JP6091955B2 - Adhesive sheet, composite sheet for forming protective film, and method for producing chip with protective film - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface of the base material. Specifically, a protective film-forming film capable of forming a protective film on the surface of a plate-like workpiece such as a semiconductor substrate, particularly a protection used for manufacturing a semiconductor device mounted by a so-called face down method. A pressure-sensitive adhesive sheet capable of forming a film-forming film on the surface of the pressure-sensitive adhesive layer side, wherein the protective film-forming composite sheet comprising the pressure-sensitive adhesive sheet and the protective film-forming film is a dicing sheet as a workpiece It is related with the adhesive sheet which functions as. Moreover, this invention relates also to the composite sheet for protective film formation provided with said adhesive sheet. Furthermore, the present invention also relates to a method for manufacturing a chip with a protective film using the composite sheet for forming a protective film.

  2. Description of the Related Art In recent years, semiconductor devices have been manufactured using a so-called “face down” mounting method. In the face-down method, a semiconductor chip (hereinafter also simply referred to as “chip”) having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a wiring board. For this reason, the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.

  Radiation curable pressure-sensitive adhesive on a substrate as a layered body having a protective film forming film for protecting the exposed chip back surface and a dicing sheet used in a dicing process of a semiconductor wafer for giving a chip. A dicing tape-integrated film for semiconductor back surface comprising a dicing tape having a layer and a flip chip type semiconductor back film provided on the pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is pre-cured by radiation irradiation A dicing tape-integrated film for semiconductor back surface is disclosed in Patent Document 1.

JP 2011-228451 A

  However, the dicing tape-integrated film for semiconductor back surface disclosed in Patent Document 1 has the following problems. That is, since the pressure-sensitive adhesive layer of the film (that is, the protective film-forming composite sheet) is pre-cured by irradiation, the adhesiveness to the flip-chip type semiconductor back film (that is, the protective film-forming film) is low. It has become. This is because when a workpiece such as a semiconductor wafer is subjected to a dicing process or the like, the workpiece is separated into individual pieces, and when the obtained chip-like member is picked up, the protective film-forming film and the adhesive are adhered. Although it contributes to making peeling easily between the adhesive layer and the adhesive layer, on the other hand, peeling between the protective film-forming film and the pressure-sensitive adhesive layer during the dicing process and expanding process of the workpiece Part of the protective film-forming film is scattered (hereinafter also referred to as “film scattering”), or a laminate of a chip-shaped member formed by dicing and the protective film-forming film is scattered (hereinafter referred to as “film scattering”). , Also referred to as “chip scattering”).

  The present invention provides a pressure-sensitive adhesive sheet in which the occurrence of the above problems (film scattering and / or chip scattering), a composite sheet for forming a protective film, and a method for manufacturing a chip with a protective film using the composite sheet for forming a protective film are provided. The task is to do. In the present specification, the “composite sheet for forming a protective film” means a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface of the base material, and the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet. It means a laminate comprising a protective film-forming film laminated on the main surface. Further, the “chip with protective film” means a laminated structure including a chip-like member in which a workpiece is separated into pieces, and a protective film attached to one surface of the chip-like member, This protective film is formed by curing a protective film-forming film.

  In order to achieve the above object, the present inventors have examined that a protective film-forming film piece that is subject to film scattering or chip scattering is a portion of the protective film-forming film that is proximal to the outer periphery (periphery It was revealed that there were many cases that were located in Therefore, the adhesiveness of the pressure-sensitive adhesive layer in contact with the peripheral portion of the protective film-forming film to the protective film-forming film is determined by the adhesion of the pressure-sensitive adhesive layer in contact with the portion other than the peripheral portion of the protective film-forming film to the protective film-forming film. It came to the knowledge that it was possible to prevent said film scattering and chip | tip scattering by making it higher than the property.

  Then, the means for changing partially the adhesiveness with respect to the film for protective film formation in an adhesive layer was further examined. As a result, the following knowledge was obtained. That is, the pressure-sensitive adhesive layer was obtained by applying a liquid composition for forming the pressure-sensitive adhesive layer (also referred to as “pressure-sensitive adhesive layer coating liquid” in this specification) onto a substrate or a process member. It is formed through a process (such as a drying process) for reducing the viscosity of the coating film. Here, the pressure-sensitive adhesive layer according to this embodiment contains a component that is cured by irradiation with energy rays in the pressure-sensitive adhesive layer coating solution, and the pressure-sensitive adhesive layer on which the protective film-forming film is laminated has energy. It has undergone a process of irradiating a line. Therefore, a mask layer made of a material that reduces the amount of energy rays reaching the pressure-sensitive adhesive layer is provided on a part of the base material, and a partial area of the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet is masked in plan view. By carrying out the step of irradiating the pressure-sensitive adhesive layer with energy rays through the base material as a region where the layer exists (this region is also referred to as “mask layer region” in this specification), the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet Protective film in a pressure-sensitive adhesive layer located in a region where a mask layer does not exist in a plan view on the main surface of the film (this region is also referred to as a “non-mask layer region” in this specification) and irradiated with energy rays It is possible to make the above-mentioned adhesiveness of the adhesive layer located in the mask layer region higher than the adhesiveness to the forming film.

  The present invention completed based on such knowledge is, firstly, a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface side of the base material, As one of the components of the composite sheet for protective film formation provided with the protective film-forming film laminated on at least one region of the pressure-sensitive adhesive sheet and the main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side, It can be used when dicing a member, and the base material reduces the transmittance of energy rays irradiated from the other main surface side of the base material to the one main surface side of the base material. Having a mask layer, the pressure-sensitive adhesive layer contains a component that undergoes a polymerization reaction upon irradiation with energy rays, and the adhesiveness to the protective film-forming film can be reduced by the polymerization reaction of the component; Said adhesive sheet A region surrounded by a mask layer region that is a region where the mask layer is present in a plan view on the principal surface on the adhesive layer side, and other than the mask layer region on the principal surface on the adhesive layer side of the adhesive sheet An energy ray transmitting region, which is a part or all of a non-mask layer region that is a region of the adhesive layer, and is a region where the adhesive layer should be irradiated with energy rays, is a main layer on the adhesive layer side of the adhesive sheet. Provided is a pressure-sensitive adhesive sheet including a protective film region, which is a region where the protective film-forming film on the surface is laminated in use (Invention 1).

  In the said invention (invention 1), the said adhesive sheet is what the energy ray was irradiated to the said adhesion layer located in the said energy ray transmission area | region from the main surface side at the said base material side, Comprising: The said energy ray transmission The adhesiveness of the adhesive layer located in the region to the protective film forming film is preferably lower than the adhesiveness of the adhesive layer located in the mask layer region to the protective film forming film (Invention 2). .

