curable protective film formation contains an energy-beam curable component (a).

The film for energy ray-curable protective film formation WHEREIN: It is preferable that it is non-hardened, and, as for the energy ray-curable component (a), it is preferable to have adhesiveness, and it is more preferable that it is non-hardened and has adhesiveness. Here, "energy-beam" and "energy-beam sclerosis|hardenability" are as having demonstrated previously.

The film for forming an energy ray-curable protective film may be only one layer (single layer), or may be a plurality of layers of two or more layers. does not

It is preferable that they are 1 micrometer or more and 100 micrometers or less, as for the thickness of the film for energy ray-curable protective film formation, it is more preferable that they are 5 micrometers or more and 75 micrometers or less, It is especially preferable that they are 5 micrometers or more and 50 micrometers or less. When the thickness of the film for energy ray-curable protective film formation is more than the said lower limit, a protective film with a higher protective ability can be formed. Moreover, when the thickness of the film for energy ray-curable protective film formation is below the said upper limit, becoming excessive thickness is suppressed.

Here, the "thickness of the film for energy ray-curable protective film formation" means the thickness of the whole film for energy ray-curable protective film formation, For example, the thickness of the film for energy ray-curable protective film formation which consists of multiple layers is an energy ray It means the thickness of the sum total of all the layers which comprise the film for curable protective film formation. On the other hand, as a method for measuring the thickness of the film for forming an energy ray-curable protective film, for example, a method of measuring the thickness using a contact thickness gauge at five arbitrary places, and calculating the average of the measured values, etc. are mentioned. have.

The curing conditions at the time of forming the protective film by affixing and curing the film for forming an energy ray-curable protective film on the back surface of the semiconductor wafer are not particularly limited as long as the protective film has a degree of hardening to the extent that the protective film sufficiently exhibits its function. What is necessary is just to select suitably according to the kind of film for use.

For example, it is preferable that the illuminances of the energy-beam at the time of hardening of the film for energy-beam curable protective film formation are 120 mW/cm<2> or more and 280 mW/cm<2> or less. And it is preferable that the light quantity of the energy ray at the time of the said hardening is 200 mJ/cm<2> or more and 1000 mJ/cm<2> or less.

<<A composition for forming an energy ray-curable protective film>>

The film for energy ray-curable protective film formation can be formed using the composition for energy ray-curable protective film formation containing the constituent material. For example, by coating the composition for forming an energy ray-curable protective film on the surface to be formed of the film for forming an energy ray-curable protective film, and drying if necessary, a film for forming an energy ray-curable protective film can be formed on the target site. . The ratio of content of components which do not vaporize at normal temperature in the composition for energy-beam curable protective film formation becomes the same as the ratio of content of the said components of the film for energy-beam curable protective film formation normally. Here, "room temperature" is as described above.

Coating of the composition for energy ray-curable protective film formation can be performed by the method similar to the case of coating of the above-mentioned adhesive composition, for example.

The drying conditions of the composition for forming an energy ray-curable protective film are not particularly limited, but when the composition for forming an energy ray-curable protective film contains a solvent to be described later, it is preferably heat-dried, and in this case, for example, 70° C. or higher It is preferable to dry under the conditions of 10 seconds or more and 5 minutes or less at 130° C. or less.

<Composition for energy ray-curable protective film formation (IV-1)>

As the composition for forming an energy ray-curable protective film, for example, a composition (IV-1) for forming an energy ray-curable protective film containing the energy ray-curable component (a) (in this specification, simply “composition (IV-1)” ' may be abbreviated) and the like.

[Energy-ray-curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation with an energy ray, and while imparting film formability and flexibility to the film for forming an energy ray-curable protective film, it is also a component for forming a hard protective film after curing. .

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 or more and 2000000 or less, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 or more and 80000 or less. can The polymer (a1) may be one in which at least a part thereof is crosslinked with a crosslinking agent, or may not be crosslinked.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 or more and 2000000 or less)

Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 or more and 2000000 or less include an acrylic polymer (a11) having a functional group capable of reacting with a group of other compounds, and a group reactive with the functional group and energy ray curability The acrylic resin (a1-1) formed by the energy-beam curable compound (a12) which has energy-beam curable groups, such as a double bond, reacts is mentioned.

The functional group capable of reacting with the group of other compounds includes, for example, a hydroxyl group, a carboxy group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms), an epoxy group, and the like. . However, it is preferable that the said functional group is groups other than a carboxy group from the point of preventing corrosion of circuits, such as a semiconductor wafer and a semiconductor chip.

Among these, it is preferable that the said functional group is a hydroxyl group.

- Acrylic polymer having a functional group (a11)

Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer not having the functional group, and in addition to these monomers, monomers other than the acrylic monomer (ratio acrylic monomer) may be copolymerized.

In addition, the said acrylic polymer (a11) may be a random copolymer or a block copolymer may be sufficient as it, and a well-known method is employable also about the polymerization method.

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

As the hydroxyl group-containing monomer, for example, (meth) acrylate hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) ) hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic-type unsaturated alcohols (unsaturated alcohol which does not have a (meth)acryloyl skeleton), such as vinyl alcohol and allyl alcohol, etc. are mentioned.

Examples of the carboxyl group-containing monomer include 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 an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

As for the acryl-type monomer which has the said functional group, a hydroxyl-containing monomer is preferable.

The number of the acrylic monomers having the functional group constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

As the acrylic monomer having no functional group, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate ) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate ) acrylate isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl (( Lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl ((meth) acrylate), pentadecyl (meth) acrylate, hexadecyl acrylate (palmityl (meth) acrylate) , (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl (meth)acrylic acid alkyl ester, etc., in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms can be heard

In addition, as an acryl-type monomer which does not have the said functional group, For example, alkoxyalkyl groups, such as (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl, (meth)acrylate ethoxyethyl containing (meth)acrylic acid ester; (meth)acrylic acid esters having an aromatic group including (meth)acrylic acid aryl esters such as (meth)acrylic acid phenyl; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid ester etc. which have non-crosslinkable tertiary amino groups, such as (meth)acrylic-acid N,N- dimethylaminoethyl, (meth)acrylic-acid N,N- dimethylaminopropyl, etc. are mentioned.

