KR102388900B1 - Composite sheet for forming support sheet and protective film - Google Patents

Abstract

This support sheet has a base material, the pressure-sensitive adhesive layer is provided on the base material, the pressure-sensitive adhesive layer side surface of the base material is an uneven surface, and a test piece is cut out from five points of the support sheet, and the cross section of the pressure-sensitive adhesive layer in these five test pieces , the average value (R value) of the ratio of (the sum of the linear distances between adjacent significant vertices)/(the linear distance in the horizontal direction to the pressure-sensitive adhesive layer) is 1.5 or more and less than 5.0. The composite sheet for protective film formation is equipped with the film for protective film formation on the adhesive layer in this support sheet.

Description

Composite sheet for forming support sheet and protective film

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

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 on the opposite side to the circuit surface of a semiconductor chip may be exposed.

On the exposed back surface of the semiconductor chip, a resin film containing an organic material is formed as a protective film, and is introduced into a semiconductor device as a semiconductor chip with a protective film in some cases. The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.

Such a protective film is formed by hardening the film for protective film formation which has sclerosis|hardenability, for example. In addition, a film for forming a non-curable protective film with controlled physical properties may be used as a protective film as it is. And the film for protective film formation is affixed on the back surface of a semiconductor wafer, and is used. The film for forming a protective film may be affixed to the back surface of a semiconductor wafer in the state of the composite sheet for protective film formation integrated with the support sheet used at the time of processing of a semiconductor wafer, for example, or a semiconductor wafer in the state which is not integrated with a support sheet. It is also affixed to the back of the

After the composite sheet for forming a protective film is affixed on the back surface of the semiconductor chip by the film for forming a protective film therein, the formation of a protective film by curing the film for forming a protective film at appropriate timings, cutting of the film or protective film for forming a protective film, semiconductor Division (dicing) of the wafer to the semiconductor chip, the film for forming a protective film after cutting, or pickup from the supporting sheet of a semiconductor chip having a protective film on the back surface (a semiconductor chip with a film for forming a protective film or a semiconductor chip with a protective film), etc. This is done appropriately. And when the semiconductor chip with the protective film formation film is picked up, this becomes a semiconductor chip with a protective film formed by hardening of the protective film formation film, and a semiconductor device is manufactured using the semiconductor chip with a protective film finally formed. Thus, the support sheet in the composite sheet for protective film formation can be utilized as a dicing sheet. On the other hand, when the film for protective film formation is non-hardening, in these each process, the film for protective film formation is handled as a protective film as it is.

On the other hand, after the film for forming a protective film is affixed to the back surface of the semiconductor wafer in a state not integrated with the support sheet, the support sheet is affixed to the exposed surface on the opposite side to the affixing surface of the semiconductor wafer of this film for forming a protective film. . Thereafter, in the same manner as in the case of using the composite sheet for forming a protective film, a semiconductor chip with a protective film or a semiconductor chip with a film for forming a protective film is obtained, and a semiconductor device is manufactured. In this case, although the film for protective film formation is affixed on the back surface of a semiconductor wafer in the state which is not integrated with a support sheet, the composite sheet for protective film formation is comprised by integration with a support sheet after sticking.

As such a composite sheet for forming a protective film, for example, a dicing tape (support sheet) having a substrate having an uneven surface and an adhesive layer laminated on the uneven processing surface side of the substrate, and on the adhesive layer of the dicing tape. A dicing tape-integrated semiconductor back surface protective film (composite sheet for protective film formation) having a semiconductor back surface protective film (protective film formation film) laminated on the dicing tape, wherein the dicing tape has a haze of 45% or less. A film is disclosed (refer to patent document 1).

However, in the composite sheet for forming a protective film disclosed in Patent Document 1 (dicing tape-integrated semiconductor back surface protective film), since the pressure-sensitive adhesive layer is laminated on the uneven surface side of the substrate, the pressure-sensitive adhesive does not sufficiently follow the unevenness of the substrate. It does not, and the area|region (non-bonding area|region) by which these are not bonded may arise between a base material and an adhesive. In addition, although printing may be performed by laser irradiation on the surface of the adhesive layer side of a protective film or a protective film formation film, depending on the shape of the unevenness|corrugation of an adhesive layer, the visibility of printing through a base material and an adhesive layer decreases. there is

Japanese Patent No. 5432853 Publication

The present invention is a support sheet constituted by providing a pressure-sensitive adhesive layer on the concave-convex surface side of a substrate, and in a composite sheet for forming a protective film having a film for forming a protective film on the pressure-sensitive adhesive layer, good adhesion between the substrate and the pressure-sensitive adhesive, and formation of a protective film or protective film It aims at providing the support sheet which can implement|achieve favorable printing visibility through the support sheet of the film for use, and the composite sheet for protective film formation provided with the said support sheet.

The present invention is a support sheet having a substrate and having a pressure-sensitive adhesive layer on the substrate, wherein the pressure-sensitive adhesive layer side surface of the substrate is an uneven surface, and a test piece is cut out from five places of the support sheet, and these five test pieces are When the cross section of the pressure-sensitive adhesive layer is observed, the average value of the ratio of (the sum of the linear distances between adjacent significant vertices)/(the linear distance in the horizontal direction to the pressure-sensitive adhesive layer) is 1.5 or more and less than 5.0.

In the support sheet of this invention, the said adhesive layer may be in direct contact with the uneven|corrugated surface of the said base material.

Moreover, this invention provides the composite sheet for protective film formation provided with the film for protective film formation on the adhesive layer in the said support sheet.

By forming the composite sheet for protective film formation using the support sheet of this invention, favorable adhesiveness of a base material and an adhesive, and favorable printing visibility through the support sheet of a protective film or film for protective film formation can be implement|achieved.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the composite sheet for forming a support sheet and a protective film which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention with a support sheet.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention with a support sheet.
Fig. 4 is an enlarged cross-sectional view of the support sheet and the composite sheet for forming a protective film shown in Fig. 1 .
It is an enlarged cross-sectional view of the composite sheet for protective film formation and the support sheet shown in FIG.

◇Composite sheet for forming support sheet and protective film

A support sheet according to an embodiment of the present invention is a support sheet having a base material and having a pressure-sensitive adhesive layer on the base material, wherein the pressure-sensitive adhesive layer side surface of the base material is an uneven surface, and a test piece is removed from five locations of the support sheet. Cut out, in these 5 test pieces, when the cross section of the adhesive layer is observed, the average value of the ratio (the sum of the linear distances between adjacent significant vertices) / (the linear distance in the horizontal direction to the adhesive layer) (this specification) In some cases, "R value") is 1.5 or more and less than 5.0.

On the other hand, in the present specification, when the cross-section of the pressure-sensitive adhesive layer is observed, the top of the convex portion where the substrate-side surface of the pressure-sensitive adhesive layer is switched from descending to rising, and the concave portion in which the substrate-side surface of the pressure-sensitive adhesive layer is switched from rising to descending If the step between the deepest portions is 1 μm or more, the step is considered significant, the apex having this significant step is specified as a significant apex of the convex portion, and the deepest portion having this significant step is specified as a significant apex of the concave portion, , of the significant vertices of the convex portion and the significant vertices of the concave portion, the distance between adjacent significant vertices is defined as the “linear distance between adjacent significant vertices”, and the sum of the linear distances between the adjacent significant vertices of the object to be observed is defined as "the sum of the linear distances between significant adjacent vertices". In addition, the distance from the starting point of the point which projected the meaningful vertex of an observation object on the plane of a horizontal direction to an adhesive layer is defined as "a linear distance in a horizontal direction to an adhesive layer".

When the cross section of the pressure-sensitive adhesive layer is observed, the average value (R value) of the ratio of (the sum of the linear distances between adjacent significant vertices)/(the linear distance in the horizontal direction to the pressure-sensitive adhesive layer) is 1.5 or more, Adhesion becomes good. When the R value is less than 5.0, scattering of transmitted light at the pressure-sensitive adhesive-base interface is suppressed, and good print visibility through the support sheet of the protective film or the film for forming a protective film can be realized.

A support sheet according to an embodiment of the present invention is a support sheet having a base material and having a pressure-sensitive adhesive layer on the base material, wherein the pressure-sensitive adhesive layer side surface of the base material is an uneven surface, and a test piece is removed from five locations of the support sheet. cut out, and when the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer are obtained in each of these five test pieces, the average value of the minimum values (in this specification, may be referred to as “S value”) is 1.5 μm or more, It is preferable that the average value of the said maximum value (in this specification, it may be called "L value") becomes 9 micrometers or less.

Moreover, the composite sheet for protective film formation which concerns on one Embodiment of this invention is equipped with the film for protective film formation on the adhesive layer in the said support sheet.

Moreover, when the S value of the said adhesive layer is 1.5 micrometers or more, the lamination|stacking property of an adhesive layer and the film for protective film formation becomes favorable easily. In this specification, "stackability" means the normality of the laminated state of the target two-layer unless otherwise stated. "Good lamination property" means, for example, that there is no non-bonding region (void portion) between two adjacent layers to be subjected to, or the number of non-bonding regions is small and the interlayer distance of the non-bonding region is small. it means.

On the other hand, when L value of the said adhesive layer is 9 micrometers or less, printing visibility through the support sheet of a protective film or the film for protective film formation becomes favorable easily.

The said test piece cuts out from 5 places of a support sheet, and is obtained by cutting|disconnecting a support sheet in the whole area of the thickness direction. The test piece is a small piece with the entire layer constituting the support sheet.

Although the size of the test piece is not particularly limited, the length of one side of the lamination surface or the exposed surface of each layer (base material, pressure-sensitive adhesive layer, etc.) constituting the test piece is preferably 2 mm or more. By using the test piece of such a size, the R value, S value, and L value of an adhesive layer are calculated|required more precisely.

The maximum value of the length of one side is not particularly limited. For example, it is preferable that the length of the said one side is 10 mm or less from the point which preparation of a test piece is easier.

The planar shape of the test piece, that is, the shape of the lamination surface or the exposed surface of each layer (base material, pressure-sensitive adhesive layer, etc.) constituting the test piece, is preferably a polygonal shape, and a rectangular shape in terms of easier cutting of the test piece more preferably.

As a preferable thing as a test piece, the lamination|stacking surface or exposed surface of each layer (base material, adhesive layer, etc.) constituting the test piece is a rectangular shape with a size of 3 mm x 3 mm, for example. However, this is an example of a preferable test piece.

In the support sheet, the cut position of the five points of the test piece is not particularly limited, but in consideration of the planned lamination position of the film for forming a protective film, which will be described later, so that the R value, S value, and L value of the pressure-sensitive adhesive layer can be obtained more precisely. You can choose.

For example, among the predetermined positions for lamination of one film for forming a protective film in the support sheet, the center (center of gravity) portion of the film for forming a protective film is scheduled to be arranged, and a portion near the periphery of the film for forming a protective film, and About this center (center of gravity) part, the position of the point target is roughly 4 places 5 places where the position is planned to be arrange|positioned is mentioned.

It is preferable that the distance between the centers (centers of gravity) of the cut position of the test piece in a support sheet is 50-200 mm. By doing in this way, the R value, S value, and L value of an adhesive layer can be calculated|required more precisely.

In order to obtain the R value of the pressure-sensitive adhesive layer from the test piece, a new cross section is formed in the test piece, and in the formed cross section, the sum of the linear distances between significant vertices adjacent to each test piece and the horizontal straight line distance to the pressure-sensitive adhesive layer measure

The cross section to be newly formed may be only one side per specimen, or may be two or more, but usually only one side is sufficient.

And what is necessary is just to calculate the R value from the sum of the linear distances of these at least five adjacent significant vertices, and the linear distance in a horizontal direction to an adhesive layer.

In order to obtain the S value and L value of the pressure-sensitive adhesive layer from the test piece, a new cross section is formed in the test piece, and in the formed cross section, the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer are measured for each test piece.

The cross section to be newly formed may be only one side per specimen, or may be two or more, but usually only one side is sufficient.

And what is necessary is just to calculate the S value and the L value from these at least five minimum and maximum values.

In the test piece, the cross section can be formed by a well-known method. For example, by using a known cross-section sample preparation apparatus (cross-section polisher), a cross-section can be formed in a test piece with high reproducibility by suppressing variation.

The sum of the linear distances of adjacent significant vertices of the adhesive layer and the linear distance in the horizontal direction to the adhesive layer can be measured by, for example, image processing the cross section of the test piece using a scanning electron microscope (SEM).

The minimum value and maximum value of the thickness of an adhesive layer can be measured by observing the said cross section of a test piece using a scanning electron microscope (SEM), for example.

The area in which the sum of the linear distances between adjacent significant vertices in the cross section of each test piece and the linear distance in the horizontal direction to the pressure-sensitive adhesive layer are measured is, with respect to the lamination direction of each layer (substrate, pressure-sensitive adhesive layer, etc.) constituting the test piece. It is preferable that it is 50-1500 micrometers in the direction orthogonal (a direction substantially parallel to the lamination|stacking surface or exposed surface of each layer). Moreover, when cutting out a test piece from a long support sheet and the composite sheet for protective film formation, it is preferable to cut out the said cross section in the width direction of a long support sheet and the composite sheet for protective film formation. By doing in this way, the sum total of the linear distances between significant vertices adjacent to each other with high efficiency and high precision, and the linear distance in a horizontal direction to an adhesive layer can be measured. The measurement of the minimum value and maximum value of the thickness of an adhesive layer is also the same.