  In the said invention (invention 1 and 2), the said to-be-processed member is arrange | positioned at the said composite sheet for protective film formation at the time of use of the said composite sheet for protective film formation in the main surface at the side of the said adhesive layer of the said adhesive sheet. It is preferable that the region for the workpiece to be the projection region of the power region includes the energy ray transmission region (Invention 3).

  In the said invention (invention 3), it is preferable that the said to-be-processed area | region is included by the said area | region for protective films (invention 4).

  In the said invention (invention 1 to 4), the jig | tool for hold | maintaining the laminated body which consists of the said composite sheet for protective film formation and the said to-be-processed member in the main surface at the side of the said adhesive layer of the said adhesive sheet is arrange | positioned. It is preferable that at least a part of the region to be formed includes the mask layer region (Invention 5).

  In the said invention (invention 1-5), the said mask layer consists of material which interrupts | blocks permeation | transmission to the one main surface side of the said base material of the energy ray irradiated from the other main surface side of the said base material. Is preferred (Invention 6).

  In the said invention (invention 1-6), it is preferable that the said mask layer is provided so that the said adhesive layer may be contact | connected (invention 7).

  In the said invention (invention 1-7), it is preferable that the main surface by the side of the said base material of the said adhesive sheet consists of the surface of the said mask layer partially (invention 8).

  In the said invention (invention 1-6), it is preferable that the said mask layer is provided in the thickness direction inside of the said base material (invention 9).

  In the said invention (invention 1 to 9), it is preferable that the said adhesive sheet is a elongate body, Comprising: The said energy ray transmission area | region spaced apart in the elongate direction is provided (invention 10).

  The present invention secondly provides an adhesive roll formed by rolling up the adhesive sheet according to the invention (Invention 10) in the longitudinal direction (Invention 11).

  Thirdly, the pressure-sensitive adhesive sheet according to the invention (inventions 2 to 9) and a protective film-forming film laminated on the protective film region on the main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side. A composite sheet for forming a protective film is provided (Invention 12).

  In the said invention (invention 12), it is preferable that the said composite sheet for protective film formation is a elongate body, Comprising: The said film for protective film formation spaced apart in the elongate direction is provided (invention 13).

  4thly this invention provides the winding body of the composite sheet for protective film formation formed by winding up the composite sheet for protective film formation which concerns on the said invention (invention 13) in a longitudinal direction (invention 14).

  Fifthly, the present invention provides a long release sheet and a plurality of adhesives according to the inventions (Inventions 1 to 9) arranged in the longitudinal direction of the release sheet while being separated from each other on the release surface of the release sheet. A laminate, wherein the pressure-sensitive adhesive sheet is laminated so that the surface on the pressure-sensitive adhesive layer side faces the release surface of the release sheet (Invention 15).

  6thly this invention provides the winding body of the laminated body formed by winding up the laminated body which concerns on the said invention (invention 15) in a longitudinal direction (invention 16).

  Seventhly, the present invention provides a long release sheet and a protective film according to the above invention (invention 12) arranged in the longitudinal direction of the release sheet while being separated from each other on the release surface of the release sheet. A laminated body, wherein the protective film-forming composite sheet is laminated so that the surface on the protective film-forming film side faces the release surface of the release sheet. (Invention 17).

  Eighthly, the present invention provides a wound body of a laminate formed by winding the laminate according to the above invention (Invention 17) in the longitudinal direction (Invention 18).

  Ninthly, the protective film-forming film-side surface of the laminate protective film-forming composite sheet according to the invention (Invention 12) is attached to one surface of a workpiece to form the protective film. The work sheet to which the composite sheet is attached is separated into pieces, and the protective film formation film is cured and protected when the protective film formation film is attached to the surface of the work member. A chip with a protective film obtained by forming a film into a chip with a protective film comprising a chip-shaped member obtained by dividing the workpiece into pieces and the protective film laminated on one surface of the chip-shaped member. A manufacturing method is provided (Invention 19).

  In the above invention (Invention 19), the singulation of the member to be processed preferably includes cutting of the member to be processed (Invention 20).

  In the above inventions (Inventions 19 and 20), it is preferable that the singulation of the workpiece includes breaking of the workpiece (Invention 21).

  In the pressure-sensitive adhesive sheet according to the present invention, since the base material has a mask layer, the adhesiveness of the pressure-sensitive adhesive layer to the protective film-forming film is different between the portion located in the mask layer region and the portion located in the non-mask layer region. Can be. Therefore, the pressure-sensitive adhesive layer in which the adhesiveness of the pressure-sensitive adhesive layer to the protective film-forming film is partially changed, specifically, the portion that is in contact with the peripheral edge of the protective film-forming film has high pressure-sensitive adhesive properties. A pressure-sensitive adhesive layer configured to have low adhesiveness can be easily obtained at a portion in contact with a portion other than the peripheral portion of the film for use. And the composite sheet for forming a protective film according to the present invention comprising the pressure-sensitive adhesive sheet having such a distribution in adhesiveness and the protective film-forming film laminated on the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet, When a laminated body in which a workpiece to be processed such as a semiconductor wafer is attached to the main surface on the protective film forming film side is subjected to a dicing process, film scattering and / or chip scattering hardly occur. Moreover, by using the composite sheet for forming a protective film according to the present invention as a dicing sheet, a chip with a protective film having excellent quality can be produced with high productivity.

It is a schematic sectional drawing of the adhesive sheet which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is the schematic plan view which looked at the adhesive sheet shown by FIG. 1 from the main surface side by the side of the adhesive layer. It is the schematic plan view which looked at the composite sheet for protective film formation shown in FIG. 2 from the main surface side at the film side for protective film formation. It is a schematic sectional drawing which shows the state after irradiating an energy ray to the adhesive sheet shown by FIG. It is a schematic sectional drawing which shows the state by which the main surface opposite to the main surface which opposes the adhesive layer of the film for protective film formation with which the composite sheet for protective film formation shown by FIG. 2 is affixed to the to-be-processed member. It is a schematic sectional drawing of the adhesive sheet which concerns on another one Embodiment of this invention. It is a schematic sectional drawing of the adhesive sheet which concerns on another one Embodiment of this invention. It is a schematic sectional drawing which shows the state in which the peeling sheet has stuck to the adhesive sheet shown by FIG.