The number of the acrylic monomers having no functional group constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; Styrene etc. are mentioned.

The number of the non-acrylic monomers constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural units derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is preferably 0.1% by mass or more and 50% by mass or less, 1 It is more preferable that they are mass % or more and 40 mass % or less, and it is especially preferable that they are 3 mass % or more and 30 mass % or less. When the ratio is within this range, the content of the energy ray curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12) is the degree of curing of the protective film. can be easily adjusted to a desired range.

The number of the acrylic polymers (a11) constituting the acrylic resin (a1-1) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

The ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent in the composition (IV-1) (that is, the content of the acrylic resin (a1-1) in the film for forming an energy ray-curable protective film) is It is preferable that they are 1 mass % or more and 70 mass % or less, It is more preferable that they are 5 mass % or more and 60 mass % or less, It is especially preferable that they are 10 mass % or more and 50 mass % or less.

・Energy-ray-curable compound (a12)

The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a11), and as the group It is more preferable to have an isocyanate group. 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.

It is preferable to have 1 or more and 5 or less of the said energy ray-curable group in 1 molecule, and, as for the said energy-beam curable compound (a12), it is more preferable to have 1 or more and 3 or less.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl)ethyl isocyanate;

Acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound, and hydroxyethyl (meth)acrylate;

The acryloyl monoisocyanate compound etc. which are obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate are mentioned.

Among these, it is preferable that the said energy-beam-curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

The number of the energy ray-curable compounds (a12) constituting the acrylic resin (a1-1) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 20 mol% or more 120 It is preferable that they are mol% or less, It is more preferable that they are 35 mol% or more and 100 mol% or less, It is especially preferable that they are 50 mol% or more and 100 mol% or less. When the ratio of the content is within such a range, the adhesive force of the protective film after curing becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is In the case of a functional compound (having two or more groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

It is preferable that they are 100000 or more and 2000000 or less, and, as for the weight average molecular weight (Mw) of the said polymer (a1), it is more preferable that they are 300000 or more and 1500000 or less.

Here, "weight average molecular weight" is as having demonstrated previously.

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

The number of the polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

(Molecular weight 100 or more and 80000 or less compound (a2) which has an energy ray-curable group)

Examples of the energy-ray-curable group that the compound (a2) having a molecular weight of 100 or more and 80000 or less has an energy-ray-curable group includes a group containing an energy-ray-curable double bond, and preferably a (meth)acryloyl group, a vinyl group, etc. can be heard

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

Examples of the low molecular weight compound having an energy ray-curable group among the compound (a2) include a polyfunctional monomer or an oligomer, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth). Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxy diethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy) ) Phenyl] propane, tricyclodecane dimethanol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentylglycol bifunctional (meth)acrylates such as di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane;

Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol Tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta polyfunctional (meth)acrylates such as erythritol poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

Polyfunctional (meth)acrylate oligomers, such as a urethane (meth)acrylate oligomer, etc. are mentioned.

As an epoxy resin which has an energy-beam curable group among the said compound (a2), and a phenol resin which has an energy-beam curable group, what is described in Paragraph 0043 of "Unexamined-Japanese-Patent No. 2013-194102" etc. can be used, for example. Although this resin also corresponds to resin which comprises the thermosetting component mentioned later, it handles as said compound (a2) in this embodiment.

It is preferable that weight average molecular weights are 100 or more and 30000 or less, and, as for the said compound (a2), it is more preferable that they are 300 or more and 10000 or less. Here, "weight average molecular weight" is as having demonstrated previously.

The number of the compound (a2) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

[Polymer (b) having no energy ray-curable group]

When the composition (IV-1) and the film for forming an energy ray-curable protective film contain the compound (a2) as the energy ray-curable component (a), the composition (IV-1) also contains a polymer (b) having no energy ray-curable group. desirable.

The polymer (b) may be crosslinked at least partially by a crosslinking agent, or may not be crosslinked.

As a polymer (b) which does not have an energy-ray-curable group, an acrylic polymer, a phenoxy resin, a urethane resin, polyester, a rubber-type resin, an acrylic urethane resin etc. are mentioned, for example.

Among these, it is preferable that the said polymer (b) is an acrylic polymer (Hereinafter, it may abbreviate as "acrylic polymer (b-1)").

The acrylic polymer (b-1) may be a known one, for example, may be a homopolymer of one type of acrylic monomer, may be a copolymer of two or more types of acrylic monomers, or may be one type or two or more types of acrylic monomer and one type. The type or copolymer of monomers (non-acrylic monomers) other than 2 or more types of acryl-type monomers may be sufficient.

As the acrylic monomer constituting the acrylic polymer (b-1), for example, (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid ester, hydroxyl group-containing ( and meth)acrylic acid esters and substituted amino group-containing (meth)acrylic acid esters. Here, the "substituted amino group" is as described above.

Examples of the (meth)acrylic acid alkyl ester include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, (meth)acrylate ) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate ) acrylate isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl (( Lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl ((meth) acrylate), pentadecyl (meth) acrylate, hexadecyl acrylate (palmityl (meth) acrylate) , (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl (meth)acrylic acid alkyl ester, etc., in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms can be heard

Examples of the (meth)acrylic acid ester having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as (meth)acrylic acid isobornyl and (meth)acrylic acid dicyclopentanyl;

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

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

(meth)acrylic acid cycloalkenyloxyalkyl esters, such as (meth)acrylic-acid dicyclopentenyloxyethyl ester, etc. are mentioned.

As said glycidyl group containing (meth)acrylic acid ester, (meth)acrylic acid glycidyl etc. are mentioned, for example.

As the hydroxyl group-containing (meth)acrylic acid ester, for example, (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxy propyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, etc. are mentioned.

As said substituted amino-group containing (meth)acrylic acid ester, (meth)acrylic-acid N-methylaminoethyl etc. are mentioned, for example.

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

Examples of the polymer (b) that do not have the energy ray-curable group at least partially crosslinked with the crosslinking agent include those in which the reactive functional group in the polymer (b) reacted with the crosslinking agent.

The reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and is not particularly limited. For example, when a crosslinking agent is a polyisocyanate compound, a hydroxyl group, a carboxy group, an amino group etc. are mentioned as said reactive functional group, Among these, a hydroxyl group with high reactivity with an isocyanate group is preferable. In addition, when the crosslinking agent is an epoxy compound, the reactive functional group includes a carboxy group, an amino group, an amide group, and the like, and among these, a carboxy group having high reactivity with an epoxy group is preferable. However, it is preferable that the said reactive functional group is a group other than a carboxy group from the point of preventing corrosion of the circuit of a semiconductor wafer or a semiconductor chip.

As a polymer (b) which does not have an energy-beam curable group which has the said reactive functional group, what was obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer may be used as a monomer constituting the acrylic polymer (b-1) having the reactive functional group. For example, the polymer (b) having a hydroxyl group as a reactive functional group includes, for example, one obtained by polymerization of a hydroxyl group-containing (meth)acrylic acid ester. and those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the above-mentioned reactive functional groups.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of structural units derived from a monomer having a reactive functional group to the total amount of structural units constituting the same is preferably 1% by mass or more and 20% by mass or less, , it is more preferable that they are 2 mass % or more and 10 mass % or less. When the ratio is in such a range, the degree of crosslinking in the polymer (b) becomes a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 or more and 2000000 or less, and more preferably 100000 or more and 1500000 or less, from the viewpoint of more favorable film-forming properties of the composition (IV-1). . Here, "weight average molecular weight" is as having demonstrated previously.

The composition (IV-1) and the polymer (b) having no energy ray-curable group contained in the film for forming an energy ray-curable protective film may be one, two or more, and in the case of two or more, the combinations and ratios thereof can be chosen arbitrarily.

Examples of the composition (IV-1) include those containing either or both of the polymer (a1) and the compound (a2). In addition, when the composition (IV-1) contains the compound (a2), it is preferable to further contain the polymer (b) having no energy ray-curable group. In this case, the composition (a1) is further contained. It is also preferable Moreover, the composition (IV-1) does not contain the said compound (a2), and may contain the said polymer (a1) and the polymer (b) which does not have an energy-ray-curable group together.

When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the content of the compound (a2) in the composition (IV-1) is It is preferable that they are 10 mass parts or more and 400 mass parts or less with respect to 100 mass parts of total content of the said polymer (a1) and the polymer (b) which does not have an energy-beam curable group, It is more preferable that they are 30 mass parts or more and 350 mass parts or less.

The ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent in the composition (IV-1) (that is, for energy ray-curable protective film formation) The total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group) of the film is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 80% by mass or less, It is especially preferable that they are 20 mass % or more and 70 mass % or less. When the said ratio of content of an energy-beam sclerosing|hardenable component is such a range, the energy-beam sclerosis|hardenability of the film for energy-beam curable protective film formation becomes more favorable.

The composition (IV-1) may contain one or two or more selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photoinitiator, a colorant, and a general-purpose additive, depending on the purpose in addition to the above energy ray-curable component. . For example, by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component, the film for forming an energy ray-curable protective film has improved adhesion to an adherend by heating, and this energy ray The strength of the protective film formed from the film for curable protective film formation also improves.

As the thermosetting component, filler, coupling agent, crosslinking agent, photoinitiator, colorant and general-purpose additive in the composition (IV-1), the thermosetting component (B) in the composition (III-1), the filler (D), The same thing as a coupling agent (E), a crosslinking agent (F), a photoinitiator (H), a coloring agent (I), and a general-purpose additive (J) is mentioned.

In the composition (IV-1), the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant, and the general-purpose additive may each be used alone, or in combination of two or more, or in combination of two or more. In this case, the combination and ratio thereof can be arbitrarily selected.

Content of the said thermosetting component, a filler, a coupling agent, a crosslinking agent, a photoinitiator, a coloring agent, and a general-purpose additive in composition (IV-1) may just adjust suitably according to the objective, and is not specifically limited.

It is preferable that the composition (IV-1) further contains a solvent from the viewpoint of improving the handleability by dilution.

Examples of the solvent contained in the composition (IV-1) include the same solvent as the solvent in the composition (III-1).

The number of solvents which the composition (IV-1) contains may be one, and 2 or more types may be sufficient as them.

<<The manufacturing method of the composition for energy-beam-curable protective film formation>>

The composition for forming an energy ray-curable protective film, such as composition (IV-1), is obtained by mix|blending each component for constituting this.

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

When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and this compounding component may be used by diluting in advance, and the solvent may be mixed with these compounding components without diluting any compounding component other than the solvent in advance. You may use it by

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

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15°C or more and 30°C.

○ Film for forming non-curable protective film

A non-hardening|hardenable component (c) is contained as a preferable film for non-hardening protective film formation, for example. In the film for forming a non-curable protective film, it is preferable that the non-curable component (c) has no curability and has an appropriate hardness in order to protect the adhesion to the support sheet and the semiconductor wafer or chip. Here, "non-hardening" is as described above.

One layer (single layer) may be sufficient as the film for non-curable protective film formation, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may be mutually the same or different, and the combination of these multiple layers is not specifically limited. .

It is preferable that they are 1 micrometer or more and 100 micrometers or less, as for the thickness of the film for non-hardening protective film formation, it is more preferable that they are 5 micrometers or more and 75 micrometers or less, It is especially preferable that they are 5 micrometers or more and 50 micrometers or less. When the thickness of the film for non-hardening protective film formation is more than the said lower limit, a protective film with a higher protective ability can be formed. Moreover, becoming excessive thickness is suppressed because the thickness of the film for non-hardening protective film formation is below the said upper limit.

Here, the "thickness of the film for non-curable protective film formation" means the thickness of the whole film for non-curable protective film formation, For example, the thickness of the non-curable protective film formation film which consists of multiple layers is for non-curable protective film formation It means the thickness of the sum of all the layers constituting the film. On the other hand, as a measuring method of the thickness of the film for non-curable protective film formation, the method of measuring thickness using a contact thickness meter in arbitrary 5 places, and calculating the average of the measured values etc. are mentioned, for example. .

<<Composition for Forming a Non-Curable Protective Film>>

The film for non-curable protective film formation can be formed using the composition for non-curable protective film formation containing the constituent material. For example, the film for non-curable protective film formation can be formed in the target site|part by coating the composition for non-curable protective film formation on the formation target surface of the film for non-curable protective film formation, and drying as needed. The ratio of content of components which do not vaporize at normal temperature in the composition for non-curable protective film formation becomes the same as the ratio of content of the said components of the film for non-curable protective film formation normally. Here, "room temperature" is as described above.