On the other hand, in the calculation of the R value, as "the sum of the linear distances between adjacent significant vertices", it is not constant how many sets of significant vertices exist in the observation area of the cross section of the test piece. For example, when the observation area|region of the cross section of a test piece is made into the area|region of 1 mm, 50-500 sets of significant vertices may be sufficient, 75-250 sets may be sufficient, and 100-200 sets may be sufficient as them.

A test piece is cut out between the support sheet in the step not forming the composite sheet for forming a protective film and the support sheet constituting the composite sheet for forming a protective film, When the average value (R value) of the ratio of the sum of the distances) / (the linear distance in the horizontal direction to the pressure-sensitive adhesive layer) is compared, these R values are the same or the support sheet constituting the composite sheet for forming a protective film The R value in is a degree to which the value of R is slightly decreased, and even when it becomes small in this way, the difference is negligible.

When the minimum value of the thickness of the pressure-sensitive adhesive layer is compared between the support sheet in the step not forming the composite sheet for forming a protective film and the support sheet constituting the composite sheet for forming a protective film, these minimum values are the same or , is a degree to which the minimum value in the support sheet constituting the composite sheet for forming a protective film becomes slightly smaller, and even when it becomes smaller in this way, the difference is negligible.

It is the same also about the maximum value of the thickness of an adhesive layer. That is, when the maximum value of the thickness of an adhesive layer is compared between the support sheet in the step which does not comprise the composite sheet for protective film formation, and the support sheet which comprises the composite sheet for protective film formation, these maximum values are mutually It is the same or the said maximum value in the support sheet which comprises the composite sheet for protective film formation is a grade which becomes small, and even when it becomes small in this way, the difference is a negligible degree.

Therefore, using a test piece cut out from the composite sheet for forming a protective film instead of the support sheet, the R value may be obtained in the same manner as in the case of using the test piece cut out from the support sheet, or the S value and L value of the pressure-sensitive adhesive layer may be obtained. Thus, when the test piece cut out from the composite sheet for protective film formation is used and R value becomes 1.5 or more and less than 5.0, this composite sheet for protective film formation reflects the effect of this invention mentioned above.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film having a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet, and a test piece is prepared from five places of the composite sheet for forming a protective film. Cut out, in these 5 test pieces, when the cross section of the adhesive layer is observed, the average value (R value) of the ratio (the sum of the linear distances between adjacent significant vertices) / (the linear distance in the horizontal direction to the adhesive layer) 1.5 or more and less than 5.0.

Similarly, using a test piece cut out from the composite sheet for forming a protective film instead of the support sheet in the step where the composite sheet for forming a protective film is not constituted, the S value and L of the pressure-sensitive adhesive layer are used in the same manner as when the test piece cut out from the support sheet is used. You can get the value. When the test piece cut out from the composite sheet for forming a protective film in this way is used, when the S value of the pressure-sensitive adhesive layer is 1.5 µm or more and the L value of the pressure-sensitive adhesive layer is 9 µm or less, this composite sheet for forming a protective film is The effect of the invention is likely to be reflected.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film having a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet, and a test piece is prepared from five places of the composite sheet for forming a protective film. cut out, and when the minimum value and the maximum value of the thickness of the pressure-sensitive adhesive layer are respectively obtained in these five test pieces, the average value (S value) of the minimum value is 1.5 µm or more, and the average value (L value) of the maximum value is 9 µm It is preferable to become the following.

On the other hand, the test piece cut out from the composite sheet for protective film formation was obtained by cutting|disconnecting the composite sheet for protective film formation in the whole thickness direction, It is a small piece provided with all the layers which comprise the composite sheet for protective film formation.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of the whole of the composite sheet for protective film formation of this invention is demonstrated, referring drawings. On the other hand, in the drawings used in the following description, in order to make the characteristics of the present invention easy to understand, there are cases where the main parts are enlarged and shown, and the dimensional ratio of each component is not limited to the same as in reality. does not

1 : is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.

The composite sheet 1A for protective film formation shown here is equipped with the base material 11, The adhesive layer 12 is provided on the base material 11, The film 13 for protective film formation on the adhesive layer 12 is provided. is provided. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1A for forming a protective film is, in other words, one side of the support sheet 10 (in this specification, the It has a structure in which the film 13 for protective film formation was laminated|stacked on 10a (sometimes referred to as "one side"). Moreover, 1 A of composite sheet|seats for protective film formation are equipped with the peeling film 15 on the film 13 for protective film formation further.

In 1A of composite sheet for protective film formation, the adhesive layer 12 is laminated|stacked on one side (in this specification, it may call a "first surface") 11a of the base material 11, The adhesive layer In (12), the protective film 13 is laminated on the entire surface of the surface (in this specification, referred to as "first surface") 12a opposite to the substrate 11 side, and the protective film is formed. Adhesive layer for jigs in a part of the surface (in this specification, it may be called "the 1st surface") 13a on the opposite side to the adhesive layer 12 side of the film 13, ie, the area|region near the periphery for a jig|tool (16) is laminated|stacked, the surface on which the adhesive bond layer 16 for jig|tools is not laminated|stacked among the 1st surface 13a of the film 13 for protective film formation, and the film for protective film formation of the adhesive bond layer 16 for jig|tools. The release film 15 is laminated|stacked on the surface 16a (upper surface and side surface) which is not in contact with (13).

In addition, in FIG. 1, the code|symbol 13b has shown the adhesive layer 12 side surface (in this specification, a "2nd surface" may be called) of the film 13 for protective film formation.

The adhesive layer 16 for a jig may have, for example, a single-layer structure containing an adhesive component, 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.

In 1 A of composite sheet|seats for protective film formation, the 1st surface 11a of the base material 11 is an uneven|corrugated surface.

Further, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (concave-convex surface) 11a of the base material 11 . For this reason, the surface (in this specification, it may call a "second surface") 12b of the base material 11 side of the adhesive layer 12 is an uneven surface.

In the composite sheet 1A for forming a protective film, the surface on the opposite side to the pressure-sensitive adhesive layer 12 side of the substrate 11 (in this specification, it may be referred to as a "second surface") 11b is an uneven surface and Although any of a smooth surface (a non-irregular surface, a glossy surface) may be sufficient, it is preferable that it is a smooth surface. The 2nd surface 11b of the base material 11 is the surface on the opposite side to the film 13 side for protective film formation of the support sheet 10 (in this specification, it may call a "second surface") 10b ) can also be said.

"Concave-convex surface" and "smooth surface" will be described in detail later.

In the composite sheet 1A for forming a protective film shown in Fig. 1, the back surface of a semiconductor wafer (not shown) is affixed to the first surface 13a of the film 13 for forming a protective film in a state in which the release film 15 is removed. Moreover, the upper surface among the surfaces 16a of the adhesive bond layer 16 for jig|tools 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 another embodiment of this invention with a support sheet.

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 component same as that shown in the figure previously demonstrated, and the detailed description is abbreviate|omitted.

The composite sheet 1B for protective film formation shown here is the same as that of 1 A of composite sheets for protective film formation shown in FIG. 1 except the point which is not equipped with the adhesive bond layer 16 for jig|tools. That is, in the composite sheet 1B for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11 , and on the entire surface of the first surface 12a of the pressure-sensitive adhesive layer 12 . The film 13 for protective film formation is laminated|stacked, and the peeling film 15 is laminated|stacked on the whole surface of the 1st surface 13a of the film 13 for protective film formation.

Also in the composite sheet 1B for protective film formation, the 1st surface 11a of the base material 11 is an uneven surface.

Further, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (concave-convex surface) 11a of the base material 11 . For this reason, the surface (2nd surface) 12b of the base material 11 side of the adhesive layer 12 is an uneven surface.

Also in the composite sheet 1B for forming a protective film, the second surface 11b of the base material 11 (that is, the second surface 10b of the support sheet 10) is one of a concave-convex surface and a smooth surface (non-convex surface). Although any may be sufficient, it is preferable that it is a smooth surface.

The composite sheet 1B for protective film formation shown in FIG. 2 is a semiconductor wafer (shown in figure) in the central part of the 1st surface 13a of the film 13 for protective film formation in the state from which the peeling film 15 was removed. abbreviation) is pasted, and the area|region in the vicinity of a periphery is pasted to jigs, such as a ring frame, and is used.

3 : is sectional drawing which shows typically the composite sheet for protective film formation which concerns on another embodiment of this invention together with a support sheet.

The composite sheet 1C for protective film formation shown here is the same as that of the composite sheet 1B for protective film formation shown in FIG. 2 except the point from which the shape of the film for protective film formation differs. That is, the composite sheet 1C for forming a protective film includes a base 11 , a pressure-sensitive adhesive layer 12 on the base 11 , and a film 23 for forming a protective film on the pressure-sensitive adhesive layer 12 . are being prepared The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 , and the composite sheet 1C for forming a protective film is, in other words, the first surface of the support sheet 10 (film 23 for forming a protective film). ) has a configuration in which a film 23 for forming a protective film is laminated on the side) 10a. Moreover, 1 C of composite sheets for protective film formation are further equipped with the peeling film 15 on the film 23 for protective film formation.

In 1 C of composite sheets for protective film formation, the adhesive layer 12 is laminated|stacked on the 1st surface 11a of the base material 11, A part of 1st surface 12a of the adhesive layer 12, ie, the center The film 23 for protective film formation is laminated|stacked in the area|region on the side. And the area|region on which the film 23 for protective film formation is not laminated|stacked among the 1st surface 12a of the adhesive layer 12, and the surface which is not in contact with the adhesive layer 12 of the film 23 for protective film formation. A release film 15 is laminated on 23a (top and side surfaces).

In addition, in FIG. 3, the code|symbol 23b has shown the adhesive layer 12 side surface (in this specification, a "2nd surface" may be called) of the film 23 for protective film formation.

When 1 C of composite sheets for protective film formation are looked down from upper direction and planar view, the film 23 for protective film formation has a smaller surface area than the adhesive layer 12, For example, it has shapes, such as a circular shape.

Also in 1 C of composite sheets for protective film formation, the 1st surface 11a of the base material 11 is an uneven surface.

Further, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (concave-convex surface) 11a of the base material 11 . For this reason, the surface (2nd surface) 12b of the base material 11 side of the adhesive layer 12 is an uneven surface.

Also in 1C of composite sheet for protective film formation, the 2nd surface 11b of the base material 11 (in other words, the 2nd surface 10b of the support sheet 10) is one of an uneven surface and a smooth surface (non-convex surface). Although any may be sufficient, it is preferable that it is a smooth surface.

In the composite sheet 1C for forming a protective film shown in Fig. 3, the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the film 23 for forming a protective film in a state in which the release film 15 is removed, The area|region on which the film 23 for protective film formation is not laminated|stacked among the 1st surface 12a of the adhesive layer 12 is affixed to jigs, such as a ring frame, and is used.

On the other hand, in 1C of composite sheet for protective film formation shown in FIG. 3, among the 1st surface 12a of the adhesive layer 12, in the area|region where the film 23 for protective film formation is not laminated|stacked, what is shown in FIG. Similarly, the adhesive bond layer for jig|tools may be laminated|stacked (not shown). As for the composite sheet 1C for protective film formation provided with such an adhesive bond layer for jigs, the upper surface of the adhesive bond layer for jigs is stuck to jigs, such as a ring frame, similarly to the composite sheet for protective film formation shown in FIG.

Thus, whatever form the support sheet and the film for protective film formation may be provided with the adhesive bond layer for jigs, the composite sheet for protective film formation may be sufficient as it. However, normally, as shown in FIG. 1, as a composite sheet for protective film formation provided with the adhesive bond layer for jigs, it is preferable that what was equipped with the adhesive bond layer for jigs on the film for protective film formation.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to that shown in Figs. What has been changed or deleted, or what has been described so far may be one in which another configuration is added.

For example, in the composite sheet for protective film formation shown in FIGS. 1-3, the intermediate|middle layer may be formed between the base material 11 and the adhesive layer 12. As shown in FIG. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be constituted by laminating the base material, the intermediate layer, and the pressure-sensitive adhesive layer in this order in the thickness direction thereof. As the intermediate layer, any one can be selected depending on the purpose.

In addition, as for the composite sheet for protective film formation shown to FIGS. 1-3, layers other than the said intermediate|middle layer may be formed in arbitrary locations.

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

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

However, as shown in Figs. 1 to 3, in the composite sheet for forming a protective film, the pressure-sensitive adhesive layer is in direct contact with the uneven surface (first surface) of the substrate, that is, an intermediate layer is formed between the substrate and the pressure-sensitive adhesive layer. It is not provided, and it is preferable that the adhesive layer is directly contacted and laminated|stacked on a base material.

Further, in the composite sheet for forming a protective film, the film for forming a protective film is in direct contact with the first surface of the pressure-sensitive adhesive layer, that is, no other layer is provided between the pressure-sensitive adhesive layer and the film for forming a protective film, the pressure-sensitive adhesive layer It is preferable that the film for protective film formation directly contacts and laminates|stacks on it.

In addition, the composite sheet for forming a protective film satisfies these conditions together, that is, it is preferable that the base material, the pressure-sensitive adhesive layer, and the film for forming a protective film are in direct contact with each other in this order in the thickness direction and are laminated and configured desirable.

The support sheet is preferably transparent.

The support sheet may be colored according to the purpose, and another layer may be vapor-deposited.

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

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 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.

In this specification, "energy-beam sclerosis|hardenability" means the property to harden|cure by irradiating an energy beam, and "non-energy-beam sclerosis|hardenability" means the property which does not harden even if it irradiates an energy beam.

In the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the 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.

The upper limit of the transmittance|permeability of the light of wavelength 375nm in a support sheet is not specifically limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When a laser beam is irradiated to the film for protective film formation or a protective film through the support sheet, and the transmittance|permeability of the said light is this range, and printing on these, it can print more clearly.