Hereinafter, embodiments of the present invention will be described.
1. Adhesive Sheet As shown in FIG. 1, an adhesive sheet 1 according to an embodiment of the present invention includes a base material 2 and an adhesive layer 3 laminated on one main surface 2A side of the base material 2. The substrate 2 includes a mask layer 21.
The pressure-sensitive adhesive sheet 1 according to this embodiment is for forming a protective film including a pressure-sensitive adhesive sheet 1 and a protective film-forming film 4 laminated on at least one region of the main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1. As one of the components of the composite sheet 10 (FIG. 2), it can be used when dicing a plate-shaped workpiece.

(1) Base Material The base material 2 included in the pressure-sensitive adhesive sheet 1 according to this embodiment includes a mask layer 21 and a base material main part 22 that is a part other than the mask layer 21.
(1-1) Base material main part The base material main part 22 of the base material 2 of the pressure-sensitive adhesive sheet 1 according to the present embodiment is not particularly limited as long as it is not broken in an expanding process performed after the dicing process. Usually, it is composed of a film mainly composed of a resin-based material. Specific examples of such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylic acid ester copolymer films; low density Polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, polyethylene film such as high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, Polyolefin film such as norbornene resin film; Polyvinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; Polyethylene terephthalate film, Polybutylene tele Polyester film of tallate films; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used. The base material main part 22 may be a film made of one of these, or may be a laminated film in which two or more of these are combined. In addition, “(meth) acrylic acid” in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.

The film constituting the substrate main part 22 preferably includes at least one of an ethylene copolymer film and a polyolefin film.
It is easy to control the mechanical characteristics of an ethylene copolymer film in a wide range by changing the copolymerization ratio. For this reason, the base material 2 provided with the ethylene-based copolymer film as the base material main part 22 is a machine required as a base material of a dicing sheet when using the composite sheet 10 for forming a protective film according to this embodiment as a dicing sheet. Easy to meet characteristics. In addition, since the ethylene copolymer film has relatively high adhesion to the pressure-sensitive adhesive layer 3, when the protective film-forming composite sheet 10 according to the present embodiment is used as a dicing sheet, the base material main portion 22 and the pressure-sensitive adhesive layer are used. 3 is hardly peeled off at the interface.

  The ethylene copolymer film and the polyolefin film are components that adversely affect the properties as a dicing sheet (for example, in the case of a polyvinyl chloride film, the plasticizer contained in the film is transferred from the substrate main part 22 to the adhesive layer. 3 and further distributed on the surface of the pressure-sensitive adhesive layer 3 on the side opposite to the side facing the base material main portion 22 to reduce the pressure-sensitive adhesiveness of the pressure-sensitive adhesive layer 3 to the adherend. Since there is little content of, it is hard to produce problems, such as the adhesiveness with respect to the adherend of the adhesive layer 3 falling. That is, the ethylene copolymer film and the polyolefin film are excellent in chemical stability.

  The base material main part 22 may contain various additives such as pigments, flame retardants, plasticizers, antistatic agents, lubricants, fillers, and the like in a film mainly composed of the resin-based material. Examples of the pigment include titanium dioxide and carbon black. Examples of the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such an additive is not particularly limited, but should be limited to a range in which the base material main portion 22 exhibits a desired function and does not lose smoothness and flexibility.

  In the case where ultraviolet rays are used as the energy rays applied to the pressure-sensitive adhesive layer 3, it is preferable that the base material main portion 22 has transparency to the ultraviolet rays. When using an electron beam as an energy beam irradiated to the adhesive layer 3, it is preferable that the base-material main part 22 has the transmittance | permeability of an electron beam.

  Further, the surface 22A of the substrate main part 22 facing the pressure-sensitive adhesive layer 3 (hereinafter also referred to as “substrate main part facing surface”) 22A is selected from the group consisting of a carboxyl group and its ions and salts. It is preferable that a component having two or more species is present. Examples of components used for forming the pressure-sensitive adhesive layer 3 such as the above-described components in the base material main part 22 and the components related to the pressure-sensitive adhesive layer 3 (components forming the pressure-sensitive adhesive layer 3 and crosslinking agent (δ)) )) Can chemically reduce the possibility of delamination between them. The specific method for making such a component exist in 22 A of base material main part opposing surfaces is not specifically limited. For example, the base material main part 22 itself is made of, for example, an ethylene- (meth) acrylic acid copolymer film, an ionomer resin film, etc., and the resin constituting the base material main part 22 is made of a carboxyl group and its ions and salts. You may have 1 type, or 2 or more types chosen from the group which consists of. As another method for causing the above-described components to exist on the base material main part facing surface 22A, the base material main part 22 is, for example, a polyolefin-based film, and a corona treatment is applied to the base material main part facing surface 22A side, or a primer A layer may be provided. Various coating films (however, those capable of transmitting energy rays) may be provided on the surface of the substrate main portion 22 opposite to the substrate main portion facing surface 22A.

  The thickness of the base material main part 22 is not particularly limited. From the viewpoint of reducing the manufacturing cost while suppressing a reduction in handling, the thickness of the base material main portion 22 is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 100 μm or less, and 50 μm or more and 90 μm or less. It is particularly preferred.

(1-2) Mask Layer The base material 2 included in the pressure-sensitive adhesive sheet 1 according to the present embodiment is irradiated from the other main surface (the main surface opposite to the main surface facing the pressure-sensitive adhesive layer 3) 2B side of the base material 2. It has the mask layer 21 which reduces the transmittance | permeability to the 1A main surface (main surface which opposes the adhesion layer 3) 2A side of the base material 2 of the made energy beam.
The mask layer 21 includes the arrangement (main surface arrangement) of the mask layer 21 when the main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1 is viewed from a direction parallel to the normal line (plan view), and the pressure-sensitive adhesive sheet 1. Each of the arrangements (cross-sectional arrangements) of the mask layer 21 in the substrate 2 when viewed from a direction parallel to the normal line of the cross-section in the thickness direction (cross-sectional view) has the following characteristics.

(1-2-1) Main Surface Arrangement The mask layer 21 is arranged so as not to occupy the entire main surface 2A in a plan view from the one main surface 2A side of the substrate 2. For this reason, the main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1 includes a mask layer region that is a region where the mask layer is present in a plan view, and a non-mask layer region that is a region where the mask layer is not present in a plan view. Have An energy ray transmitting region 1a which is a part or all of the non-mask layer region, is a region surrounded by the mask layer region in plan view, and is a region where the adhesive layer 3 is to be irradiated with energy rays. (In FIG. 3, which is a view of the pressure-sensitive adhesive sheet 1 from the main surface 1 </ b> A side, it is shown as a region surrounded by a broken line.) Is a protective film formation on the main surface 1 </ b> A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1. Included in the protective film region 1b, which is a region where the film 4 is laminated (shown as a region surrounded by a two-dot chain line in FIG. 3, which is a view of the pressure-sensitive adhesive sheet 1 from the main surface 1A side). Is done.