Coating of the composition for non-curable protective film formation can be performed by the method similar to the case of coating of the above-mentioned adhesive composition, for example.

Although the drying conditions of the composition for non-curable protective film formation are not specifically limited, When the composition for non-curable protective film formation contains the solvent mentioned later, it is preferable to heat-dry, In this case, for example, 70 degreeC or more and 130 degreeC. It is preferable to dry under the conditions of 10 second or more and 5 minutes or less below.

<Composition for non-curable protective film formation (V-1)>

As the composition for forming a non-curable protective film, for example, a composition (V-1) for forming a non-curable protective film containing a non-curable component (c) (in this specification, simply abbreviated as “composition (V-1)” in some cases) and the like.

The non-hardening component (c) is a thermoplastic resin, for example, an acrylic polymer etc. are mentioned, It is not limited to these. As said acrylic polymer, the thing similar to what was illustrated as said acrylic polymer (b-1) is mentioned.

Composition (V-1) may contain 1 type(s) or 2 or more types selected from the group which consists of a filler, a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose additive according to the objective other than the said non-curable component (c).

As the filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the composition (V-1), the filler (D), coupling agent (E), crosslinking agent (F), and colorant in composition (III-1), respectively (I) and the same as general-purpose additive (J) are mentioned.

In the composition (V-1), the filler, the coupling agent, the crosslinking agent, the colorant, and the general-purpose additive may each be used individually by 1 type, may use 2 or more types together, When using 2 or more types, these Combinations and ratios can be arbitrarily selected.

Content of the said filler, a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose additive in a composition (V-1) may just adjust suitably according to the objective, and is not specifically limited.

It is preferable that the composition (V-1) further contains a solvent from the point which the handleability improves by dilution.

Examples of the solvent contained in the composition (V-1) include the same solvent as the solvent in the composition (III-1).

The number of solvents which the composition (V-1) contains may be one, and 2 or more types may be sufficient as them.

<<The manufacturing method of the composition for non-curable protective film formation>>

The composition for forming a non-curable protective film, such as composition (V-1), is obtained by mix|blending each component for constituting this.

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

When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and this compounding component may be used by diluting in advance, and the solvent may be mixed with these compounding components without diluting any compounding component other than the solvent in advance. You may use it by

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

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15°C or more and 30°C.

In one aspect of the present invention, in the composite sheet for forming a protective film, a film for forming a protective film containing the components shown below, a pressure-sensitive adhesive layer containing the components shown below, and a substrate having the configuration shown below are laminated in this order. .

The film for forming a protective film is specifically,

An acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate as the polymer component ((A)-1) (weight average molecular weight: 350,000 to 400,000, preferably 370,000, glass transition temperature: 3 to 9° C., preferably 6° C.) 100 to 200 parts by mass, preferably 150 parts by mass;

50 to 70 parts by mass, preferably 60 parts by mass, of a bisphenol A epoxy resin (epoxy equivalent: 180 to 200 g/eq, preferably 184 to 194 g/eq) as the epoxy resin ((B1)-1);

5 to 15 parts by mass, preferably 10 parts by mass, of a bisphenol A epoxy resin (epoxy equivalent: 750 to 950 g/eq, preferably 800 to 900 g/eq) as the epoxy resin ((B1)-2);

20 to 40 parts by mass, preferably 30 parts by mass, of a dicyclopentadiene type epoxy resin (epoxy equivalent: 250 to 270 g/eq, preferably 255 to 260 g/eq) as the epoxy resin ((B1)-3); ;

1 to 3 parts by mass, preferably 2 parts by mass, of a thermoactive latent epoxy resin curing agent (dicyandiamide, active hydrogen amount: 20 to 25 g/eq, preferably 21 g/eq) as the thermosetting agent (B2);

1 to 3 parts by mass of 2-phenyl-4,5-dihydroxymethylimidazole as the curing accelerator (C), preferably 2 parts by mass;

300-340 parts by mass, preferably 320 parts by mass, of a silica filler (average particle diameter: 0.1 to 1 µm, preferably 0.5 µm) as the filler (D);

1 to 3 parts by mass of a silane coupling agent as the coupling agent (E), preferably 2 parts by mass;

As a coloring agent (I), 16-20 mass parts of black pigments are contained, Preferably 18 mass parts is contained.

The pressure-sensitive adhesive layer is specifically,

90 to 110 mass of a precopolymer having a weight average molecular weight of 800000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer parts, preferably 100 parts by mass;

35-60 mass parts of trifunctional xylylene diisocyanate type crosslinking agent, Preferably it contains 40-50 mass parts.

The substrate is specifically a polypropylene film having a thickness of 70 to 90 µm, preferably 80 µm. Further, the substrate has a matte surface (surface roughness (Ra): 0.20 to 1.30 µm, preferably 0.20 to 1.20 µm) and a glossy surface, or a non-matte surface (surface roughness (Ra): 0.05 to 0.15 µm, preferably 0.10). -0.15 μm).

On the other hand, the pressure-sensitive adhesive layer is laminated on the mat surface of the substrate.

Alternatively, the substrate has a matte surface roughness (Ra) (surface roughness (Ra): 0.30 µm or less, preferably 0.20 µm) and a glossy surface, or a matte surface (surface roughness (Ra): 0.05 to 0.15 µm, preferably preferably 0.10 to 0.15 μm), the pressure-sensitive adhesive layer is laminated on the glossy or matte surface of the substrate.

Moreover, one aspect of this invention WHEREIN: The composite sheet for protective film formation has the film for protective film formation containing the said component, the adhesive layer containing the component shown below, and the base material of the said structure.

The pressure-sensitive adhesive layer is specifically,

90 to 110 mass of a precopolymer having a weight average molecular weight of 800000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer parts, preferably 100 parts by mass;

15-25 mass parts of trifunctional xylylene diisocyanate type crosslinking agent, Preferably 20 mass parts;

It is 5-15 mass parts of silicone resin microparticles|fine-particles, Preferably it contains 10 mass parts.