The upper limit of the transmittance|permeability of the light of wavelength 532nm in a support sheet is not specifically limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When a laser beam is irradiated to the film for protective film formation or a protective film through the support sheet, and the transmittance|permeability of the said light is this range, and printing on these, it can print more clearly.

The upper limit of the transmittance|permeability of the light of wavelength 1064 nm in a support sheet is not specifically limited. For example, the transmittance of the light may be 95% or less.

It is preferable that the transmission clarity of a support sheet is 30 or more, It is more preferable that it is 100 or more, It is especially preferable that it is 200 or more. When the said transmission clarity is such a range, confirmation of the float peeling of the film for protective film formation through a support sheet, the problem of printing, a defect, etc. becomes easier.

The transmission clarity of the support sheet is not particularly limited. For example, the transmission clarity may be 430 or less.

The transmission clarity of the supporting sheet can be measured in accordance with JIS K7374-2007.

Next, each layer which comprises a support sheet and the composite sheet for protective film formation is demonstrated in detail.

○ Mention

The substrate is in the form of a sheet or a film and has an uneven surface.

In this specification, the "iron surface" means the surface whose maximum height roughness Rz prescribed|regulated to JISB0601:2013 is 0.01 micrometer or more.

In addition, a "smooth surface" is not an uneven surface, but a surface with high smoothness is meant, and a "non-irregular surface" or a "glossy surface" may be called. For example, the smooth surface includes a surface with an extremely small degree of unevenness that does not correspond to the uneven surface.

In the base material, only one surface may be an uneven surface, and both surfaces may be uneven surfaces, but it is preferable that only one surface is an uneven surface. In other words, in the above substrate, it is preferable that only one surface is a smooth surface. In a support sheet, the uneven|corrugated surface of a base material turns into the surface on the side provided with an adhesive layer.

The substrate may be composed of one layer (single layer), may be composed of two or more layers, or if 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

When a base material consists of multiple layers, the surface (the surface closest to an adhesive layer, or both surfaces of the surface closest to an adhesive layer, and a farthest surface) of the outermost layer among these multiple layers becomes the said uneven|corrugated surface.

In this specification, it is not limited to the case of a description, "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" means, and "a plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

In the uneven surface (first surface) on the side provided with the pressure-sensitive adhesive layer of the substrate, the R value of the substrate is preferably 1.3 or more and less than 4.8. It is preferable that it is 1.5 or more, and it is more preferable that it is 1.7 or more, For example, any of 2.1 or more, 2.5 or more, 2.8 or more, and 3.3 or more may be sufficient. When R value of the said base material is more than the said lower limit, R value of an adhesive can be adjusted favorably. Here, the R value of the substrate is when a test piece is cut out from 5 places on the substrate, and the cross section of the substrate is observed in these five specimens, (sum of the linear distances between adjacent significant vertices)/(to the substrate It refers to the average value of the ratio of straight-line distances in the horizontal direction).

Moreover, it is preferable that the maximum height roughness (Rz) measured based on JISB0601:2013 in the uneven|corrugated surface (1st surface) of the side provided with the adhesive layer of a base material is 0.01-8 micrometers, and 0.1-7 micrometers It is more preferable, and it is especially preferable that it is 0.5-6 micrometers. When the said Rz of a base material is more than the said lower limit, generation|occurrence|production of the problem at the time of winding up and unwinding a base material independently in roll shape is suppressed. Moreover, generation|occurrence|production of the problem at the time of winding up and unwinding similarly also about the laminated body containing a base material in the manufacturing process of a support sheet or the composite sheet for protective film formation is suppressed. On the other hand, when said Rz of a base material is below the said upper limit, both the lamination|stacking property of an adhesive layer and the film for protective film formation, and the printing visibility through the support sheet of a protective film or the film for protective film formation become favorable.

When both surfaces of a base material are uneven|corrugated surfaces, the unevenness|corrugation degree of these both surfaces may mutually be same or different.

As a constituent material of the said base material, various resin is mentioned, 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 the resin other than that, 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 illustrated so far are bridge|crosslinking resin; 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 the present specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group", and "(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.

It is preferable to exist in the range of 50-300 micrometers, and, as for the thickness of a base material, it is more preferable to exist in the range of 60-150 micrometers. When the thickness of a base material exists in such a range, the flexibility of the said composite sheet for protective film formation, and the sticking property to a semiconductor wafer or a semiconductor chip improve more.

Since the base material has an uneven surface as described above, its thickness fluctuates depending on the site of the base material. Therefore, the minimum value of the thickness of a base material may be more than the said lower limit, and the maximum value of the thickness of a base material may be less than the said upper limit.

In addition, 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 thickness of the sum total of all the layers which comprise a base material.

The thickness of the substrate can be measured, for example, by observing the side or cross-section of the substrate using a scanning electron microscope (SEM).

The cross section of the substrate can be formed, for example, in the same manner as in the case of the cross section in the test piece of the support sheet and the composite sheet for forming a protective film described above.

For example, similarly to the method described above, a test piece is cut out from a plurality of locations (for example, five locations) of a support sheet or a composite sheet for forming a protective film, and the minimum and maximum values of the thickness of the substrate in this test piece are obtained, and these Further, when the average value of these minimum values and the average value of the maximum values is obtained from the value of .

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.

The substrate is preferably transparent.

The base material may be colored according to the purpose, and another layer may be vapor-deposited.

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

The substrate is oxidized by corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc. in order to improve adhesion with a layer in direct contact such as an adhesive layer formed thereon A treatment or the like may be applied to the surface.

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

In addition, the substrate may include an antistatic coating layer; When the composite sheet for forming a protective film is stacked and stored, the substrate may have a layer or the like that prevents the substrate from adhering to another sheet or from adhering the substrate to the adsorption table.

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.

In the case of using a substrate having no concavo-convex surface (that is, a substrate having smooth surfaces on both sides), the smooth surface of the substrate may be subjected to concavo-convex treatment.

The unevenness treatment can be performed by a known method. For example, by using a metal roll or a metal plate having an uneven surface, and pressing the uneven surface to the smooth surface of the substrate, the smooth surface of the substrate can be treated to be uneven. At this time, it is preferable to press the heated metal roll or metal plate to the smooth surface of the substrate.

For example, in addition to being able to manufacture a substrate having a desired uneven surface by using metal rolls having different unevenness, even if metal rolls having the same unevenness are used, the temperature of the metal rolls is changed or the gap between the metal rolls is By changing the pressing force, it is possible to manufacture a substrate having a desired uneven surface. In addition, the smooth surface of the substrate may be roughened by sand blasting or solvent treatment. Even if the unevenness|corrugation is produced by any method, the effect of invention is not affected.

○Adhesive layer

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

In the pressure-sensitive adhesive layer, in general, regardless of the presence or absence of an intermediate layer between the base material and the pressure-sensitive adhesive layer, the surface of the base material is affected by the concave-convex surface, and at least the surface on the side of the base material is the concave-convex surface.

The pressure-sensitive adhesive layer may consist of one layer (single layer), may be composed of multiple layers 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 particularly limited doesn't happen

When an adhesive layer consists of multiple layers, the surface (surface closest to a base material) of an outermost layer among these multiple layers turns into the said uneven|corrugated surface.

Here, the base material and the pressure-sensitive adhesive layer will be described in more detail with reference to the drawings.

4 is an enlarged cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Here, 1 A of composite sheets for protective film formation shown in FIG. 1 are mentioned as an example and demonstrated. In addition, in FIG. 4, illustration of a peeling film is abbreviate|omitted.

As described above, the first surface 11a of the substrate 11 is an uneven surface. In addition, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (concave-convex surface) 11a of the substrate 11, and the second surface 12b of the pressure-sensitive adhesive layer 12 is made of the substrate 11 It is made easy to follow one surface 11a. Accordingly, the second surface 12b of the pressure-sensitive adhesive layer 12 also becomes an uneven surface.

The linear distance between adjacent significant vertices is not constant, and fluctuates depending on the portion of the pressure-sensitive adhesive layer 12 . Here, the linear distances between significant adjacent vertices are denoted by symbols L _a1 , L _b1 , L _a2 , L _b2 ... is indicated by In addition, symbols L _a1 , L _b1 , L _a2 , L _b2 ... Among the line segments indicated by , the line segments indicated by the symbols L _a1 and L _b1 are projected onto the pressure-sensitive adhesive layer on a horizontal plane, the line segments are indicated by L ₁ , and the line segments indicated by the symbols L _a2 and L _b2 are placed on the pressure-sensitive adhesive layer on the horizontal plane. The projected line segment is indicated by L ₂ .

In 1A of composite sheet for protective film formation, a test piece is cut out from the five places, a cross section is formed in these five test pieces, In this newly formed cross section, all adjacent significant vertices of each adhesive layer are linear distances between each other. (The code|symbol L _a1 , L _b1 , L _a2 , L _b2 ...) and the linear distance in a horizontal direction are calculated|required for the adhesive layer in between. And (sum of the linear distances between all adjacent significant vertices (the above symbols L _a1 , L _b1 , L _a2 , L _b2 …)) / (the horizontal linear distance to the pressure-sensitive adhesive layer (the above symbols L ₁ , L ₂ …) The sum of the lengths of the line segments represented by ))) is calculated, and the average value (the R value) is calculated from the values of at least five ratios to be 1.5 or more and less than 5.0.

5 is an enlarged cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Here, 1 A of composite sheets for protective film formation shown in FIG. 1 are mentioned as an example and demonstrated. In addition, in FIG. 5, illustration of a peeling film is abbreviate|omitted.

The thickness Ta of the pressure-sensitive adhesive layer 12 _is not constant and fluctuates depending on the portion of the pressure-sensitive adhesive layer 12 . Here, the minimum value of the thickness of the adhesive layer 12 is shown by code|symbol T _a1 , and the maximum value of the thickness of the adhesive layer 12 is shown by code|symbol T _a2 .

In 1A of composite sheet for protective film formation, a test piece is cut out from the five places, a cross section is formed in these five test pieces, In this newly formed cross section, the minimum value ( _Ta1 ) and the maximum of the thickness of an adhesive layer, respectively. A value T _a2 is found. And, when the average value (the S value) is obtained from at least five values of _Ta1 , it is preferably 1.5 µm or more, and when the average value (the L value) is obtained from the values of at least five _Ta2 values, it is 9 µm or less it is preferable

Cutting of the test piece from the composite sheet 1A for forming a protective film, formation of a cross section in the test piece, measurement of the R value of the pressure-sensitive adhesive layer in the cross section, and the minimum value ( _Ta1 ) of the thickness of the pressure-sensitive adhesive layer and The measurement of maximum value _Ta2 can be performed similarly to the case where a test piece is cut out from the support sheet which does not comprise the composite sheet for protective film formation as mentioned above.

In addition, the enlarged sectional view of the support sheet which does not comprise the composite sheet for protective film formation is the same as that which abbreviate|omitted illustration of the film 13 for protective film formation in FIG.4 and FIG.5.

As 1A of composite sheet for protective film formation, here, between the base material 11 and the adhesive layer 12, these are not bonded area|region (in this specification, it may call a "non-bonding area|region") (91) indicates that it exists. However, even if 1A of composite sheet|seat for protective film formation has such non-bonding area|region 91, the magnitude|size of the non-bonding area|region 91 in the thickness direction of 1 A of composite sheet|seats for protective film formation is 0.5 micrometer, for example. The following composite sheet|seat 1A for protective film formation has favorable lamination|stacking property of the base material 11 and the adhesive layer 12, and it can be said that it has favorable characteristics.

In addition, in this specification, "the size of the non-bonding area|region in the thickness direction of the composite sheet for protective film formation" means "the interlayer distance in the thickness direction of the said sheet of two adjacent layers in the composite sheet for protective film formation" , and is sometimes referred to simply as an “interlayer distance”. For example, the "size of the non-bonding area|region 91 in the thickness direction of 1 A of composite sheets for protective film formation" mentioned above" is "the base material 11 and the adhesive in the thickness direction of 1 A of said sheets." interlayer distance between the layers 12 .

When the size (interlayer distance) of one non-bonding area|region fluctuates, the maximum value is employ|adopted as the magnitude|size (interlayer distance) of a non-bonding area|region.

The magnitude|size (interlayer distance) of a non-bonding area|region can be measured by the method similar to the case of R value of the above-mentioned adhesive layer, for example. That is, a cross section is formed in the test piece of the composite sheet for protective film formation by the method similar to when calculating|requiring the R value of an adhesive layer, and the magnitude|size of a non-bonding area|region can be calculated|required in this cross section. Or a cross section may be formed with composite sheet itself for protective film formation, without producing a test piece, and the magnitude|size of a non-bonding area|region may be calculated|required in this cross section.

The size (the interlayer distance) of the non-bonding region 91 may be, for example, any one of 0.4 µm or less, 0.3 µm or less, 0.2 µm or less, and 0.1 µm or less.

In 1 A of composite sheets for protective film formation, the non-bonding area|region 91 does not exist at all in some cases. In this specification, when the non-bonding area|region 91 does not exist at all, the magnitude|size (interlayer distance) of the non-bonding area|region 91 may be expressed by 0 micrometer.

Here, although the base material and adhesive layer were demonstrated taking 1 A of composite sheets for protective film formation as an example, the composite sheet for protective film formation of other embodiment, such as the composite sheet 1B for protective film formation, and the composite sheet 1C for protective film formation. Also in the case of the sheet, the base material and the pressure-sensitive adhesive layer are the same.