  That is, as shown in FIG. 4, when the protective film-forming film 4 is laminated on the main surface 1A on the pressure-sensitive adhesive layer 3 side of the adhesive sheet 1 to form the protective film-forming composite sheet 10, the laminated protective film The peripheral edge portion 4a of the forming film 4 (inner side than the outer periphery of the protective film forming film 4 and outside the outer periphery of the energy ray transmitting region 1a indicated by a broken line in FIG. 4) is the adhesive of the adhesive sheet 1. It contacts the mask layer region on the main surface 1A on the agent layer 3 side.

  As such a configuration, when energy rays are irradiated from the main surface 1B side of the base material 2 side of the pressure-sensitive adhesive sheet 1, as shown in FIG. 5, in the portion 3b located in the energy ray transmission region 1a in the pressure-sensitive adhesive layer 3, The polymerization reaction of the components constituting the agent layer 3 proceeds, and the adhesiveness of the portion 3b to the protective film forming film 4 decreases. On the other hand, in the portion 3a located in the mask layer region of the pressure-sensitive adhesive layer 3, the polymerization reaction of the components constituting the pressure-sensitive adhesive layer 3 hardly proceeds or does not substantially proceed. Therefore, the protective film forming film of the portion 3a The adhesion to 4 remains relatively high.

  As a result, the adhesiveness to the adhesive layer 3 in the peripheral edge 4a of the protective film forming film 4 is higher than the adhesiveness to the adhesive layer 3 in the portion 4b other than the peripheral edge 4a of the protective film forming film 4. Is realized. Therefore, when the composite sheet 10 for forming a protective film is used as a dicing sheet, film scattering or chip scattering that scatters from a portion located at the peripheral edge 4a of the protective film forming film 4 during the dicing process. Is suppressed.

  Further, a plate-shaped workpiece (for example, a semiconductor wafer) W is disposed on the protective film-forming composite sheet 10 when the protective film-forming composite sheet 10 is used on the main surface 1A on the pressure-sensitive adhesive layer 3 side of the adhesive sheet 1. As shown in FIG. 6, it is preferable that the workpiece region 1c, which is the projection region of the region to be included, includes the energy ray transmission region 1a.

  As shown in FIG. 6, when the workpiece region 1c includes the energy ray transmission region 1a, the pressure-sensitive adhesive layer 3 present at a position corresponding to the peripheral portion Wa of the workpiece W is formed with a protective film. The pressure-sensitive adhesive layer 3 present at a position corresponding to a region other than the peripheral edge Wa of the workpiece W has a relatively low pressure-sensitive adhesive property to the protective film-forming film 4. Therefore, during the dicing process or the expanding process using the protective film forming composite sheet 10, the chip-shaped member obtained by separating the peripheral edge Wa of the workpiece W is the protective film forming film 4 or Chip scattering is difficult to occur with the small pieces of the protective film formed by curing the protective film forming film 4.

  Further, as shown in FIG. 6, the workpiece member region 1 c is preferably included in the protective film region 1 b. In this case, the protective film-forming film 4 is affixed to the workpiece W so as to be in contact with the entire main surface of the workpiece W. For this reason, chip | tip scattering based on the to-be-processed member W not contacting the composite sheet 10 for protective film formation in a part of the main surface does not arise easily.

  Here, the relationship among the energy ray transmission region 1a, the protective film region 1b, and the workpiece member region 1c will be summarized. The protective film region 1b includes an energy ray transmission region 1a. Therefore, outside the outer periphery of the energy ray transmitting region 1a, there is a region that corresponds to the protective film region 1b but does not correspond to the energy ray transmitting region 1a. The relationship between the workpiece member region 1c with respect to the energy ray transmitting region 1a and the protective film region 1b is not particularly limited. As described above, it is most preferable that the protective film region 1b includes the workpiece member region 1c and the workpiece member region 1c includes the energy ray transmission region 1a. As long as the protective film region 1b includes the workpiece member region 1c, the entire region of the workpiece member region 1c may be the energy beam transmission region 1a, or the energy beam transmission region 1a may be the workpiece member. The use area 1c may be included. If there is no problem in practice (specifically, the protective film may not be attached to the periphery of the workpiece), the workpiece region 1c includes the protective film region 1b. May be. Furthermore, the entire region of the workpiece member region 1c may be the protective film region 1b.

  A jig for holding a laminate composed of the protective film-forming composite sheet 10 and the workpiece W on the main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1 (a specific example is a ring frame). It is preferable that at least a part of a region (indicated by reference numeral 1Aa in FIG. 6) where the layer is disposed is a mask layer region. In the case where the jig is a ring frame, a region 1Aa on the main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1 is a mask layer positioned so as to surround the energy ray transmission region 1a. Includes part of the region. As described above, the pressure-sensitive adhesive layer 3 located in the mask layer region has a lower degree of progress of the polymerization reaction in the component in which the polymerization reaction is caused by irradiation with energy rays than the pressure-sensitive adhesive layer 3 located in the non-mask layer region ( This polymerization reaction may not substantially proceed.) Therefore, the pressure-sensitive adhesive layer 3 located in the region 1Aa is also excellent in adhesiveness to the ring frame. Therefore, the ring frame is less likely to be detached from the protective film-forming composite sheet 10 during use (during the dicing process or the expanding process).

  Note that the protective film-forming composite sheet 10 and the ring frame are not in direct contact with each other, and a jig adhesive layer provided on the main surface 1A on the pressure-sensitive adhesive layer 3 side of the adhesive sheet 1 of the protective film-forming composite sheet 10 is interposed. In such a case, even in such a case, because the adhesiveness of the adhesive layer 3 located in the region 1Aa on the main surface 1A on the adhesive layer 3 side of the adhesive sheet 1 is high, During use, the ring frame is less likely to be detached from the protective film-forming composite sheet 10. As a jig | tool adhesion layer, the layer which consists of a double-sided adhesive sheet which has a core material, and the single layer of an adhesive can be employ | adopted.

(1-2-2) Cross-sectional arrangement The cross-sectional arrangement of the mask layer 21 in the substrate 2 is not particularly limited.
As shown in FIG. 1, the mask layer 21 may be provided in contact with the pressure-sensitive adhesive layer 3. In this case, when the amount of energy rays reaching the pressure-sensitive adhesive layer 3 is adjusted by the mask layer 21 by irradiating energy rays from the main surface 1B side of the pressure-sensitive adhesive sheet 1 on the base material 2 side, The influence of the material and thickness of the portion 22 on the degree of adjustment can be reduced.