Moreover, one aspect of this invention WHEREIN: The composite sheet for protective film formation has the film for protective film formation containing the said component, the adhesive layer containing the component shown below, and the base material of the said structure.

The pressure-sensitive adhesive layer is specifically,

90 to 110 mass of a precopolymer having a weight average molecular weight of 800000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer parts, preferably 100 parts by mass;

15-25 mass parts of trifunctional xylylene diisocyanate type crosslinking agent, Preferably 20 mass parts;

It is 3-30 mass parts of epoxy resins, Preferably 5-25 mass parts is contained.

Moreover, one aspect of this invention WHEREIN: The composite sheet for protective film formation has the film for protective film formation containing the said component, the adhesive layer containing the component shown below, and the base material of the said structure.

The pressure-sensitive adhesive layer is specifically,

90 to 110 mass of a precopolymer having a weight average molecular weight of 800000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer parts, preferably 100 parts by mass;

15-25 mass parts of trifunctional xylylene diisocyanate type crosslinking agent, Preferably 20 mass parts;

3-7 mass parts of a titanium oxide type white pigment, Preferably it contains 5 mass parts.

Moreover, one aspect of this invention WHEREIN: The composite sheet for protective film formation has the film for protective film formation containing the said component, the adhesive layer containing the component shown below, and the base material of the said structure.

The pressure-sensitive adhesive layer is specifically,

90 to 110 mass of a precopolymer having a weight average molecular weight of 800000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer parts, preferably 100 parts by mass;

15-25 mass parts of trifunctional xylylene diisocyanate type crosslinking agent, Preferably 20 mass parts;

5-15 mass parts of acrylic polymer microparticles|fine-particles, Preferably it contains 10 mass parts.

◇ Manufacturing method of composite sheet for forming protective film

The said composite sheet for forming a protective film can be manufactured by laminating|stacking each layer mentioned above one by one so that it may become a corresponding positional relationship. A method of forming each layer is the same as described above.

For example, in the case of manufacturing a composite sheet for forming a protective film, in the case of further laminating a film for forming a protective film on the pressure-sensitive adhesive layer laminated on the substrate, a composition for forming a thermosetting protective film and an energy ray-curable protective film are formed on the pressure-sensitive adhesive layer It is possible to directly form the film for protective film formation by coating the composition for use in the composition or the composition for forming a non-curable protective film. In this way, when a laminated structure of two consecutive layers is formed using several compositions, it is possible to form a new layer by further coating the composition on the layer formed from the composition. However, the layer to be laminated later among these two layers is previously formed using the composition on another release film, and the exposed surface of the formed layer opposite to the side in contact with the release film is exposed to the remaining layers already formed. It is preferable to form the laminated structure of two continuous layers by bonding together with a surface. At this time, it is preferable to apply the said composition to the peeling process surface of a peeling film. What is necessary is just to remove a peeling film after formation of a laminated structure as needed.

That is, in the case of manufacturing the composite sheet for forming a protective film, the pressure-sensitive adhesive composition is coated on the base material and dried if necessary, the pressure-sensitive adhesive layer is laminated on the base material, and separately the composition for forming a thermosetting protective film on the release film, energy rays By coating the composition for forming a curable protective film or the composition for forming a non-curable protective film and drying if necessary, a film for forming a protective film is formed on the release film, and the exposed surface of the film for forming a protective film is laminated on a substrate. The composite sheet for protective film formation is obtained by bonding together with the exposed surface of a layer and laminating|stacking the film for protective film formation on an adhesive layer.

On the other hand, in the case of laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive composition is coated on the release film and dried as necessary, thereby forming the pressure-sensitive adhesive on the release film. You may laminate|stack an adhesive layer on a base material by forming a layer and bonding the exposed surface of this adhesive layer with one surface of a base material.

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

In this way, all layers (adhesive layer, film for forming a protective film) other than the base material constituting the composite sheet for forming a protective film are formed in advance on the release film and laminated by a method of bonding to the surface of the target layer. Therefore, what is necessary is just to select suitably the layer which employ|adopts such a process as needed, and just to manufacture the composite sheet for protective film formation.

On the other hand, the composite sheet for protective film formation is normally stored in the state by which the peeling film was pasted on the surface of the outermost layer (for example, film for protective film formation) on the opposite side to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting protective film, a composition for forming an energy ray-curable protective film, or a composition for forming a non-curable protective film, on this release film (preferably the release-treated surface thereof) Coating and drying if necessary, a layer constituting the outermost layer is formed on the release film, and the remaining layers are placed on the exposed surface opposite to the side in contact with the release film of this layer by several methods described above. The composite sheet for protective film formation is obtained also by laminating|stacking with and setting it as the state bonded together without removing a peeling film.

In addition, in this specification, a "release film" is a film having a peeling function, and specifically, in order to protect the film for forming a protective film before sticking to a semiconductor wafer or a support sheet, it is affixed on both surfaces of the film for forming a protective film. It refers to a film that has been made, and it is used by peeling it during work.

Examples of the release film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, poly Butylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, Transparent films, such as a polyimide film and a fluororesin film, are used. Moreover, these crosslinked films are also used. Moreover, these laminated|multilayer films may be sufficient. Moreover, the film which colored these, an opaque film, etc. can be used. As a release agent, release agents, such as silicone type, a fluorine type, and a long-chain alkyl group containing carbamate, are mentioned, for example.

The thickness of a peeling film is 10 micrometers or more and 500 micrometers or less normally, Preferably they are 15 micrometers or more and 300 micrometers or less, Especially preferably, they are about 20 micrometers or more and 250 micrometers or less.

Here, the "thickness of a peeling film" means the thickness of the whole peeling film, for example, the thickness of the peeling film which consists of multiple layers means the thickness of the sum total of all the layers which comprise a peeling film. On the other hand, as a measuring method of the thickness of a peeling film, the method of measuring thickness using a contact-type thickness meter in 5 arbitrary places, and calculating the average of a measured value etc. are mentioned, for example.

◇ How to use the composite sheet for forming a protective film

The composite sheet for protective film formation of this embodiment can be used by the method shown below, for example.