The R value of the pressure-sensitive adhesive layer is not particularly limited as long as it is 1.5 or more and less than 5.0, but is preferably 1.7 or more, more preferably 1.9 or more, for example, out of 2.3 or more, 2.7 or more, 3.1 or more, and 3.5 or more. Any one may be sufficient. When the said R value is more than the said lower limit, the adhesiveness of a base material and an adhesive becomes more favorable.

On the other hand, the R value of the pressure-sensitive adhesive layer may be, for example, 4.5 or less, or 4.0 or less. Such an adhesive layer becomes favorable in printing visibility through the support sheet of a protective film or the film for protective film formation.

The R value of the pressure-sensitive adhesive layer can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower limit and upper limit values. For example, R value of an adhesive layer becomes like this. Preferably it is 1.5-4, More preferably, it is 1.7-4, More preferably, it is 1.9-4, for example, 2.3-4, 2.7-4, 3.1-4, And any one of 3.5-4 may be sufficient. However, these are examples of the R value of an adhesive layer.

Although the S value of an adhesive layer is not specifically limited unless the effect of this invention is impaired, It is 1.5 micrometers or more, and it is preferable that it is less than 9 micrometers. It is more preferable that it is 1.7 micrometers or more, and it is especially preferable that it is 1.9 micrometers or more, For example, any one of 2.3 micrometers or more, 2.7 micrometers or more, 3.1 micrometers or more, and 3.5 micrometers or more may be sufficient. When the said S value is more than the said lower limit, the lamination|stacking property of an adhesive layer and the film for protective film formation becomes more favorable.

In addition, the S value of an adhesive layer may be 8 micrometers or less, for example. Such a pressure-sensitive adhesive layer can be formed more easily.

The S value of the pressure-sensitive adhesive layer can be appropriately adjusted within the range set by arbitrarily combining the above-described preferred lower limit and upper limit values. For example, the S value of the pressure-sensitive adhesive layer is preferably 1.5 to 8 µm, more preferably 1.7 to 8 µm, still more preferably 1.9 to 8 µm, for example, 2.3 to 8 µm and 2.7 to 8 µm. , 3.1 to 8 µm, and any one of 3.5 to 8 µm may be sufficient. However, these are examples of the S value of an adhesive layer.

Although the L value of an adhesive layer is not specifically limited unless the effect of this invention is impaired, The case where it is 9 micrometers or less, and larger than 1.5 micrometers is preferable. It is more preferable that it is 8.6 micrometers or less, It is especially preferable that it is 8.3 micrometers or less, For example, any one of 7.7 micrometers or less, 7.3 micrometers or less, 6.9 micrometers or less, and 6.5 micrometers or less may be sufficient. When the said L value is below the said upper limit, the printing visibility through the support sheet of a protective film or the film for protective film formation becomes more favorable.

In addition, 2.5 micrometers or more may be sufficient as L value of an adhesive layer, for example. Such a pressure-sensitive adhesive layer can be formed more easily.

The L value of the pressure-sensitive adhesive layer can be appropriately adjusted within the range set by arbitrarily combining the preferable lower limit and upper limit described above. For example, L value of an adhesive layer becomes like this. Preferably it is 2.5-9 micrometers, More preferably, it is 2.5-8.6 micrometers, More preferably, it is 2.5-8.3 micrometers, for example, 2.5-7.7 micrometers, 2.5-7.3 micrometers. , 2.5 to 6.9 µm, and any one of 2.5 to 6.5 µm may be sufficient.

The thickness (eg, T _a ) of the pressure-sensitive adhesive layer is not particularly limited as long as the effects of the present invention are not impaired, but it is preferable to satisfy the conditions of the S value and the L value described above.

For example, the thickness of an adhesive layer may be 1.5-9 micrometers.

In addition, 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 thickness of the sum total of all the layers which comprise an adhesive layer. From this point of view, the minimum and maximum values of the thickness of the above-described pressure-sensitive adhesive layer are defined.

The pressure-sensitive adhesive layer contains a pressure-sensitive 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.

As used herein, the term "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, for example, not only the resin itself has adhesiveness, but also in combination with other components such as additives. Resin which shows adhesiveness by this, resin etc. which show adhesiveness by presence of triggers, such as heat or water, are also included.

It is preferable that an adhesive layer is transparent.

The pressure-sensitive adhesive layer may be colored according to the purpose.

For example, when the film for protective film formation is 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. 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 as needed. The more specific formation method of an adhesive layer is demonstrated in detail later with the formation method of other layers. The ratio of content of the 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 the present specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and for example, a temperature of 15 to 25°C and the like.

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 Mayer bar. The method using various coaters, such as a coater and a kiss coater, is mentioned.

Although the drying conditions of an adhesive composition are not specifically limited, When the adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. It is preferable to dry the adhesive composition containing a solvent on conditions for 10 second - 5 minutes at 70-130 degreeC, for example.

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 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 at least (meth)acrylic-acid alkylester 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 it, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Examples of the (meth)acrylic acid alkyl ester include those having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the alkyl group is preferably linear or branched.

More specifically, as (meth)acrylic acid alkyl ester, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) Isobutyl acrylate, (meth)acrylate sec-butyl, (meth)acrylate tert-butyl, (meth)acrylate pentyl, (meth)acrylate hexyl, (meth)acrylate heptyl, (meth)acrylic acid 2-ethylhexyl, (meth) 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)acrylic acid ) 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 (meth)acrylic-acid alkylester whose carbon number of the said alkyl group is 4 or more at the point which the adhesive force of an adhesive layer improves. And it is preferable that it is 4-12, and, as for carbon number of the said alkyl group, it is more preferable that it is 4-8 at the point which the adhesive force of an adhesive layer improves more. Moreover, it is preferable that C4 or more of the said alkyl group (meth)acrylic-acid alkylester is an acrylic acid alkylester.

It is preferable that the said acrylic polymer has the structural unit derived from a functional group containing monomer further other than 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, it is possible to introduce an unsaturated group into the side chain of the acrylic polymer. can be heard to do

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) acrylic acid 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.

It is preferable that content of the structural unit derived from a functional group containing monomer in the said acrylic polymer is 1-35 mass % with respect to the total amount of structural units, It is more preferable that it is 2-30 mass %, It is 3-27 mass % Especially preferred.

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

The other monomer is not particularly limited as long as it can be copolymerized with (meth)acrylic acid alkylester or the like.

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, what made the functional group in the said acrylic polymer react the unsaturated-group containing compound which has an energy-beam polymerizable unsaturated group (energy-beam polymeric group) can be used as the above-mentioned energy-beam 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 adhesive resin (I-1a) in an adhesive composition (I-1) is 5-99 mass %, It is more preferable that it is 10-95 mass %, It is especially preferable that it is 15-90 mass % .

[Energy-ray-curable compound]

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

Among the energy ray-curable compounds, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth). polyvalent (meth)acrylates such as acrylate, 1,4-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.

Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerization of the monomers exemplified above.

An energy ray-curable compound has a comparatively large molecular weight, and urethane (meth)acrylate and a urethane (meth)acrylate oligomer are preferable at the point that it is hard to reduce the storage elastic modulus of an adhesive layer.

The number of the said energy-beam curable compound 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 said adhesive composition (I-1), it is preferable that content of the said energy-beam sclerosing|hardenable compound is 1-95 mass %, It is more preferable that it is 5-90 mass %, It is especially preferable that it is 10-85 mass %.

[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 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.

It is preferable that the crosslinking agent is an isocyanate type crosslinking agent from points, such as the point which improves the cohesive force of an adhesive, and improves the adhesive force of an adhesive layer, and an acquisition is easy.

The number of crosslinking agents 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 may be arbitrarily selected.

It is preferable that content of a crosslinking agent in the said adhesive composition (I-1) is 0.01-50 mass parts with respect to content of 100 mass parts of adhesive resin (I-1a), It is more preferable that it is 0.1-20 mass parts, It is 0.3-15 mass parts It is especially preferable that it is a mass part.

[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.

One type may be sufficient as the photoinitiator which adhesive composition (I-1) 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-1) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound. It is particularly preferred.

[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 of this invention.

Examples of the above 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. .

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

Content of other additives in an 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 surface to be coated.

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.

The solvent 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), for example, the solvent used in the production of the pressure-sensitive adhesive resin (I-1a), or the pressure-sensitive adhesive resin (I-1a) A solvent of the same or different type as that used in the preparation of I-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.

In the adhesive composition (I-1), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<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.

Examples of the energy ray polymerizable unsaturated group include a (meth)acryloyl group, a vinyl group (also called an ethenyl group), an allyl group (also called a 2-propenyl group), and the like, and 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) 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.

It is preferable that it is 5-99 mass % with respect to the gross mass of an adhesive composition (I-2), and, as for content of adhesive resin (I-2a) in an adhesive composition (I-2), it is more preferable that it is 10-95 mass % and it is especially preferable that it is 10-90 mass %.

[Crosslinking agent]

When using, for example, the above-mentioned acrylic polymer having structural units derived from the same functional group-containing monomer as in the adhesive resin (I-1a) as the 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 adhesive composition (I-2) may be one, two or more types may be sufficient, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

It is preferable that content of a crosslinking agent in the said adhesive composition (I-2) is 0.01-50 mass parts with respect to content 100 mass parts of adhesive resin (I-2a), It is more preferable that it is 0.1-20 mass parts, It is 0.3-15 mass parts It is especially preferable that it is a mass part.

[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 an adhesive composition (I-2), the thing similar to the photoinitiator in an 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.

It is preferable that content of a photoinitiator in an adhesive composition (I-2) is 0.01-20 mass parts with respect to content 100 mass parts of adhesive resin (I-2a), It is more preferable that it is 0.03-10 mass parts, 0.05-5 It is especially preferable that it is a mass part.

[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 of this invention.

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 an adhesive composition (I-2), 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-2) 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-2), the content of the solvent 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 it is 5-99 mass % with respect to the gross mass of an adhesive composition (I-3), and, as for content of adhesive resin (I-2a) in an adhesive composition (I-3), it is more preferable that it is 10-95 mass % and 15-90 mass % is especially preferable.

[Energy-ray-curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy-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 ratios can be selected arbitrarily.

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

[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.

One type may be sufficient as the photoinitiator 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.

It is preferable that content of a photoinitiator in adhesive composition (I-3) is 0.01-20 mass parts with respect to 100 mass parts of total content of adhesive resin (I-2a) and the said energy-beam curable compound, It is 0.03-10 mass parts More preferably, it is especially preferable that it is 0.05-5 mass parts.

[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 of this invention.

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, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Content of other additives in an 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, these combinations and ratios can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<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 these contained components is an overall pressure-sensitive adhesive composition other than these three types of pressure-sensitive adhesive compositions. (In this specification, "Adhesive compositions other than adhesive compositions (I-1) to (I-3)" are called) and can be used similarly.

As an adhesive composition other than adhesive composition (I-1) - (I-3), a non-energy-ray-curable adhesive composition is also mentioned other than an 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 two or more types of crosslinking agents, and the content thereof is the same as in the above-described pressure-sensitive adhesive composition (I-1) and the like. 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 it is 5-99 mass % with respect to the gross mass of an adhesive composition (I-4), and, as for content of adhesive resin (I-1a) in an adhesive composition (I-4), it is more preferable that it is 10-95 mass % and 15-90 mass % is especially preferable.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total content of all components other than the solvent (that is, the content of the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive layer) is 30 to 90 It is preferable that it is mass %, It is more preferable that it is 40-85 mass %, It is especially preferable that it is 50-80 mass %.

[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, two or more types may be sufficient, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

It is preferable that content of a crosslinking agent in the said adhesive composition (I-4) is 0.01-50 mass parts with respect to content of 100 mass parts of adhesive resin (I-1a), It is more preferable that it is 0.3-50 mass parts, It is more preferable, It is 1-50 It is more preferable that it is a mass part, for example, any one of 10-50 mass parts, 15-50 mass parts, 20-50 mass parts, etc. may be sufficient.

[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 of this invention.

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

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

Content of a solvent in adhesive composition (I-4) is not specifically limited, What is necessary is just to adjust suitably.

In the composite sheet for forming a protective film, the pressure-sensitive adhesive layer is preferably non-energy ray-curable. This is because if an adhesive layer is energy-beam sclerosis|hardenability, when hardening the film for protective film formation by irradiation of an energy-beam, it may not be able to suppress that an adhesive layer also hardens simultaneously. When an adhesive layer hardens|cures simultaneously with the film for protective film formation, the film for protective film formation after hardening (namely, a protective film) and an adhesive layer may stick to the extent that peeling is impossible in these interfaces. In that case, it becomes difficult to peel the cured film for forming a protective film, that is, a semiconductor chip having a protective film on its back surface (semiconductor chip with a protective film formed thereon) from the supporting sheet provided with the cured adhesive layer, and the semiconductor chip with a protective film is normally removed cannot be picked up. By making the adhesive layer non-energy-ray-curable in the said support sheet, such a problem can be avoided reliably, and the semiconductor chip with a protective film can be picked up more easily.

Here, although the effect in the case where an adhesive layer is non-energy-ray-curable was demonstrated, even if the layer which is in direct contact with the film for protective film formation of a support sheet is a layer other than an adhesive layer, if this layer is non-energy-ray-curable, the same show the effect.

<<The manufacturing method of an adhesive composition>>

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

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.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent and the compounding component may be used by diluting this compounding component in advance. You may use by mixing with these compounding components.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a 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.