  Further, as shown in FIG. 7, the mask layer 21 constitutes a part of the surface of the main surface 1 </ b> B on the base material 2 side of the pressure-sensitive adhesive sheet 1, that is, the main surface of the pressure-sensitive adhesive sheet 1 on the pressure-sensitive adhesive layer 3 side. A part of the main surface 1B opposite to 1A may be made of the surface of the mask layer 21. In this case, the chemical influence which the material which comprises the mask layer 21 has on the adhesive layer 3 can be reduced. In addition, the mask layer 21 can be laminated as the final step of the laminating step relating to the pressure-sensitive adhesive sheet 1 or the laminating step relating to the protective film-forming composite sheet 10, and the coating to be applied to the protective film-forming composite sheet 10. It is also possible to stack the mask layer 21 in accordance with the shape of the processed member W.

  Moreover, the mask layer 21 may be provided in the thickness direction inside of the base material 2, as FIG. 8 shows. In the case of such a configuration, even when the mask layer 21 is thin, such as a metal vapor deposition layer, the mask layer 21 is peeled off when a deformation force such as folding is applied to the protective film-forming composite sheet 10. Therefore, it is difficult to cause a problem that the composite sheet 10 for forming the protective film falls off.

(1-2-3) Material, etc. The material constituting the mask layer 21 is the transmittance of energy rays used for advancing the polymerization reaction of a component that causes a polymerization reaction by irradiation of energy rays contained in the pressure-sensitive adhesive layer 3. It is not limited as long as it has a function of lowering. If the case where the energy rays are ultraviolet rays is described as an example, the energy rays may be composed of a metallic material such as aluminum or copper, or may be composed of a coating film formed from a paint containing a component capable of absorbing ultraviolet rays. May be. Alternatively, the mask layer 21 may be configured by roughening a part of the main surface of the base material main portion 22. In this case, the amount of ultraviolet rays reaching the pressure-sensitive adhesive layer 3 can be reduced by scattering the incident ultraviolet rays.

  The thickness of the mask layer 21 is not particularly limited as long as it can fulfill its function. In the case where the mask layer 21 is made of a metal-based material, it may be able to function sufficiently with a thickness of 1 μm or less. When the mask layer 21 is composed of a coating film, the thickness is usually about 1 μm to 50 μm.

(1-3) Characteristics of Substrate 2 The substrate 2 according to the present embodiment has heat resistance, and specifically, preferably has the following characteristics (a) to (c).
(A) The elements constituting the substrate 2 (specifically, the mask layer 21 and the substrate main part 22 are included) have a melting point exceeding 130 ° C. or no melting point.
(B) The thermal contraction rate of the base material 2 when heated at 130 ° C. for 2 hours is −5% or more and + 5% or less, and (c) the elongation at break in both the MD direction and the CD direction of the base material 2 The degree is 100% or more and the tensile stress at 25% strain is 100 MPa or less.

  When the melting point of the element constituting the substrate 2 is 130 ° C. or less, or the thermal shrinkage rate of the substrate 2 is outside the above range, the protective film forming film 4 is a thermosetting film. There is a possibility that the base material 2 melts at the time of curing, and it becomes difficult for the base material 2 to maintain its shape. Moreover, the base material 2 may be fused with a peripheral device (for example, an oven) in the process of processing the workpiece W. When the protective film-forming composite sheet 10 is configured using the base material 2 having a thermal shrinkage of less than −5% or more than + 5% and the workpiece W is held and thermosetting is performed. Because of the weight of the workpiece W, the peripheral portion (the base material 2 on the outer peripheral portion of the pressure-sensitive adhesive sheet 1) that does not correspond to the workpiece W is elongated rather than contracted, and the protective film-forming composite sheet 10 is slackened. It becomes easy. As a result, subsequent machining such as a dicing step becomes difficult, or the laminate of the chip-like member and the protective film-forming film 4 or the protective film formed by separating the workpiece W from the pressure-sensitive adhesive sheet 1 is peeled off. (Pickup) may be difficult.

  It is more preferable that the element constituting the substrate 2 has a melting point of 140 ° C. or higher or no melting point, particularly preferably a melting point of 200 ° C. or higher or no melting point. Moreover, it is more preferable that the thermal contraction rate of the base material 2 when heated at 130 ° C. for 2 hours is −4% to + 4%. By making the melting point of the elements constituting the base material 2 and the thermal shrinkage rate of the base material 2 within the above ranges, the base material 2 is superior in heat resistance, and when the above-described protective film forming film 4 is cured by heat. The shape retention of the base material 2 is kept good.

In addition, the thermal contraction rate of the base material 2 at the time of heating at 130 degreeC for 2 hours is calculated | required by a following formula from the area of the base material 2 before and behind throwing a base film in a 130 degreeC environment.
Thermal contraction rate (%) = {(area of substrate 2 before loading) − (area of substrate 2 after loading)} / area of substrate 2 before loading × 100

  The elongation at break of the substrate 2 in this embodiment is preferably 100% or more, more preferably 120% or more and 1000% or less, as a value measured at 23 ° C. and a relative humidity of 50%. % To 1000% is particularly preferable. Here, the breaking elongation is an elongation ratio of the length of the test piece at the time of breaking the test piece with respect to the original length in the tensile test based on JIS K7161: 1994 (ISO 527-1 1993). The base material 2 having a breaking elongation of 100% or more is not easily broken during the expanding process after the dicing process, and the chip-like member is easily separated.

  Further, the tensile stress at 25% strain of the substrate 2 in the present embodiment is preferably 100 MPa or less, more preferably 80 MPa or less, and particularly preferably 15 MPa or more and 70 MPa or less. Here, the tensile stress at 25% strain is measured by a test according to JIS K7161: 1994. If the tensile stress at 25% strain is more than 100 MPa, the expandability is lowered, and there is a possibility that a problem occurs when the chip-shaped member is separated.

  The elongation at break and the tensile stress at 25% strain are the longitudinal direction (MD direction) of the original fabric in the base material 2 and the direction in the main surface of the base material 2 and perpendicular to the MD direction (CD direction). ), It is preferable that the measurement is satisfied.

  As a film which comprises the base-material main part 22 which gives the base material 2 provided with said characteristic (a)-(c), a polypropylene film, a polybutylene terephthalate film, an acrylic resin film, a heat-resistant polyurethane film etc. are mentioned, for example. It is done. In addition, these cross-linked films and modified films by radiation and discharge can also be used. The film constituting the base material main part 22 may be a laminate of the above film as long as the base material 2 can have the above characteristics (a) to (c).