That is, the composite sheet for protective film formation is affixed with the film for protective film formation on the back surface (surface opposite to an electrode formation surface) of a semiconductor wafer. Next, a heating or an energy ray is irradiated to the film for protective film formation as needed, the film for protective film formation is hardened, and it is set as a protective film. Or, in the case of the composition for non-hardening protective film formation contained in the film for protective film formation, you may use as a protective film with non-hardening. Next, the semiconductor wafer is divided into a protective film by dicing to obtain a semiconductor chip. Then, the semiconductor chip is separated from the support sheet and picked up while the protective film is affixed (that is, as a semiconductor chip on which the protective film is formed).

Thereafter, in the same manner as in the conventional method, the obtained semiconductor chip of the semiconductor chip provided with the protective film is flip-chip connected to the circuit surface of the substrate, and then, a semiconductor package is obtained. And what is necessary is just to produce the target semiconductor device using this semiconductor package.

On the other hand, when curing the film for protective film formation by irradiating a heating or an energy ray, the timing may be before dicing as mentioned above, and may be after dicing. Especially, it is preferable that the timing which irradiates a heating or an energy ray to harden the film for protective film formation is before dicing.

In addition, when curing the film for protective film formation by irradiating a heating or an energy ray, the timing of laser printing may be before hardening, and may be after hardening. Especially, when heating and hardening the film for protective film formation, it is preferable that the timing of laser printing is after hardening.

Example

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

The component used for manufacture of the composition for protective film formation is shown below.

・Polymer component

(A)-1: acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 370,000, glass transition temperature: 6°C)

· Thermosetting ingredients

(B1)-1: Bisphenol A type epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g/eq)

(B1)-2: Bisphenol A epoxy resin (JER1055 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800 to 900 g/eq)

(B1)-3: dicyclopentadiene type epoxy resin (Dainippon Ink Chemical Co., Ltd. Epiclone HP-7200HH, epoxy equivalent 255 to 260 g/eq)

(B2)-1: thermally active latent epoxy resin curing agent (dicyandiamide (Adeka Hardner EH-3636AS manufactured by ADEKA, active hydrogen amount 21 g/eq))

・Cure accelerator

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

・Fillers

(D)-1: Silica filler (SC2050MA manufactured by Admatex, average particle diameter of 0.5 µm)

・Coupling agent

(E)-1: Silane coupling agent (A-1110 manufactured by Unica Japan)

·coloring agent

(I)-1: black pigment (manufactured by Dainichi Seika Co., Ltd.)

[Example 1]

<Production of the composite sheet for forming a protective film>

(Preparation of composition (III-1) for forming a protective film)

By solid weight ratio, a polymer component ((A)-1 (150 mass parts)), a thermosetting component ((B1)-1 (60 mass parts), (B1)-2 (10 mass parts), (B1)-3 ( 30 parts by mass), (B2)-1 (2 parts by mass)), curing accelerator ((C)-1 (2 parts by mass)), filler ((D)-1 (320 parts by mass)), coupling agent (( E)-1 (2 parts by mass)) and the colorant ((I)-1 (18 parts by mass)) are dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate and stirred at 23° C. to form a thermosetting protective film A composition (III-1) was obtained.

(Preparation of adhesive composition ((I-4)-1))

It contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and further as a solvent, methyl ethyl ketone; The solid content concentration containing the mixed solvent of toluene and ethyl acetate prepared the non-energy-ray-curable adhesive composition ((I-4)-1) whose solid content concentration is 30 mass %. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass).

(Manufacture of support sheet)

By coating the pressure-sensitive adhesive composition ((I-4)-1) obtained above on the release treatment surface of a release film in which one side of a film made of polyethylene terephthalate is subjected to a release treatment by silicone treatment, and heat drying at 120° C. for 2 minutes , a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 15 µm was formed.

Next, on the exposed surface of this pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 µm (manufactured by Mitsubishi Resin Co., Ltd., matte surface (surface roughness (Ra): 1.20 µm)/glossy surface (surface roughness (Ra): 0.10 µm) substrate) A support sheet ((10)-1) was produced by bonding the mat surfaces of

(Manufacture of a composite sheet for forming a protective film)

The composition for forming a protective film (III-1) obtained above on the release-treated surface of a release film (“SP-PET381031” manufactured by Lintec, 38 µm thick) in which one side of the polyethylene terephthalate film has been peeled off by silicone treatment. The 25-micrometer-thick film ((13)-1) for thermosetting protective film formation was produced by coating with a knife coater and drying at 100 degreeC for 2 minutes.

Next, the exposed surface of the film for forming a protective film ((13)-1) obtained above is bonded to the pressure-sensitive adhesive layer of the supporting sheet ((10)-1) obtained above, and the base material, the pressure-sensitive adhesive layer and the film for forming a protective film (( 13)-1) produced the composite sheet for protective film formation which laminated|stacked in this order in these thickness direction. On the other hand, in the produced composite sheet for protective film formation, the width|variety of the support sheet was 270 mm, and the outer diameter of the film for protective film formation was 210 mm.

<Evaluation of the support sheet>

(Haze evaluation)

It measured based on JISK7136-2000 using "NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. On the other hand, it measured by the structure of the "base material + adhesive layer" which peeled the peeling film from the support sheet ((10)-1). A result is shown in Table 1.

(Evaluation of Transmission Sharpness)

It measured based on JISK7374-2007 using Suga Test Instruments Co., Ltd. product finish measuring machine "ICM-10P". The total value of five types of slits (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) was shown as transmission clarity. On the other hand, it measured by the structure of the "base material + adhesive layer" which peeled the peeling film from the support sheet ((10)-1). A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

(Evaluation of mounter aptitude (alignment (adjustment of tape tip position))

With respect to the composite sheet for forming a protective film and the ring frame, it was checked whether the tape tip position could be adjusted using a tape mounter RAD2700 manufactured by Lintec for an 8-inch semiconductor wafer (thickness: 200 µm). A result is shown in Table 1.

In addition, the evaluation criteria of mounter aptitude were set as follows.

A… Alignment possible

B… alignment not possible

(Evaluation of laser print visibility)

With respect to the film for forming a protective film affixed on an 8-inch semiconductor wafer, using a laser printing apparatus CSM300M manufactured by EO Technics, the protective film layer is printed over the support sheet, and when visually observed, whether or not characters can be visually recognized judged Printing was performed with respect to the uncured protective film layer. The character size was 0.3 mm x 0.2 mm. A result is shown in Table 1.