◎Film for forming a protective film

The film for forming a protective film becomes a protective film with or without curing as it is. This protective film is for protecting the back surface (the surface opposite to the electrode formation surface) of a semiconductor wafer or a semiconductor chip. The film for protective film formation is soft and can be affixed to a sticking target object easily.

Sclerosis|hardenability may be sufficient as the said film for protective film formation, and non-hardening may be sufficient as it.

Any of thermosetting and energy-beam sclerosis|hardenability may be sufficient as the film for curable protective film formation, and may have the characteristic of both thermosetting and energy-beam sclerosis|hardenability.

The film for protective film formation can be formed using the composition for protective film formation containing the constituent material.

In this specification, "non-curable" means the property which does not harden|cure by any means, such as a heating and irradiation of an energy ray.

In the present invention, even after the film for forming a protective film is cured, as long as the laminate structure of the support sheet and the cured product of the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, this laminate is referred to as "forming a protective film". Composite sheet for use".

Regardless of the kind, the film for 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 protective film formation consists of multiple layers, these multiple layers may mutually be same or different.

Here again, the film for forming the pressure-sensitive adhesive layer and the protective film will be described in more detail with reference to FIG. 4 .

As described above, the first surface 11a of the substrate 11 is an uneven surface. However, in the adhesive layer 12, when the R value is less than 5.0, the influence of this uneven surface is suppressed, and the unevenness degree in the 1st surface 12a of the adhesive layer 12 becomes small easily. . For this reason, the lamination|stacking property of the adhesive layer 12 and the film 13 for protective film formation tends to become favorable. Moreover, when the said S value is 1.5 micrometers or more, the influence of this uneven|corrugated surface is suppressed, and the unevenness|corrugation degree in the 1st surface 12a of the adhesive layer 12 becomes small. For example, even if the area|region (non-bonding area|region) 92 in which these are not bonded exists between the adhesive layer 12 and the film 13 for protective film formation, the number is 1 A of composite sheets for protective film formation. Over the whole formation area of the film 13 for protective film formation in inside, it becomes 3 places or less, etc., and it becomes very few. The said non-bonding area|region 92 can be confirmed easily by observing 1 A of composite sheets for protective film formation from the base material 11 side, for example.

Moreover, even if 1 A of composite sheet|seat for protective film formation has such non-bonding area|region 92, the magnitude|size (interlayer distance) of the non-bonding area|region 92 in the thickness direction of 1 A of composite sheets for protective film formation (interlayer distance) is yes For example, the composite sheet 1A for protective film formation of 0.5 micrometer or less has more favorable lamination|stacking property of the adhesive layer 12 and the film 13 for protective film formation. Here, the "size (interlayer distance) of the non-bonding area|region 92" is "interlayer distance between the adhesive layer 12 in the thickness direction of 1 A of composite sheets for protective film formation, and the film 13 for protective film formation" ' means.

The size (the interlayer distance) of the non-bonded region 92 is preferably 0.5 μm or less, similar to the interlayer distance (size) of the non-bonded region 91 described above, for example, 0.4 μm or less, 0.3 μm or less. , 0.2 µm or less and 0.1 µm or less may be sufficient.

The size (interlayer distance) of the non-bonding region 92 is obtained in the same manner as in the case of the above-described non-bonding region 91 size (interlayer distance), except that, for example, the target two-layer combination is different. can

In 1 A of composite sheets for protective film formation, the non-bonding area|region 92 does not exist at all in some cases. In this specification, when the non-bonding area|region 92 does not exist at all, the magnitude|size (interlayer distance) of the non-bonding area|region 92 may be expressed by 0 micrometer.

On the other hand, as mentioned above, the unevenness|corrugation in the 1st surface 12a of the adhesive layer 12 becomes small easily. For this reason, although thickness T _p of the film 13 for protective film formation is not constant and fluctuates with the site|part of the film 13 for protective film formation (adhesive layer 12), the fluctuation range is very small.

Moreover, since the unevenness|corrugation in the 1st surface 12a of the adhesive layer 12 tends to become small as mentioned above, the adhesive layer 12 side surface (2nd surface) of the film 13 for protective film formation ( 13b) is smooth or tends to have small irregularities. Therefore, the external appearance of the film 13 for protective film formation is hard to be inhibited.

And also in the protective film formed from the film 13 for protective film formation, the surface (2nd surface) on the side (2nd surface) of the adhesive layer 12 is smooth, or unevenness|corrugation becomes small, and the external appearance of a protective film is easy to remain unimpeded.

Thus, in 1 A of composite sheet|seats for protective film formation, the film 13 for protective film formation and a protective film can make both into the thing excellent in designability.

In the 2nd surface 13b of the film 13 for protective film formation, it is preferable that the largest height difference between the highest part of a convex part and the deepest part of a recessed part is 2 micrometers or less, for example, 1.5 micrometers or less and 1 micrometer or less Either one may be sufficient. The film 13 for forming a protective film and the protective film are particularly excellent in designability.

The said maximum height difference in the 2nd surface 13b of the film 13 for protective film formation is cross-section in the test piece of the composite sheet for protective film formation or the composite sheet itself for protective film formation by the method described above, for example. It can be calculated|required by forming and observing this cross section using a scanning electron microscope (SEM).

Here, although 1 A of composite sheet for protective film formation was taken as an example and the film for adhesive layer and protective film formation was demonstrated, the protective film of other embodiment, such as the composite sheet 1B for protective film formation, and the composite sheet 1C for protective film formation Also in the case of the composite sheet for formation, the film for adhesive layer and protective film formation is the same.

In the composite sheet for forming a protective film of the present invention, the thickness (for example, T _p ) of the film for forming a protective film is preferably 1 to 100 µm, more preferably 3 to 75 µm, and 5 to 50 µm Especially preferred. When the thickness of the film for protective film formation is more than the said lower limit, a protective film with a higher protective ability can be formed. When the thickness of the film for protective film formation is below the said upper limit, becoming excessive thickness is suppressed.

When the thickness of the film for protective film formation fluctuates with the site|part of the film for protective film formation, the minimum value of the thickness of the film for protective film formation may be more than the said lower limit, Even if the maximum value of the thickness of the film for protective film formation is less than the said upper limit do.

In addition, the "thickness of the film for protective film formation" means the thickness of the whole film for protective film formation, For example, the thickness of the film for protective film formation which consists of multiple layers is the sum total of all the layers which comprise the film for protective film formation. means the thickness of

The thickness of the film for protective film formation can be measured, for example by observing the side surface or cross section of the film for protective film formation using a scanning electron microscope (SEM).

The cross section of the film for protective film formation can be formed by the method similar to the case of the cross section in the test piece of the support sheet and the composite sheet for protective film formation mentioned above, for example.

For example, by the method described above, a test piece is cut out from a plurality of places (for example, five places) of the composite sheet for forming a protective film, and the minimum and maximum values of the thickness of the film for forming a protective film in this test piece are obtained, and these Further, when the average value of these minimum values and the average value of the maximum values is obtained from the value of It may be below the upper limit of thickness.

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

Coating of the composition for protective formation may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, The method of using various coaters, such as a Mayer bar coater and a kiss coater, is mentioned.

Although the drying conditions of the composition for protective film formation are not specifically limited, When the composition for protective film formation contains the solvent mentioned later, it is preferable to heat-dry. And, it is preferable to dry the composition for protective film formation containing a solvent under conditions for 10 second - 5 minutes at 70-130 degreeC, for example. However, when the composition for protective film formation is thermosetting, it is preferable to dry the composition for protective film formation so that the film for protective film formation formed may not thermoset.

Hereinafter, the film for protective film formation and the composition for protective film formation are demonstrated in detail for each type.

○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.

The thermosetting component (B) is a component capable of curing (polymerization) reaction by using heat as a trigger of the reaction. On the other hand, in the present invention, the polymerization reaction also includes a polycondensation reaction.

After affixing the film for forming a thermosetting protective film on the back surface of the semiconductor wafer, curing conditions at the time of thermosetting are not particularly limited as long as the cured product has a degree of hardening to the extent that it sufficiently exhibits its function, Types of the film for forming a thermosetting protective film It should be selected appropriately.

For example, it is preferable that it is 100-200 degreeC, as for the heating temperature at the time of thermosetting of the film for thermosetting protective film formation, it is more preferable that it is 110-180 degreeC, It is especially preferable that it is 120-170 degreeC. The curing time is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.

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

Preferred compositions for forming a thermosetting protective film include, 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)” ' is sometimes abbreviated) and the like.

[Polymer component (A)]

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

The number of polymer components (A) 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.

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

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

It is preferable that it is 10000-2000000, and, as for the weight average molecular weight (Mw) of acrylic resin, it is more preferable that it is 100000-1500000. 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 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 it is -60-70 degreeC, and, as for the glass transition temperature (Tg) of acrylic resin, it is more preferable that it is -30-50 degreeC. When Tg of acrylic resin is more than the said lower limit, the adhesive force of the hardened|cured material of the film for protective film formation (namely, protective film) and a support sheet is suppressed, for example, and the peelability of a support sheet improves suitably. Moreover, when Tg of acrylic resin is below the said upper limit, the adhesive force with the to-be-adhered body of the film for thermosetting protective film formation and a protective film improves.

On the other hand, it is not limited to an acrylic resin, and Tg of the resin in the present specification is, for example, using a differential scanning calorimeter (DSC) at a temperature increase rate or temperature decrease rate of 10°C/min, and is between -70°C and 150°C. It can be calculated|required by changing the temperature of a measurement object and confirming an inflection point.

As acrylic resin, For example, 1 type(s) or the polymer of 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.

The (meth)acrylic acid ester constituting the acrylic resin includes, 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) acrylic acid tridecyl, (meth) acrylic acid tetradecyl ((meth) acrylate myristyl), (meth) acrylic acid pentadecyl, (meth) acrylate hexadecyl ((meth) Palmityl acrylate), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl (meth)acrylic acid alkyl ester, in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms. ;

(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, for example, in addition to the (meth) acrylic acid ester, (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide one or two or more types of monomers selected from What is formed by copolymerization may be sufficient.

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 couple|bond 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 with another compound directly 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 invention, 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 in combination with the acrylic resin. You can do it. By using the above-mentioned thermoplastic resin, the peelability of the protective film from the supporting sheet is improved, 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 it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

It is preferable that it is -30-150 degreeC, and, as for the glass transition temperature (Tg) of the said thermoplastic resin, it is more preferable that it is -20-120 degreeC.

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) ) is preferably 5-85 mass%, more preferably 5-75 mass%, for example, 5-65 mass%, 5-50 mass%, 10-35 mass%, etc. Either one may be sufficient.

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

[thermosetting component (B)]

A thermosetting component (B) is a component for hardening the film for thermosetting protective film formation.

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 to 30000, more preferably 300 to 10000, from the viewpoint of the curability of the film for forming a thermosetting protective film and the strength and heat resistance of the protective film after curing. And it is especially preferable that it is 300-3000.

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

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

In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of 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 carboxyl group, and a group in which an acid group is anhydrideized, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrideized is preferable, and a phenolic hydroxyl group, an amino group, or an acid group is an anhydride group. It is more preferable that it is a hydroxyl group or 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.

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 phenolic 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 resin components such as polyfunctional phenol resins, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins is preferably 300 to 30000, It is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

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

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.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (B1). Preferably, any one of 1-100 mass parts, 1-50 mass parts, 1-25 mass parts, and 1-10 mass parts etc. may be sufficient, for example. 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 100 content of the polymer component (A) It is preferable that it is 20-500 mass parts with respect to mass part, It is more preferable that it is 30-300 mass parts, It is still more preferable that it is 40-150 mass parts, For example, 45-100 mass parts, 50-80 mass parts, etc. Either one may be sufficient. When the said content of a thermosetting component (B) is such a range, the adhesive force of the hardened|cured material of the film for protective film formation, and a support sheet is suppressed, for example, 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).

Preferred curing accelerators (C) include, for example, 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 a curing accelerator (C) is used, the content of the curing accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is 0.01 to 10 parts by mass with respect to 100 parts by mass of the content of the thermosetting component (B) It is preferable, and it is more preferable that it is 0.1-7 mass parts. 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 and segregates in the film for forming a thermosetting protective film under high temperature and high humidity conditions The effect of suppressing a thing increases, 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), it becomes easier to control the water absorption rate and the change rate of the adhesive force within the target ranges. In addition, the film for forming a thermosetting protective film and the protective film contain the filler (D), so that the control of the coefficient of thermal expansion becomes easier, and by optimizing this coefficient of thermal expansion for the film for forming a thermosetting protective film or the object to be formed, the protective film is formed The reliability of the semiconductor chip with a protective film obtained using the composite sheet improves more. Moreover, the film for thermosetting protective film formation can reduce the moisture absorption of a protective film, or can also improve heat dissipation by containing a filler (D).

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, it is preferable that it is a silica or an alumina, and, as for an inorganic filler, it is more preferable that it is a silica.

The number of fillers (D) 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, these combinations and ratios can be arbitrarily selected.

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) ) is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, for example, any one of 20 to 65 mass%, 30 to 65 mass%, and 40 to 65 mass%. do. When content of a filler (D) is such a range, adjustment of the said thermal expansion coefficient becomes easier, and the intensity|strength of the film for protective film formation and a protective film improves more.

[Coupling agent (E)]

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 without impairing heat resistance of the hardened|cured material (protective film) of the film for thermosetting protective film formation by using a coupling agent (E).