  When marking is performed by irradiating the protective film forming film 4 or the protective film formed by curing the laser beam through the pressure-sensitive adhesive sheet 1, the base material 2, particularly the base material main part 22 is marked. It is preferable that it has the transparency with respect to the laser beam for. Examples of the wavelength of the laser beam for marking are 532 nm and 1064 nm. The total light transmittance of the pressure-sensitive adhesive sheet 1 at these wavelengths is preferably 70% or more, more preferably 75% or more.

  The thickness of the base material 2 is not particularly limited as long as there is no problem that it is cut in the dicing process or broken in the expanding process or the picking process. Preferably they are 20 micrometers or more and 450 micrometers or less, More preferably, they are 25 micrometers or more and 400 micrometers or less, Especially preferably, they are the range of 50 micrometers or more and 350 micrometers or less.

(2) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer 3 included in the pressure-sensitive adhesive sheet 1 according to the present embodiment is composed of an energy ray polymerization-type pressure-sensitive adhesive composition containing a component that causes a polymerization reaction upon irradiation with energy rays. The pressure-sensitive adhesive composition is not limited in any way, but for example, rubber-based, acrylic-based, silicone-based, polyvinyl ether, or other pressure-sensitive adhesive compositions can be used. Examples of the energy rays for polymerization include X-rays, electromagnetic waves such as ultraviolet rays, and electron beams. Among these energy rays, ultraviolet rays that are low in cost for installation of equipment and excellent in workability are preferable.

  As an example of the pressure-sensitive adhesive composition that can be polymerized by ultraviolet rays, an acrylic polymer (α) and an energy beam polymerizable compound (β) described below, and a storage elastic modulus modifier (γ) and a crosslinking agent (if necessary) and an adhesive composition containing δ) and the like.

(2-1) Acrylic polymer (α)
An example of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to the present embodiment contains an acrylic polymer (α). In the pressure-sensitive adhesive layer 3 formed from this pressure-sensitive adhesive composition, at least a part of the acrylic polymer (α) may be contained as a cross-linked product by performing a cross-linking reaction with a cross-linking agent (δ) described later. .

  A conventionally known acrylic polymer can be used as the acrylic polymer (α). The weight average molecular weight (Mw) of the acrylic polymer (α) is a coating liquid (this specification) comprising the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 or a composition obtained by adding a solvent to this. These coating liquids are generally referred to as “adhesive layer-forming coating liquids” in terms of film-forming properties at the time of coating, and preferably from 10,000 to 2,000,000. More preferably, it is 10,000 or less. The glass transition temperature Tg of the acrylic polymer (α) is preferably in the range of −70 ° C. or higher and 30 ° C. or lower, more preferably −60 ° C. or higher and 20 ° C. or lower. The glass transition temperature can be calculated from the Fox equation.

  The acrylic polymer (α) may be a homopolymer formed from one type of acrylic monomer, or may be a copolymer formed from a plurality of types of acrylic monomers, It may be a copolymer formed from one or more types of acrylic monomers and monomers other than acrylic monomers. Specific types of the compound to be an acrylic monomer are not particularly limited, and specific examples include (meth) acrylic acid, itaconic acid, (meth) acrylic acid ester, and derivatives thereof (acrylonitrile, etc.).

  Specific examples of (meth) acrylic acid esters include chain skeletons such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Cyclic skeletons such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and imide acrylate (Meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate, N-methylamino Having a reactive functional group other than hydroxyl group, such as chill (meth) acrylate (meth) acrylate. Examples of monomers other than acrylic monomers include olefins such as ethylene and norbornene, vinyl acetate, and styrene. When the acrylic monomer is alkyl (meth) acrylate, the alkyl group preferably has 1 to 18 carbon atoms.

  When the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to this embodiment contains a cross-linking agent (δ) that can cross-link the acrylic polymer (α) as described later, acrylic The type of the reactive functional group that the system polymer (α) has is not particularly limited, and may be appropriately determined based on the type of the crosslinking agent (δ). For example, when the crosslinking agent (δ) is a polyisocyanate compound, examples of the reactive functional group of the acrylic polymer (α) include a hydroxyl group, a carboxyl group, and an amino group. These polar functional groups have the effect of improving the compatibility between the acrylic polymer (α) and the storage elastic modulus modifier (γ) described later, in addition to the function of reacting with the crosslinking agent (δ). Among these, when the crosslinking agent (δ) is a polyisocyanate compound, it is preferable to employ a hydroxyl group having high reactivity with the isocyanate group as the reactive functional group. The method for introducing a hydroxyl group as a reactive functional group into the acrylic polymer (α) is not particularly limited. As an example, the acrylic polymer (α) may contain a structural unit based on an acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate in the skeleton.

  When the acrylic polymer (α) has a reactive functional group, the mass ratio of the reactive functional group to all monomers is 1% by mass or more in terms of monomer for forming the acrylic polymer (α). It is preferable to set it as about mass% or less, and it is more preferable to set it as 2 mass% or more and 10 mass% or less.

(2-2) Energy ray polymerizable compound (β)
The energy ray polymerizable compound (β) contained in the pressure sensitive adhesive composition for forming the pressure sensitive adhesive layer 3 according to the present embodiment has an energy ray polymerizable group and is irradiated with energy rays such as ultraviolet rays and electron beams. The specific configuration is not particularly limited as long as the polymerization reaction can be received. When the energy beam polymerizable compound (β) is polymerized, the adhesiveness of the pressure-sensitive adhesive layer 3 to the protective film-forming film 4 can be reduced.

  The kind of energy beam polymerizable group is not particularly limited. Specific examples thereof include a functional group having an ethylenically unsaturated bond such as a vinyl group or a (meth) acryloyl group. In the case where the pressure-sensitive adhesive composition contains a crosslinking agent (δ), the energy ray polymerizable group is ethylenic from the viewpoint of reducing the possibility of functional overlap with the site where the crosslinking agent (δ) undergoes a crosslinking reaction. A functional group having an unsaturated bond is preferable, and among them, a (meth) acryloyl group is more preferable from the viewpoint of high reactivity when irradiated with energy rays.

  The molecular weight of the energy beam polymerizable compound (β) is not particularly limited. When the molecular weight is excessively small, there is a concern that the compound volatilizes during the production process of the pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer 3, and at this time, the stability of the composition of the pressure-sensitive adhesive layer 3 decreases. Therefore, the molecular weight of the energy beam polymerizable compound (β) is preferably 100 or more, more preferably 200 or more, and particularly preferably 300 or more, as a weight average molecular weight (Mw).