In addition, the evaluation criteria of laser printing visibility were set as follows.

A… able to admit

B… Slightly blurry but visible

C… poet impossible

(evaluation of character thickness for printing)

The film for forming a protective film affixed on an 8-inch semiconductor wafer was irradiated with ultraviolet rays from the supporting sheet side using an ultraviolet irradiation device (manufactured by Lintec, RAD2000m/8, irradiation conditions: illuminance: 195 mW/cm 2 , light quantity 170 mJ/cm 2 ). did. Next, after peeling a support sheet from a protective film, the printing on a protective film was observed with the optical microscope manufactured by Keyence, and the thickness of a character was measured. A result is shown in Table 1.

[Example 2]

<Production of the composite sheet for forming a protective film>

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-2))

Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (50 parts by mass (solid content)), and further, methyl ethyl ketone as a solvent The non-energy-ray-curable adhesive composition ((I-4)-2) whose solid content concentration to contain is 30 mass % was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-2) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-4)-2) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-2) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 3]

<Production of the composite sheet for forming a protective film>

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-1))

A pressure-sensitive adhesive composition ((I-4)-1) was obtained in the same manner as in Example 1.

(Manufacture of support sheet)

On the exposed surface of the pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 µm (manufactured by Mitsubishi Resin Co., Ltd., matte surface (surface roughness (Ra): 1.20 µm)/glossy surface (surface roughness (Ra): 0.10 µm) base) Instead, the mat side of a 80 μm thick polypropylene film (manufactured by Gunze Co., Ltd., matte surface (surface roughness (Ra): 0.20 μm)/unmatte surface (surface roughness (Ra): 0.15 μm) base material) was bonded. Except that, the support sheet (10)-3 was manufactured using the same method as in Example 1.

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-3) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 4]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-3))

Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and silicone resin microparticles ("Tospearl 145" manufactured by Tanak Corporation) ') (10 parts by mass (solid content)), and a solid content concentration of 30 mass % containing methyl ethyl ketone as a solvent prepared a specific energy ray-curable pressure-sensitive adhesive composition ((I-4)-3). The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-4) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-4)-3) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-4) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 5]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-1)-1))

Acrylic polymer (100 parts by mass, solid content), a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)) and an epoxy resin (“JER834” manufactured by Mitsubishi Chemical Corporation) ( 25 mass parts (solid content)), and solid content concentration further containing methyl ethyl ketone as a solvent prepared the energy-beam curable adhesive composition ((I-1)-1) whose solid content concentration is 30 mass %. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-5) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-1)-1) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-5) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 6]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-1)-2))

Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)) and epoxy resin (“JER1055” manufactured by Mitsubishi Chemical Corporation) ( 5 mass parts (solid content)), and solid content concentration containing methyl ethyl ketone as a solvent prepared the energy-beam curable adhesive composition ((I-1)-2) whose solid content concentration is 30 mass %. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-6) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-1)-2) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-6) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 7]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-4))

Acrylic polymer (100 parts by mass, solid content), a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and a titanium oxide white pigment (manufactured by Dainichi Seika Co., Ltd.) "N-DYM8054") (5 parts by mass (solid content)), and a solid content concentration of 30 mass % containing methyl ethyl ketone as a solvent ((I-4)-4) was prepared The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-7) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-4)-4) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-7) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 8]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-5))

Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and acrylic polymer fine particles (“215 manufactured by Dainichi Seika Corporation”) (MD) White") (10 parts by mass (solid content)), and further containing methyl ethyl ketone as a solvent, a non-energy ray-curable pressure-sensitive adhesive composition ((I-4)-5) having a solid content concentration of 30 mass% was prepared The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-8) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-4)-5) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-8) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 9]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-2))

Using the method similar to Example 2, solid content concentration prepared the non-energy-ray-curable adhesive composition ((I-4)-2) whose solid content concentration is 30 mass %.

(Manufacture of support sheet)

Using the pressure-sensitive adhesive composition ((I-4)-2) instead of the pressure-sensitive adhesive composition ((I-4)-1), on the exposed surface of the pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 µm (manufactured by Mitsubishi Resin Co., Ltd., matte surface ( Instead of the mat surface of the surface roughness (Ra): 1.20 µm)/glossy surface (surface roughness (Ra: 0.10 µm) base), a polypropylene film (manufactured by Gunze Corporation, matte surface (surface roughness (Ra)) having a thickness of 80 µm ): 0.20 µm)/non-matte surface (surface roughness (Ra): 0.15 µm) A support sheet ((10)-9) was obtained in the same manner as in Example 1, except that the mat surface was bonded together. .

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-9) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Example 10]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-2))

Using the method similar to Example 2, solid content concentration prepared the non-energy-ray-curable adhesive composition ((I-4)-2) whose solid content concentration is 30 mass %.

(Manufacture of support sheet)

The pressure-sensitive adhesive composition ((I-4)-2) was used instead of the pressure-sensitive adhesive composition ((I-4)-1), and a polypropylene film having a thickness of 80 μm on the exposed surface of the pressure-sensitive adhesive layer (manufactured by Mitsubishi Resin Co., Ltd., matte surface) Instead of the mat surface of (surface roughness (Ra): 1.20 µm)/glossy surface (surface roughness (Ra): 0.10 µm) substrate), a polypropylene film having a thickness of 80 µm (manufactured by Gunze Corporation, matte surface (surface roughness ( A support sheet ((10)-10) was used in the same manner as in Example 1, except that Ra): 0.20 µm)/un-matte surface (surface roughness (Ra: 0.15 µm) substrate) was pasted together. got

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-10) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Comparative Example 1]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-1))

A pressure-sensitive adhesive composition ((I-4)-1) was obtained in the same manner as in Example 1.

(Manufacture of support sheet)

A support sheet (10)-9 was produced in the same manner as in Example 1 except that a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 µm was formed instead of a thickness of 15 µm.