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) 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 coupling agent (E), content of a coupling agent (E) in composition (III-1) and the film for thermosetting protective film formation is 100 mass parts of total content of a polymer component (A) and a thermosetting component (B) It is preferable that it is 0.03-20 mass parts with respect to it, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.1-5 mass parts. When the content of the coupling agent (E) is equal to or greater than the lower limit, the improvement of the dispersibility of the filler (D) to the resin, the improvement of the adhesion of the film for forming a thermosetting protective film to the adherend, etc., when using the coupling agent (E) effect is obtained more significantly. 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)]

When 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 with other compounds such as the above-mentioned acrylic resin is used, composition (III-1) ) and the film for thermosetting protective film formation may contain the crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking by bonding the functional group in the polymer component (A) with other compounds, and by crosslinking in this way, 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 polyvalent isocyanate compound, and an alicyclic polyhydric 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" refers to the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound, and a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. means the reactant. As an example of the said adduct body, the xylylene diisocyanate adduct of trimethylol propane as mentioned later, etc. are mentioned. 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-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; 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 the crosslinking agent (F) of composition (III-1) is 0.01-20 mass parts with respect to 100 mass parts of content of a polymer component (A), It is 0.1-10 mass parts It is more preferable, and it is especially preferable that it is 0.5-5 mass parts. 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 ray-curable resin (G) is obtained by superposing|polymerizing (hardening) an energy-beam curable compound.

As said energy-beam-curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, 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)acryl Rate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) (meth)acrylates containing a chain aliphatic skeleton such as acrylates; 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 it is 100-30000, and, as for the weight average molecular weight of the said energy-beam curable compound, it is more preferable that it is 300-10000.

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

The number of energy ray-curable resin (G) contained in the composition (III-1) may be one, two or more types may be sufficient, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

When using energy-beam curable resin (G), it is preferable that content of energy-beam curable resin (G) with respect to the total content of all components other than the solvent of composition (III-1) is 1-95 mass %, 5 It is more preferable that it is -90 mass %, and it is especially preferable that it is 10-85 mass %.

[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, two or more types may be sufficient, and when 2 or more types, these combinations and ratio can be selected arbitrarily.

When using a photoinitiator (H), it is preferable that content of the photoinitiator (H) of composition (III-1) is 0.1-20 mass parts with respect to content of 100 mass parts of energy ray-curable resin (G), 1 to It is more preferable that it is 10 mass parts, and it is especially preferable that it is 2-5 mass parts.

[Colorant (I)]

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 dioxazine 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 colorant (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 mark of the back surface of a semiconductor wafer. Taking this point into consideration, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all 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 it is -10 mass %, It is more preferable that it is 0.1-7.5 mass %, It is especially preferable that it is 0.1-5 mass %. 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 of this invention.

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 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]

The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent becomes favorable in handling property.

The solvent is not particularly limited, but preferably, 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, two or more types may be sufficient, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

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.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent and the compounding component may be used by diluting this compounding component in advance. You may use by mixing with these compounding components.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a 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.

○Film for energy ray-curable protective film formation

What contains an energy-beam curable component (a) is mentioned as a film for energy-beam curable protective film formation, It is preferable to contain an energy-beam curable component (a) and a filler.

In the film for energy ray-curable protective film formation, it is preferable that the energy ray-curable component (a) is non-hardened, 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 previously demonstrated.

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

For example, it is preferable that the illuminance of the energy ray at the time of hardening of the film for energy ray-curable protective film formation is 120-280 mW/cm<2>. And it is preferable that the light quantity of the energy ray at the time of the said hardening is 100-1000 mJ/cm<2>.

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

As a preferable composition for energy-ray-curable protective film formation, for example, the composition (IV-1) for energy-beam-curable protective film formation containing the said energy-beam curable component (a) (in this specification, simply "composition (IV-1) )"), etc. are mentioned.

[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 to 2000000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000. . As for the said polymer (a1), at least one part may be crosslinked by the crosslinking agent, and the thing which is not crosslinked may be sufficient as it.

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

As the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000, for example, an acrylic polymer (a11) having a functional group capable of reacting with a group of other compounds, 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 a group 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 having the functional group (a11) include those obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer not having the functional group. In addition to these monomers, monomers other than the acrylic monomer ( Non-acrylic monomer) may be copolymerized.

In addition, a random copolymer may be sufficient as the said acrylic polymer (a11), and 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) acrylic acid 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 can be arbitrarily selected.

The acrylic monomer having no functional group includes, 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 (( Also called lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also called myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ((meth) (also called palmityl acrylate), (meth) acrylate heptadecyl, (meth) acrylate octadecyl (also called (meth) stearyl (meth) acrylate), wherein the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms (meth) ) acrylic acid alkyl ester;

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 which has 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 to 50% by mass, and 1 to 40 It is more preferable that it is mass %, and it is especially preferable that it is 3-30 mass %. When the ratio is within this range, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12), the content of the energy ray-curable group depends on the curing of the protective film. The degree can be easily adjusted to a desired range.

The number of the acrylic polymer (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 it is 1-70 mass %, It is more preferable that it is 5-60 mass %, It is especially preferable that it is 10-50 mass %.

・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 1-5 pieces of the said energy-beam curable groups in 1 molecule, and, as for the said energy-beam-curable compound (a12), it is more preferable to have 1-3 pieces.

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.

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) in the acrylic resin (a1-1) is 20 to 120 mol% It is preferable that it is 35-100 mol%, It is more preferable, It is especially preferable that it is 50-100 mol%. 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 per molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) In the case of a polyfunctional (having two or more groups in one molecule) compound, the upper limit of the content ratio may exceed 100 mol%.

It is preferable that it is 100000-200000, and, as for the weight average molecular weight (Mw) of the said polymer (a1), it is more preferable that it is 300000-150000.

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

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

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80000)

Examples of the energy-ray-curable group in the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80000 include a group containing an energy-ray-curable double bond, and preferable examples include a (meth)acryloyl group, a vinyl group, and the like. can

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.

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

As the acrylate-based compound, for example, 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, ditrimethylol propane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyfunctional (meth)acrylates such as dipentaerythritol poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

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

Among the compounds (a2), as an epoxy resin having an energy ray-curable group and a phenol resin having an energy ray-curable group, those described in Paragraph 0043 of “Unexamined Patent Application Publication No. 2013-194102” can be used. Although such a resin also corresponds to resin which comprises the thermosetting component mentioned later, in this invention, it handles as said compound (a2).

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said compound (a2), it is more preferable that it is 300-10000.

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 one in which at least a part thereof is crosslinked 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 (meth)acrylic acid esters containing a substituted amino group. 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 (( (meth) acrylic acid lauryl), (meth) acrylic acid tridecyl, (meth) acrylic acid tetradecyl ((meth) acrylate myristyl), (meth) acrylic acid pentadecyl, (meth) acrylic acid hexadecyl ((meth) acrylate palmityl) , (meth)acrylic acid alkyl ester, wherein the alkyl group constituting the alkyl ester such as heptadecyl (meth)acrylate and octadecyl (meth)acrylate (stearyl (meth)acrylate) has a chain structure having 1 to 18 carbon atoms. there is.

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) having no 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 the case where the crosslinking agent is an epoxy compound, the reactive functional group includes a carboxy group, an amino group, and an amide group, 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 ray-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 and non-acrylic monomers used as monomers constituting the acrylic polymer (b-1) may be those having the reactive functional group. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerization of a hydroxyl group-containing (meth)acrylic acid ester. What was obtained by superposing|polymerizing the monomer which consists of the above hydrogen atoms substituted with the said reactive functional group is mentioned.

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

Since the film-forming property of a composition (IV-1) becomes more favorable, it is preferable that it is 10000-200000, and, as for the weight average molecular weight (Mw) of the polymer (b) which does not have an energy-ray-curable group, it is more preferable that it is 100000-1500000 . Here, the "weight average molecular weight" is as described above.

The number of polymers (b) which does not contain an energy-ray-curable group which the composition (IV-1) and the film for energy-ray-curable protective film formation contain may be one, or two or more types may be sufficient, and when 2 or more types, these combinations and ratio can be arbitrarily selected.

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, and in this case, further containing (a1) It is also desirable 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 it is 10-400 mass parts 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, and it is more preferable that it is 30-350 mass parts.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (that is, for energy ray-curable protective film formation) It is preferable that it is 5-90 mass %, and, as for the total content of the said energy-beam curable component (a) and the polymer (b) which does not have an energy-beam curable group of a film), it is more preferable that it is 10-80 mass %, It is 20-70 It is especially preferable that it is mass %. 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.

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 energy ray-curable component. do.

For example, in the film for forming an energy ray-curable protective film formed by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component, the adhesive force to the adherend is improved by heating, and this energy ray The strength of the protective film formed from the film for curable protective film formation also improves.

In addition, the film for forming an energy ray-curable protective film formed by using the composition (IV-1) containing the energy ray-curable component and the colorant has the same effect as when the above-described film for forming a thermosetting protective film contains the colorant (I) to express

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 photoinitiator, 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.

Contents 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 are 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) described above.

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.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent and the compounding component may be used by diluting this compounding component in advance. You may use by mixing with these compounding components.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a 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.

○Film for non-curable protective film formation

Although the said film for non-curable protective film formation does not show the change of the characteristic by hardening, in this invention, it is considered that the protective film was formed in the step of sticking to the target location, such as the said back surface of a semiconductor wafer.

As a preferable film for non-hardening protective film formation, the thing containing a thermoplastic resin is mentioned, for example.

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

As the composition for forming a non-curable protective film, for example, the composition (V-1) for forming a non-curable protective film containing the above-mentioned thermoplastic resin (in this specification, it may be simply abbreviated as "composition (V-1)" ) and the like.

[Thermoplastic resin]

The said thermoplastic resin is not specifically limited.

More specifically, as the thermoplastic resin, for example, curability of acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. and the same resin as the other resins.

The number of the thermoplastic resins contained in the composition (V-1) and the film for forming a non-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.

It is preferable that the ratio of the content of the thermoplastic resin to the total content of components other than the solvent in the composition (V-1) (that is, the content of the thermoplastic resin in the film for forming a non-curable protective film) is 5 to 90% by mass, , For example, any one of 10-80 mass %, 20-70 mass %, etc. may be sufficient.

Composition (V-1) may contain 1 type(s) or 2 or more types chosen 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 thermoplastic resin.

For example, the film for forming a non-curable protective film formed by using the composition (V-1) containing the thermoplastic resin and the colorant has the same effect as when the above-described film for forming a thermosetting protective film contains the colorant (I). to manifest

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

In the composition (V-1), each of the filler, coupling agent, crosslinking agent, colorant and general-purpose additive may be used alone, in combination of two or more, or in combination of two or more. and the ratio can be arbitrarily selected.

Content of the said filler in a composition (V-1), a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose additive 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) described above.

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>>

A composition for forming a non-hardening 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.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent and the compounding component may be used by diluting this compounding component in advance. You may use by mixing with these compounding components.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a 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.

◎Other floors

The said support sheet may be equipped with other layers, such as the said intermediate|middle layer, in addition to a base material and an adhesive layer within the range which does not impair the effect of this invention.

In addition, the composite sheet for forming a protective film may include other layers other than the base material, the pressure-sensitive adhesive layer and the film for forming a protective film within the range that does not impair the effects of the present invention, and in this case, the other layer is a support sheet The other layer provided may be sufficient, and it may be arrange|positioned, without direct contact with a support sheet.

The other layer may be arbitrarily selected according to the purpose, and the type thereof is not particularly limited.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer includes at least the acrylic polymer having a structural unit derived from (meth)acrylic acid alkylester and a crosslinking agent. The content of the crosslinking agent with respect to 100 parts by mass of the content of the acrylic polymer in the pressure-sensitive adhesive layer is 0.3 to 50 parts by mass, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 μm. can be heard

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer includes at least the acrylic polymer having a structural unit derived from (meth)acrylic acid alkylester and a crosslinking agent. The content of the crosslinking agent with respect to 100 parts by mass of the content of the acrylic polymer in the pressure-sensitive adhesive layer is 0.3 to 50 parts by mass, and the acrylic polymer has a structural unit and a hydroxyl group derived from (meth)acrylic acid alkylester having 4 or more carbon atoms in the alkyl group. What has a structural unit derived from a containing monomer and the said maximum height roughness (Rz) of the 1st surface of a base material is 0.01-8 micrometers is mentioned.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer includes at least the acrylic polymer having a structural unit derived from (meth)acrylic acid alkylester and a crosslinking agent. The content of the crosslinking agent with respect to 100 parts by mass of the content of the acrylic polymer in the pressure-sensitive adhesive layer is 0.3 to 50 parts by mass, and the acrylic polymer has a structural unit and a hydroxyl group derived from (meth)acrylic acid alkylester having 4 or more carbon atoms in the alkyl group. It has a structural unit derived from a containing monomer, and in the said acrylic polymer, content of the structural unit derived from a hydroxyl-containing monomer is 1-35 mass % with respect to the total amount of a structural unit, and the said maximum height roughness of the 1st surface of a base material (Rz) of 0.01-8 micrometers is mentioned.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer includes at least the acrylic polymer having a structural unit derived from (meth)acrylic acid alkylester and a crosslinking agent. The content of the crosslinking agent with respect to 100 parts by mass of the content of the acrylic polymer in the pressure-sensitive adhesive layer is 0.3 to 50 parts by mass, and the acrylic polymer has a structural unit and a hydroxyl group derived from (meth)acrylic acid alkylester having 4 or more carbon atoms in the alkyl group. It has a structural unit derived from a containing monomer, and in the acrylic polymer, the content of the structural unit derived from the hydroxyl group-containing monomer is 1-35 mass % with respect to the total amount of the structural unit, the crosslinking agent is an isocyanate-based crosslinking agent, and It is mentioned that the said maximum height roughness (Rz) of a 1st surface is 0.01-8 micrometers.