  At least a part of the energy beam polymerizable compound (β) has a molecular weight of 4,000 or less as a weight average molecular weight (Mw), and preferably has properties as a storage elastic modulus modifier (γ) described later. . The energy ray polymerizable compound (β) having such properties as a storage elastic modulus modifier (γ) is a group consisting of monofunctional monomers and polyfunctional monomers having an energy ray polymerizable group and oligomers of these monomers. The compound which consists of 1 type, or 2 or more types chosen from is illustrated.

  The specific composition of the above compound is not particularly limited. Specific examples of the above compounds include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth). ) Acrylate, 1,4-butylene glycol di (meth) acrylate, alkyl (meth) acrylate having a chain skeleton such as 1,6-hexanediol di (meth) acrylate; dicyclopentadiene dimethoxydi (meth) acrylate, isobornyl Alkyl (meth) acrylate having a cyclic skeleton such as (meth) acrylate; polyethylene glycol di (meth) acrylate, oligoester (meth) acrylate, urethane (meta Acrylate oligomer, epoxy-modified (meth) acrylate, polyether (meth) acrylate, and acrylate compounds such as itaconic acid oligomer. Among these, acrylate compounds are preferred because of their high compatibility with acrylic polymers (α).

  The number of energy beam polymerizable groups that the energy beam polymerizable compound (β) has in one molecule is not limited, but is preferably a plurality, more preferably 3 or more, and particularly preferably 5 or more. .

  When the energy ray-polymerizable compound (β) contained in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to this embodiment has properties as a storage elastic modulus modifier (γ), energy rays The content of the polymerizable compound (β) is preferably 50 parts by mass or more and 300 parts by mass or less, and 75 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the acrylic polymer (α). More preferred. In the present specification, “part by mass” indicating the content of each component means an amount as a solid content. By setting the content of the energy ray-polymerizable compound (β) in such a range, the adhesiveness to the protective film forming film 4 of the pressure-sensitive adhesive layer 3 in the portion irradiated with the energy rays and the portion not irradiated with the energy rays The difference with the adhesiveness with respect to the film 4 for protective film formation of the adhesive layer 3 in can fully be ensured.

  As an example of the case where the energy beam polymerizable compound (β) is not a material having properties as a storage elastic modulus modifier (γ), the energy beam polymerizable compound (β) is an acrylic polymer, The case where it has the structural unit which has group in a principal chain or a side chain is mentioned. In this case, since the energy beam polymerizable compound (β) has properties as an acrylic polymer (α), the composition of the composition for forming the pressure-sensitive adhesive layer 3 is simplified. 3 has advantages such as easy control of the density of the energy beam polymerizable group in 3 and less shrinkage due to polymerization.

  The energy beam polymerizable compound (β) having the properties of the acrylic polymer (α) as described above can be prepared, for example, by the following method. Acrylic copolymer which is a copolymer comprising a structural unit based on (meth) acrylate and a structural unit based on alkyl (meth) acrylate containing a functional group such as hydroxyl group, carboxyl group, amino group, substituted amino group, and epoxy group By reacting a polymer with a compound having a functional group capable of reacting with the above functional group and an energy ray polymerizable group (for example, a group having an ethylenic double bond) in one molecule, the above acrylic heavy polymer is reacted. An energy beam polymerizable group can be added to the polymer.

When ultraviolet rays are used as energy rays for curing the energy ray polymerizable compound (β), near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling. The amount of ultraviolet rays may be appropriately selected depending on the thickness of the type and pressure-sensitive adhesive layer 3 of the energy beam polymerizable compound (beta), it is usually 50 to 500 mJ / cm ² about, 100~450mJ / cm ² is 200 to 400 mJ / cm ² is more preferable. Moreover, ultraviolet illuminance is about 50-500 mW / cm < ² > normally, 100-450 mW / cm < ² > is preferable and 200-400 mW / cm < ² > is more preferable. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a metal halide lamp, UV-LED etc. are used.

  When an electron beam is used as the energy beam, the acceleration voltage may be appropriately selected according to the type of the energy beam polymerizable compound (β) and the thickness of the pressure-sensitive adhesive layer 3. It is preferably about 000 kV. Moreover, what is necessary is just to set an irradiation dose in the range which an energy-beam polymeric compound ((beta)) hardens | cures appropriately, and is normally selected in the range of 10-1,000 krad. The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

(2-3) Storage elastic modulus modifier (γ)
The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to this embodiment may contain a storage elastic modulus adjuster (γ). The storage elastic modulus modifier (γ) has a weight average molecular weight of 4,000 or less, and has a storage elastic modulus at 23 ° C. before irradiation with energy rays of the pressure-sensitive adhesive layer 3 (in this specification, “storage elastic modulus before irradiation”). The composition of the pressure-sensitive adhesive layer 3 is not particularly limited as long as the adhesiveness of the pressure-sensitive adhesive layer 3 to the protective film-forming film 4 can be increased in a state before being irradiated with energy rays. It may be composed of one type of compound or may be composed of a plurality of types of compounds. From the viewpoint of more stably lowering the storage elastic modulus of the pressure-sensitive adhesive layer 3 before irradiation, the weight average molecular weight of the storage elastic modulus modifier (γ) is preferably 2,500 or less, and preferably 2,000 or less. Is particularly preferred. The lower limit of the weight average molecular weight of the storage elastic modulus modifier (γ) is not particularly limited, but if it is too low, it tends to volatilize and there is a concern that the composition stability of the above-mentioned adhesive composition will be reduced. Therefore, the weight average molecular weight of the storage elastic modulus modifier (γ) is preferably 300 or more, more preferably 500 or more, and particularly preferably 700 or more. The weight average molecular weight can be measured using a GPC device (HLC-8220, manufactured by Tosoh Corp.) and a column (TSK-GEL GMHXL, manufactured by Tosoh Corp.).

  As described above, the energy beam polymerizable compound (β) contained in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 may have a property as a storage elastic modulus modifier (γ). The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 may contain a storage elastic modulus adjusting agent (γ) separately. Examples of such separately contained storage modulus modifier (γ) include tackifying resins and long-chain alkyl acrylic oligomers.

  The content of the storage modulus modifier (γ) is preferably 50 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (α), from the viewpoint of stably exhibiting the function, and 75 parts by mass. More preferably, it is more preferably 100 parts by mass or more. Moreover, in order to maintain the cohesiveness of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 3 to an appropriate level, the content of the storage elastic modulus modifier (γ) is 500 with respect to 100 parts by mass of the acrylic polymer (α). It is preferable to set it as a mass part or less, It is more preferable to set it as 400 mass parts or less, It is especially preferable to set it as 350 mass parts or less.