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-9) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Comparative Example 2]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-6))

It contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (30 parts by mass (solid content)), and further, methyl ethyl ketone as a solvent The non-energy-ray-curable adhesive composition ((I-4)-6) whose solid content concentration to contain is 30 mass % was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

A support sheet ((10)-10) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-4)-6) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-10) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Comparative Example 3]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-7))

Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (5 parts by mass (solid content)), and further, methyl ethyl ketone as a solvent The non-energy-ray-curable adhesive composition ((I-4)-7) whose solid content concentration to contain is 30 mass % was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

By coating the pressure-sensitive adhesive composition ((I-4)-7) obtained above on the release-treated surface of a release film in which one side of a film made of polyethylene terephthalate is subjected to a release treatment by silicone treatment, and heat-drying at 120°C for 2 minutes , a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 µm was formed.

Next, on the exposed surface of this pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 µm (manufactured by Mitsubishi Resin Co., Ltd., matte surface (surface roughness (Ra): 0.50 µm)/glossy surface (surface roughness (Ra): 0.10 µm) substrate) A support sheet ((10)-11) was manufactured by bonding the glossy surfaces of

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-11) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Comparative Example 4]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-7))

A non-energy-ray-curable pressure-sensitive adhesive composition ((I-4)-7) was prepared using the same method as in Comparative Example 3.

(Manufacture of support sheet)

A support sheet ((10)-12) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition ((I-4)-7) was used instead of the pressure-sensitive adhesive composition ((I-4)-1).

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-12) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

[Comparative Example 5]

(Preparation of composition (III-1) for forming a protective film)

A composition (III-1) for forming a thermosetting protective film was obtained in the same manner as in Example 1.

(Preparation of adhesive composition ((I-4)-7))

A non-energy-ray-curable pressure-sensitive adhesive composition ((I-4)-7) was prepared using the same method as in Comparative Example 3.

(Manufacture of support sheet)

By coating the pressure-sensitive adhesive composition ((I-4)-7) obtained above on the release-treated surface of a release film in which one side of a film made of polyethylene terephthalate is subjected to a release treatment by silicone treatment, and heat-drying at 120°C for 2 minutes , a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 µm was formed.

Next, on the exposed surface of this pressure-sensitive adhesive layer, a polypropylene film having a thickness of 60 µm (manufactured by Riken Technos, matte surface (surface roughness (Ra): 0.50 µm)/glossy surface (surface roughness (Ra): 0.10 µm) substrate) A support sheet ((10)-13) was manufactured by bonding the glossy surfaces of

(Manufacture of a composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that ((10)-13) was used instead of the supporting sheet ((10)-1).

<Evaluation of the support sheet>

Haze and transmission clarity were evaluated using the same method as in Example 1. A result is shown in Table 1.

<Evaluation of the composite sheet for forming a protective film>

Mounter aptitude, laser printing visibility, and printing character thickness were evaluated using the same method as in Example 1. A result is shown in Table 1.

In Table 1, about pass judgment, mounter aptitude was A evaluation, and the thing of laser printing visibility A or B evaluation was made into "pass", and other than that was made into "failure".

From Table 1, when the haze of a support sheet is 46 % or more, mounter aptitude becomes A evaluation. It was speculated that this was because the haze of the support sheet was 46% or more and had a certain degree of turbidity (biliary duct), so that the position of the tip of the support sheet could be detected by laser irradiation in the optical sensor for adjusting the position of the tip of the tape. .

In addition, from Table 1, when the haze of a support sheet is 46 % or more, and when the transmission clarity is 100 or more, laser printing visibility becomes B evaluation or more, when it is 200 or more, laser printing visibility becomes A evaluation. It was estimated that this was because the visibility of laser printing improved because the light scattering in the outer surface of the base material located in the bottom face of a support sheet was suppressed. In addition, when the haze of the support sheet is 46% or more and has a certain degree of turbidity (phlegm), it is possible to appropriately scatter laser light in the inside of the support sheet to increase the thickness of printed text, contributing to the improvement of the visibility of laser printing It was assumed that it was because

From the above, it became clear that the composite sheet for protective film formation which was excellent in the laser printing property with respect to a protective film and also excellent in the visibility of printing of a protective film by making the haze and transmission clarity of a support sheet into an appropriate range is obtained.

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

1A, 1B, 1C, 1D, 1E… A composite sheet for forming a protective film, 10 ... support sheet, 10a... The surface of the support sheet, 11... Subscription, 11a... The surface of the substrate, 12 ... pressure-sensitive adhesive layer, 12a... The surface of the adhesive layer, 13... Film for forming a protective film, 13a... The surface of the film for protective film formation, 15... release film, 16... Adhesive layer for a jig, 16a... The surface of the adhesive layer for a jig, 17... middle layer, 17a... the surface of the intermediate layer

Claims (9)

A substrate is provided, and a pressure-sensitive adhesive layer and a film for forming a protective film are laminated in this order on the substrate,
The haze of the support sheet, which is a laminate of the base material and the pressure-sensitive adhesive layer, is more than 45% and 90% or less,
A composite sheet for forming a protective film in which the transparency of the support sheet is 100 or more. The method of claim 1,
The composite sheet for protective film formation provided with the adhesive bond layer for jig|tools in the area|region where the said protective film formation film is not laminated|stacked among the surface of the said adhesive layer on the side provided with the said protective film formation film. 3. The method according to claim 1 or 2,
The composite sheet for forming a protective film, wherein the film for forming a protective film is energy ray-curable. 3. The method according to claim 1 or 2,
The composite sheet for forming a protective film, wherein the film for forming a protective film is thermosetting. 3. The method according to claim 1 or 2,
The composite sheet for forming a protective film, wherein the film for forming a protective film is non-curable. 3. The method according to claim 1 or 2,
A composite sheet for forming a protective film wherein the pressure-sensitive adhesive layer is energy ray-curable or non-energy-curable. 3. The method according to claim 1 or 2,
A composite sheet for forming a protective film, wherein the pressure-sensitive adhesive layer has a thickness of 3 to 20 μm. 3. The method according to claim 1 or 2,
A composite sheet for forming a protective film, wherein the surface roughness (Ra) of one surface of the substrate is 0.11 µm or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness. 3. The method according to claim 1 or 2,
A composite sheet for forming a protective film, wherein a surface of the substrate exposed as an outer surface of the support sheet has a surface roughness (Ra) of 0.15 µm or less.

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