◇Manufacturing method of composite sheet for protective film formation

The composite sheet for forming a protective film is, for example, a step of producing a laminated sheet in which a base material, a pressure-sensitive adhesive layer, and a film for forming a protective film are laminated in this order in their thickness direction (in this specification, “laminated sheet production process”) (1)"), and a process of preserving the laminated sheet while pressurizing in its thickness direction (in this specification, it may be referred to as a "laminated sheet storage process"); In the specification, it may be referred to as "manufacturing method (S1)").

The formation method of each layer (the base material, the adhesive layer, and the film for protective film formation) is as described above.

Hereinafter, the manufacturing method (S1) will be described in more detail for each step.

◎Manufacturing method (S1)

<<Laminated sheet manufacturing process (1)>>

In the said laminated sheet manufacturing process (1), the laminated sheet comprised by laminating|stacking a base material, an adhesive layer, and the film for protective film formation in these thickness direction in these order is produced.

In this step, for example, by laminating each of the above-described layers (base material, pressure-sensitive adhesive layer, film for forming a protective film, etc.) in a corresponding positional relationship, a laminate sheet having the same laminate structure as the target composite sheet for forming a protective film to produce

In the present specification, the term "laminated sheet" means that, unless otherwise specified, it has the same laminated structure as that of the composite sheet for forming a protective film for the same purpose as described above, and the laminated sheet storage step is not performed. .

For example, when manufacturing a support sheet and laminating|stacking an adhesive layer on a base material, what is necessary is just to coat the adhesive composition mentioned above on a base material, and to dry as needed.

On the other hand, for example, in the case of further laminating the film for forming a protective film on the pressure-sensitive adhesive layer laminated on the substrate, it is possible to directly form the film for forming the protective film by coating the composition for forming a protective film on the pressure-sensitive adhesive layer. Layers other than the film for forming a protective film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming the layer. In this way, when any one composition is used to form a laminated structure of two consecutive layers, 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 on the opposite side 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 as needed after formation of a laminated structure.

For example, a composite sheet for forming a protective film in which a pressure-sensitive adhesive layer is laminated on a substrate and a film for forming a protective film is laminated on the pressure-sensitive adhesive layer (a composite sheet for forming a protective film in which the support sheet is a laminate of a substrate and an adhesive layer) In the case of doing, by coating the pressure-sensitive adhesive composition on the substrate and drying as necessary, the pressure-sensitive adhesive layer is laminated on the substrate, and separately coating the composition for forming a protective film on the release film, and drying as necessary, the release film A film for forming a protective film is formed thereon. And the said lamination sheet is obtained by bonding the exposed surface of this film for protective film formation together with the exposed surface of the adhesive layer laminated|stacked on the base material, and laminating|stacking the film for protective film formation on the 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 applied on the release film and dried as necessary, thereby forming the pressure-sensitive adhesive layer on the release film. may be formed and the pressure-sensitive adhesive layer may be laminated on the substrate by bonding the exposed surface of this layer to one surface of the substrate.

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

In this way, all layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming in advance on the release film and bonding to the surface of the target layer. What is necessary is just to select a layer suitably and to manufacture the said lamination|stacking sheet.

For example, the composite sheet for protective film formation is normally stored in the state by which the peeling film was pasted by the surface of the outermost layer (for example, film for protective film formation) on the opposite side to the support sheet. Therefore, on this peeling film (preferably, the peeling process surface), the composition for forming layers which comprise outermost layers, such as a composition for protective film formation, is coated, and by drying as needed, the outermost layer on a peeling film. A state in which a layer constituting a release film is formed, and the remaining respective layers are laminated on the exposed surface opposite to the side in contact with the release film of this layer by any one of the methods described above, and are bonded without removing the release film. Also by setting it as it is, the said lamination|stacking sheet is obtained.

In the case where the composite sheet for forming a protective film includes the other layer, the step of forming the other layer may be appropriately added so that an arrangement position suitable for a suitable timing of the above-described laminated sheet production step (1) may be obtained.

The shape of the said lamination sheet produced in the lamination sheet preparation process (1) is not specifically limited. For example, in order to wind up as a roll shape, although a preferable long lamination sheet may be produced, you may produce the lamination sheet of a shape other than elongate.

<<Lamination sheet preservation process>>

In the said lamination sheet storage process, it preserve|saves, pressurizing the said lamination sheet in the thickness direction.

As a method of preserving the laminated sheet while pressurized in this step, for example, the long laminated sheet is wound in a roll shape, the wound laminated sheet is left as it is, and the pressure generated by winding is applied to the laminated sheet. method of preserving while applying to one or both sides of A method of storing the long laminated sheet in an expanded state without winding it up in a roll shape, or a method of storing the long laminated sheet while applying pressure to one side or both surfaces of the non-long laminated sheet.

When winding up a long lamination sheet in roll shape, it is preferable to wind up a lamination sheet in the longitudinal direction.

When winding the laminated sheet, for example, the winding tension is preferably 150 to 170 N/m, the winding speed is preferably 45 to 55 m/min, and the taper ratio (reduction rate) of the winding tension is 85 to 95%. It is preferable to be By employing such winding conditions, the laminated sheet can be stored under pressure at a more suitable pressure. Such winding conditions are particularly preferable to be applied to, for example, a laminated sheet having a thickness of 100 to 300 μm, a width of 300 to 500 mm, and a length of 40 to 60 m, but the size of the laminated sheet is not limited thereto.

The lamination sheet may be wound under normal temperature or room temperature, for example, and as will be described later, the laminated sheet may be wound under the same temperature conditions as when the wound lamination sheet is stored under heat and pressure.

Although the lamination sheet wound up in roll shape may be stored under normal temperature or room temperature, it is preferable to preserve|save, heating. Thus, by heat-pressing preservation|save, the composite sheet for protective film formation more excellent in the lamination property of an adhesive layer and the film for protective film formation, and printing visibility through the support sheet of a protective film or the film for protective film formation is obtained.

When a lamination sheet is wound up in roll shape, although the heating temperature at the time of storage is not specifically limited, It is preferable that it is 53-75 degreeC, It is more preferable that it is 55-70 degreeC, It is especially preferable that it is 57-65 degreeC.

The storage time when the laminated sheet is wound into a roll is not particularly limited, but it is preferably 24 to 720 hours (1 to 30 days), more preferably 48 to 480 hours (2 to 20 days), and 72 to It is especially preferable that it is 240 hours (3-10 days).

In a laminated sheet wound in roll shape, for example, a film for forming a protective film and a support sheet are processed into a specific shape, and a plurality of laminates of the support sheet and film for forming a protective film processed in this way are formed on the film side for forming a protective film. WHEREIN: While bonding to the elongate peeling film, in the longitudinal direction of this peeling film, it may arrange and arrange|position. It is preferable that the film for protective film formation in this case has the same or substantially the same planar shape (normally circular shape) as a semiconductor wafer. In addition, it is preferable that the support sheet in this case has the same or substantially the same outer peripheral shape as the jig for fixing the support sheet in a dicing apparatus. Moreover, in this case, it is preferable that the strip|belt-shaped sheet|seat is formed in the vicinity of the periphery of the width direction among the bonding surfaces of the said laminated body of a peeling film so that it may not overlap with the said laminated body in this case. This sheet is for suppressing the occurrence of a level difference (in this specification, sometimes referred to as a "lamination trace") on the surface of the laminate when the laminated sheet is wound into a roll. The lamination traces indicate that the lamination positions of the laminates (the laminate of the processed support sheet and the film for forming a protective film) among the rolls of the laminated sheet do not coincide in the radial direction of the roll, so that a high pressure is applied to the surface of the laminate. arises as a burden. When the sheet is formed in the vicinity of the periphery, such a high pressure is not applied to the surface of the laminate, and the generation of traces of the lamination is suppressed.

In the case where the elongated lamination sheet is not wound in a roll shape and is in an expanded state, and when the lamination sheet is not long, it is preferable to further laminate and store a plurality of these lamination sheets. In addition, when laminating|stacking a lamination sheet in this way, it is preferable to make into the state which matched the direction of these lamination|stacking sheets and the position of a periphery of a plurality of sheets with each other.

The shape and size of the non-long laminated sheet (that is, the sheet laminated sheet) are not particularly limited. For example, in accordance with the shape and size of the semiconductor wafer and the shape and size of a jig for fixing the support sheet in the dicing apparatus, the shape of the laminated sheet is suitable for processing one semiconductor wafer using the dicing apparatus. And it is preferable that the size is adjusted.

The laminated sheet in the laminated state may be stored at room temperature or at room temperature, but is preferably stored while heating. Thus, by heat-pressing preservation|save, the composite sheet for protective film formation more excellent in the lamination property of an adhesive layer and the film for protective film formation, and printing visibility through the support sheet of a protective film or the film for protective film formation is obtained.

In addition, both the heating temperature and storage time in the case of pressurizing the said laminated sheet in a laminated state can be made the same as that when the above-mentioned laminated sheet is wound up in roll shape.

In manufacturing method (S1), after completion|finish of a laminated sheet preservation|save process, the target composite sheet for protective film formation is obtained by canceling|releasing the pressurization of a laminated sheet and heating as needed.

In the lamination sheet preparation step (1) of the manufacturing method (S1), the order of lamination (bonding) of the base material, the pressure-sensitive adhesive layer, and the film for forming a protective film is not particularly limited, but the support sheet is prepared in advance (adhesive in advance on the base material) layers) to separately prepare a film for forming a protective film in advance, and when laminating the film for forming a protective film on a support sheet, either one or both of the support sheet and the film for forming a protective film alone, before laminating them You may pressurize and preserve|save by the method similar to the case of the laminated sheet mentioned above. By pressure-preserving independently the support sheet before lamination|stacking, generation|occurrence|production of the said non-bonding area|region between a base material and an adhesive layer can be suppressed more effectively. In addition, by pressure-preserving the film for forming a protective film before lamination alone, the unevenness of the pressure-sensitive adhesive layer side surface (second surface) of the film for forming a protective film and the protective film becomes small (smoothness increases), and the film for forming a protective film and the protective film Designability is improved.

That is, the composite sheet for forming a protective film is, for example, by laminating the film for forming a protective film on the pressure-sensitive adhesive layer of the support sheet on which the base material and the pressure-sensitive adhesive layer are laminated, so that the substrate, the pressure-sensitive adhesive layer and the film for forming the protective film are formed in this order. A step of producing a laminated sheet configured to be laminated in the thickness direction of having a step (preservation step), and before the lamination sheet production step (2) (that is, before laminating the support sheet and the film for forming a protective film), either or both of the support sheet and the film for forming a protective film, respectively; The process of preserving while pressurizing in the thickness direction (In this specification, the process of preserving a support sheet is called "support sheet preservation process", and the process of preserving the film for protective film formation is called "film preservation process for protective film formation." It can manufacture by the manufacturing method (in this specification, it may call "manufacturing method (S2)") further having).

◎Manufacturing method (S2)

The manufacturing method (S2) performs the laminated sheet manufacturing process (2) as the above-described laminated sheet manufacturing process (1), and further performs either or both of the support sheet preservation process and the film preservation process for forming a protective film. Except for the point, it is the same as the above-mentioned manufacturing method (S1).

<<Laminated sheet manufacturing process (2)>>

In the lamination sheet production step (2), as described above, a support sheet is prepared in advance, a film for forming a protective film is separately prepared in advance, and a film for forming a protective film is laminated on the support sheet, so the lamination order of each layer It is the same as that of the lamination sheet preparation process (1) in manufacturing method (S1) except the point where is limited.

<<support sheet preservation process, film preservation process for protective film formation>>

The support sheet preservation step and the film storage step for forming a protective film can be performed in the same manner as the stacked sheet preservation step in the manufacturing method (S1), except that the storage object is a support sheet or a film for forming a protective film, rather than a laminated sheet, respectively. there is.

In this case, for example, the storage time of the support sheet and the film for forming a protective film is, as in the case of the laminated sheet, each independently 24-720 hours (1-30 days), 48-480 hours (2-20 days), and Any of 72 to 240 hours (3 to 10 days) may be sufficient.

On the other hand, the support sheet preservation step and the film preservation step for forming a protective film are added to change the storage object as described above, respectively, and also change the storage time of the storage object (support sheet or film for forming a protective film), and these You may perform similarly to the lamination sheet preservation|save process in manufacturing method S1 except a change point.

In this case, for example, the storage times of the support sheet and the film for forming a protective film are each independently 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours (0.5 to 10 days) may be used. However, this is an example of the said retention time.

Example

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

<The raw material for manufacturing the composition for forming a protective film>

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

・Polymer component (A)

(A)-1: Acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight 370000, glass transition temperature 6°C)

· Thermosetting component (B1)

(B1)-1: Bisphenol A 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 (“Epiclon HP-7200HH” manufactured by DIC, epoxy equivalent 255 to 260 g/eq)

· Thermosetting agent (B2)

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

・Cure accelerator (C)

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

·Filling material (D)

(D)-1: Silica filler ("SC2050MA" manufactured by Admatex, silica filler surface-modified with an epoxy compound, average particle diameter of 0.5 µm)

・Coupling agent (E)

(E) -1: 3-aminopropyl trimethoxysilane ("A-1110" manufactured by NUC)

・Colorant (I)

(I)-1: black pigment (manufactured by Dainichi Chemical Company)

[Example 1]

<Manufacture of a support sheet>

(Preparation of adhesive composition (I-4))

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 , Toluene, and the solid content concentration containing the mixed solvent of ethyl acetate produced the 30 mass % non-energy-ray-curable adhesive composition (I-4). 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-hydroxylethyl acrylate (HEA) (20 parts by mass).

(Manufacture of support sheet)

Using 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 pressure-sensitive adhesive composition (I-4) obtained above is applied to the peeling-treated surface was coated and dried by heating at 120°C for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer. At this time, conditions were set so that the thickness of an adhesive layer might be set to 4 micrometers, and the adhesive composition (I-4) was coated.

A polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., thickness 80 μm) is sandwiched between a metal roll having an uneven surface and a metal roll having a smooth surface, and the uneven surface of the metal roll is heated to 60° C. on one surface of the polypropylene film. By rotating and pressurizing it while it was being pressurized, the base material whose one surface is an uneven surface and the other surface is a smooth surface (glossy surface) was produced. It was 1.8 micrometers when the R value of the base material was measured similarly to the R value of an adhesive layer about the uneven|corrugated surface of this base material.

Next, by bonding the uneven surface of the said base material to the exposed surface of the adhesive layer obtained above, the base material, an adhesive layer, and a peeling film were laminated|stacked in these thickness directions in this order, and the support sheet comprised was obtained. The width of the obtained support sheet (that is, the width of the base material and the pressure-sensitive adhesive layer) was 400 mm, and the length was 250 m.

By the above, the support sheet of this invention was obtained.

Then, about this support sheet, evaluation about the non-bonding area|region between the base material mentioned later and an adhesive layer immediately was performed. In addition, this support sheet was used for manufacture of the composite sheet for protective film formation mentioned later in the state.

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

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

Polymer component ((A)-1) (150 parts by mass), thermosetting component ((B1)-1) (60 parts by mass), ((B1)-2) (10 parts by mass), ((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. , the solid content concentration obtained a composition (III-1) for forming a thermosetting protective film of 51 mass%. In addition, all the compounding quantities shown here are solid content.

(Production of film for forming a protective film)

A release film (second 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 is used, and a knife coater is used on the peeling treatment surface The 25-micrometer-thick film for thermosetting protective film formation was manufactured by coating the composition (III-1) for protective film formation obtained above, and drying at 100 degreeC for 2 minutes.

Furthermore, by bonding the peeling surface of the peeling film (1st peeling film, Lintec company "SP-PET381031", 38 micrometers) to the exposed surface of the side which is not equipped with the 2nd peeling film of the obtained film for protective film formation by bonding. The 1st peeling film was provided in one side of the film for protective film formation, and the laminated|multilayer film provided with the 2nd peeling film in the other side was obtained. The width (that is, the film for protective film formation, the 1st peeling film, and the 2nd peeling film) of the obtained laminated|multilayer film was 400 mm.

(Manufacture of composite sheet for forming a protective film)

One set (two) of rolls having a diameter of 5 cm and a region having a depth of 3 mm from the surface of which is made of a heat-resistant silicone rubber having a hardness of 50 degrees was prepared.

The peeling film was removed from the adhesive layer of the support sheet obtained above. Moreover, the 1st peeling film was removed from the laminated|multilayer film obtained above.

Then, the exposed surface of the pressure-sensitive adhesive layer formed by removing the release film and the exposed surface of the protective film forming film formed by removing the first release film are made to face each other, and these supporting sheets and the protective film forming film are overlapped and laminated While using water, this laminate was heat-pressed (heat laminated) at a pressure of 0.5 MPa by passing through the gap between these rolls whose temperature was set to 60 degreeC at a speed|rate of 0.3 m/min. Thereby, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film, and the second release film are laminated in this order in their thickness direction, and a laminate sheet having the same laminate structure as the target composite sheet for forming a protective film (before storage composite sheet for forming a protective film) was produced.

In the obtained laminated sheet, the width (that is, the width of the support sheet) was 400 mm.

Next, the overall size of the laminated sheet obtained above is 400 mm x 250 m, the longitudinal direction is the winding direction, and the winding tension is 160 N/m, the winding speed is 50 m/min, and the ABS resin under the conditions of a taper rate of 90% of the winding tension. It was wound around the core of , and wound up in roll shape. At this time, the laminated sheet was wound up with the base material facing outward in the radial direction of the roll (that is, the second release film was brought into contact with the core).

Next, this roll-shaped lamination sheet was left still and stored for 7 days (168 hours) on the temperature condition of 60 degreeC in an air atmosphere.

By the above, the composite sheet for protective film formation of this invention which has a structure shown in FIG. 2 was obtained.

Next, the items shown below were evaluated about the composite sheet for protective film formation of this invention after completion|finish of storage under such heating and pressurization conditions.

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

(Measurement of R value of the pressure-sensitive adhesive layer)

A test piece having a size of 3 mm x 3 mm was cut out from five locations of the composite sheet for forming a protective film obtained above. The cut-out positions of these five places were one corresponding to the central portion and four portions in the vicinity of the periphery of the circular protective film formation film, and four positions corresponding to approximately the position of the point with respect to the central portion. Among the cutting positions of these five places, the distance between the centers of one place corresponding to the center and four places in the vicinity of the periphery other than that was 100 mm.

Using a cross-section sample preparation device (“Cross Section Polisher SM-09010” manufactured by JEOL), the intermittent shutter conditions were set to “in” for 10 seconds and “out” for 5 seconds, the voltage of the ion source was set to 3 kV, and the total polish Time was set to 24 hours, and the cross section was formed from the said test piece. The cross section to be newly formed was made into only one side per specimen of one sheet.

Using a scanning electron microscope (SEM), the newly formed cross-sections of these five test pieces were observed, and for each test piece, the (sum of the linear distances between adjacent significant vertices) of the pressure-sensitive adhesive layer/(linear distance in the horizontal direction to the pressure-sensitive adhesive layer) ) of the rain was obtained. The observation area of the cross section of the test piece at this time was made into the area|region of 1 mm in the width direction of the said cross section.

And the average value of these ratios was employ|adopted as R value of an adhesive layer. A result is shown in Table 1.

In addition, the measuring method and calculating|requiring method of R value of a base material are the same as the measuring method and calculating|requiring method of R value of an adhesive layer.

(Evaluation of print visibility of protective film)

The 2nd peeling film was removed from the composite sheet for protective film formation obtained above, and the exposed surface (surface opposite to the adhesive layer side) of the film for protective film formation produced by this was affixed on the back surface of an 8-inch semiconductor wafer. The affixing at this time was performed using the tape mounter ("RAD2700" by Lintec Corporation). Thereby, the 1st laminated structure comprised by laminating|stacking a base material, an adhesive layer, the film for protective film formation, and a semiconductor wafer in these thickness direction in this order was produced.

Next, using a laser printing device ("CSM300M" manufactured by EO Technics Co., Ltd.), in the protective film formation film in the first laminated structure, the pressure-sensitive adhesive layer side surface (second surface) was printed by irradiating a laser beam through a support sheet. . At this time, a character having a size of 0.3 mm x 0.2 mm was printed.

Next, the printing (laser printing) of this film for protective film formation was visually observed through the support sheet, and the following reference|standard evaluated the visibility of printing (character). A result is shown in Table 1. It can be considered that the printing visibility of the film for protective film formation evaluated here is equivalent to the printing visibility of a protective film.

A: Printing is clear and can visually recognize easily.

B: Printing is slightly cloudy and cannot be visually recognized easily.

C: Printing is unclear and cannot be recognized.

Next, the support sheet (base material and adhesive layer) was peeled from this film for protective film formation. And the thickness of the line|wire of the printing|printing (letter) currently formed in the film for protective film formation was measured using the optical microscope. As a result, the thickness of the line was 40 µm or more, and it was clearly printed.

(Evaluation of the adhesion between the base material and the pressure-sensitive adhesive layer)

According to JIS K 5600-5-6, 100 grids were given in a grid shape of 1 mm in width and length with a rotary cutter to the pressure-sensitive adhesive layer of the support sheet, and the pressure-sensitive adhesive tape (Cellotape [Nichiban Corporation, registered trademark]) was pressed. Then, the adhesive tape was tested about the adhesiveness of a base material and an adhesive layer by counting the number of remaining grids in 100 grids when the adhesive tape was peeled at an angle of about 60 degrees in 0.5 second - 1.0 second. Adhesive evaluation was performed on the following criterion. And the following reference|standard evaluated the adhesiveness of a base material and an adhesive layer. A result is shown in Table 1.

A: The number of remaining grids is 90 or more.

B: The number of remaining grids is 70 or more and less than 90.

C: The number of remaining grids is less than 70.

<Production of a support sheet and a composite sheet for forming a protective film, and evaluation of a support sheet and a composite sheet for forming a protective film>

[Example 2]

In Example 1, when the concave-convex surface of the metal roll is rotated and pressed while heating to 60° C. on one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., thickness 80 µm), a metal roll having an uneven surface and a smooth surface In the same manner as in Example 1, except that the gap between the metal rolls having As a result of measuring the R value of the base material with respect to the uneven surface of this base material, it was 2.8. A support sheet was prepared and evaluated in the same manner as in Example 1, except that this base material was used.

And the composite sheet for protective film formation was manufactured and evaluated by the method similar to the case of Example 1 except the point using such a support sheet.

A result is shown in Table 1.

[Example 3]

In Example 2, when the uneven surface of the metal roll is rotated and pressed while heating to 60° C. on one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., thickness 80 μm), the metal roll having an uneven surface and a smooth surface In the same manner as in Example 2, except that the gap between the metal rolls having As a result of measuring the R value of the base material with respect to the uneven surface of this base material, it was 3.7. A support sheet was prepared and evaluated in the same manner as in Example 1, except that this base material was used.

And the composite sheet for protective film formation was manufactured and evaluated by the method similar to the case of Example 1 except the point using such a support sheet.

A result is shown in Table 1.

[Comparative Example 1]

In Example 1, when the concave-convex surface of the metal roll is rotated and pressed while heating to 60° C. on one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., thickness 80 µm), a metal roll having an uneven surface and a smooth surface In the same manner as in Example 1, except that the gap between the metal rolls having It was 1.0 as a result of measuring the R value of the base material with respect to the uneven|corrugated surface of this base material. A support sheet was prepared and evaluated in the same manner as in Example 1, except that this base material was used.

And the composite sheet for protective film formation was manufactured and evaluated by the method similar to the case of Example 1 except the point using such a support sheet.

A result is shown in Table 1.

[Comparative Example 2]

In Example 3, when the concave-convex surface of the metal roll is rotated and pressed while heating to 60° C. on one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., thickness 80 µm), a metal roll having an uneven surface and a smooth surface In the same manner as in Example 3, except that the gap between the metal rolls having As a result of measuring the R value of the base material with respect to the uneven surface of this base material, it was 5.7. A support sheet was prepared and evaluated in the same manner as in Example 1, except that this base material was used.

And the composite sheet for protective film formation was manufactured and evaluated by the method similar to the case of Example 1 except the point using such a support sheet.

And the composite sheet for protective film formation was manufactured and evaluated by the method similar to the case of Example 1 except the point using such a support sheet.

A result is shown in Table 1.

Evidently from the said result, in Examples 1-3, R value of an adhesive layer was 2 or more (2-4), and it was especially excellent in the adhesiveness of a base material and an adhesive. Moreover, in these Examples, R value of the said adhesive layer was less than 5.0 (2-4), and it was especially excellent in the printing visibility through the support sheet of the protective film and the film for protective film formation.

On the other hand, in the comparative example 1, R value of an adhesive layer was 1.2, the adhesiveness between a base material and an adhesive was not enough, and the non-bonding area|region existed between a base material and an adhesive.

Moreover, in the comparative example 2, R value of the adhesive layer was 6.0, and there existed a very thick area|region in the adhesive layer. For this reason, the printing visibility of the protective film (film for protective film formation) via the support sheet was inferior.

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

1A, 1B, 1C… A composite sheet for forming a protective film, 10 ... support sheet, 10a... The film-side surface for forming a protective film of the supporting sheet (the first surface), 11... Subscription, 11a... The pressure-sensitive adhesive layer side surface of the substrate (the first surface, the concave-convex surface), 12 . pressure-sensitive adhesive layer, 12a... The surface on the opposite side to the base material side of the pressure-sensitive adhesive layer (first surface), 12b... The substrate-side surface (second surface) of the pressure-sensitive adhesive layer, 13, 23... Film for forming a protective film, 13b... Adhesive layer side surface (2nd surface) of the film for protective film formation, L _a1 , L _b1 , L _a2 , L _b2 ... Linear distance between significant adjacent vertices, L ₁ , L ₂ … A line segment projected on a plane in the horizontal direction on the pressure-sensitive adhesive layer, T _a ... The thickness of the pressure-sensitive adhesive layer, T _a1 … The minimum value of the thickness of the adhesive layer, T _a2 ... Maximum value of the thickness of the pressure-sensitive adhesive layer

Claims (3)

A support sheet comprising a base material and comprising a pressure-sensitive adhesive layer on the base material, the support sheet comprising:
The pressure-sensitive adhesive layer side surface of the substrate is a concave-convex surface,
When a test piece is cut out from 5 places of the said support sheet, and the cross section of the said adhesive layer is observed in these 5 test pieces, (sum of the linear distances between adjacent significant vertices) / (linear distance in the horizontal direction to the adhesive layer) ) of the support sheet having an average value of the ratio of 1.5 or more and less than 5.0. The method of claim 1,
The support sheet in which the said adhesive layer is in direct contact with the uneven|corrugated surface of the said base material. The composite sheet for protective film formation provided with the film for protective film formation on the adhesive layer in the support sheet of Claim 1 or 2.

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