  In the case where the storage modulus modifier (γ) contains a tackifying resin, the type of the tackifying resin is not particularly limited. Polymerized rosin, esterified rosin, disproportionated rosin, and rosin-based tackifying resins such as hydrogenated resins thereof, or terpene-based tackifying resins such as α-pinene resin may be used. Further, it may be a petroleum resin such as a hydrocarbon resin. Alternatively, aromatic tackifying resins such as coumarone resins, alkyl / phenol resins, and xylene resins may be used.

  By using a combination of these different types of tackifying resins, the compatibility of the storage modulus modifier (γ) with the acrylic polymer (α) is increased, and preferable characteristics may be obtained. As an example, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 contains a polymerized rosin ester (C1) as a storage elastic modulus modifier (γ), a hydrogenated rosin ester (C2), and a hydrocarbon resin. The case where at least one of (C3) is contained is mentioned. When the tackifying resin is contained, the content of the polymerized rosin ester (C1) in the composition for forming the pressure-sensitive adhesive layer 3 is 20 masses per 100 mass parts of the acrylic polymer (α). Part or less, more preferably 5 parts by weight or more and 18 parts by weight or less, and particularly preferably 7 parts by weight or more and 15 parts by weight or less. The total of the content of the hydrogenated rosin ester (C2) and the content of the hydrocarbon resin (C3) in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 is the aggregation of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 3 From the viewpoint of enhancing the properties, it is preferably 50 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (α), more preferably 70 parts by mass or more and 200 parts by mass or less, and 90 parts by mass or more and 170 parts by mass. It is particularly preferred that the amount is not more than parts.

  The long-chain alkyl acrylic oligomer is an oligomer obtained by polymerizing an alkyl (meth) acrylate having 4 to 18 carbon atoms, and the specific structure of the alkyl group portion is not particularly limited. A specific example of the monomer for forming such an oligomer is butyl acrylate.

(2-4) Crosslinking agent (δ)
As described above, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to this embodiment may contain a crosslinking agent (δ) that can react with the acrylic polymer (α). In this case, the pressure-sensitive adhesive layer 3 according to this embodiment contains a cross-linked product obtained by a cross-linking reaction between the acrylic polymer (α) and the cross-linking agent (δ).

  Examples of the crosslinking agent (δ) include, for example, epoxy compounds, isocyanate compounds, metal chelate compounds, aziridine compounds and other polyimine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides, metals Examples include salts. Among these, it is preferable that the crosslinking agent (δ) is a polyisocyanate compound because it is easy to control the crosslinking reaction.

  Here, the polyisocyanate compound will be described in some detail. The polyisocyanate compound is a compound having two or more isocyanate groups per molecule, for example, aromatic polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; dicyclohexylmethane-4,4′-diisocyanate, bicycloheptane Alicyclic isocyanate compounds such as triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, hydrogenated xylylene diisocyanate; isocyanates having a chain skeleton such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate Can be mentioned.

  Also, biuret bodies, isocyanurate bodies of these compounds, adduct bodies that are reaction products of these compounds with non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, castor oil, etc. A modified product of can also be used. The polyisocyanate compound may be one type or a plurality of types.

  When the pressure-sensitive adhesive layer 3 according to this embodiment has a cross-linked product based on the acrylic polymer (α) and the cross-linking agent (δ), the cross-linking density related to the cross-linked product contained in the pressure-sensitive adhesive layer 3 is adjusted. By doing so, characteristics, such as a storage elastic modulus before irradiation, of the adhesive layer 3 can be controlled. This crosslinking density can be adjusted by changing the content of the crosslinking agent (δ) contained in the composition for forming the pressure-sensitive adhesive layer 3.

  Specifically, when the crosslinking agent (δ) is composed of the above-mentioned isocyanate compound, the content of the crosslinking agent (δ) in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 is determined based on the acrylic polymer. (Α) By setting the amount to 5 parts by mass or more with respect to 100 parts by mass, it becomes easy to control the storage elastic modulus before irradiation of the pressure-sensitive adhesive layer 3 to an appropriate range. From the viewpoint of enhancing the controllability, the content of the cross-linking agent (δ) is more preferably 10 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (α). Is particularly preferred. The upper limit of the content of the cross-linking agent (δ) is not particularly limited, but when the content is excessively high, depending on the content of the storage elastic modulus modifier (γ), the storage elastic modulus before irradiation is a range described later. Therefore, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less with respect to 100 parts by mass of the acrylic polymer (α). When the crosslinking agent (δ) is composed of the above epoxy compound, the content of the crosslinking agent (δ) should be about 0.1 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (α). There can be.

  When the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to the present embodiment contains a crosslinking agent (δ), an appropriate crosslinking accelerator is added depending on the type of the crosslinking agent (δ). It is preferable to contain. For example, when the crosslinking agent (δ) is a polyisocyanate compound, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 preferably contains an organic metal compound-based crosslinking accelerator such as an organic tin compound. .

(2-5) Other components The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 included in the pressure-sensitive adhesive sheet 1 according to the present embodiment includes, in addition to the above components, a photopolymerization initiator, a dye, a pigment, and the like. You may contain various additives, such as a coloring material, a flame retardant, and a filler.

  Here, the photopolymerization initiator will be described in some detail. Examples of photopolymerization initiators include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones. 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, β-chloranthraquinone 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.

(2-6) Thickness The thickness of the pressure-sensitive adhesive layer 3 included in the pressure-sensitive adhesive sheet 1 according to this embodiment is not particularly limited. From the viewpoint of appropriately maintaining the adhesiveness of the pressure-sensitive adhesive layer 3 to the adherend (protective film-forming film 4, jig, etc.), the thickness of the pressure-sensitive adhesive layer 3 is preferably 1 μm or more, and 2 μm or more. More preferably, it is more preferably 3 μm or more. On the other hand, from the viewpoint of reducing the possibility of chip chipping during the dicing process, the thickness of the pressure-sensitive adhesive layer 3 is preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 50 μm or less.

(3) Release Sheet As shown in FIG. 9, the pressure-sensitive adhesive sheet 1 according to this embodiment is a pressure-sensitive adhesive layer until the protective film-forming film 4 is laminated on the surface 1 </ b> A on the pressure-sensitive adhesive layer 3 side. For the purpose of protecting 3, the release surface 5A of the release sheet 5 may be bonded to the surface 1A on the pressure-sensitive adhesive layer 3 side. The configuration of the release sheet 5 is arbitrary, and examples include a plastic film that has been subjected to a release treatment with a release agent or the like. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable. Although there is no restriction | limiting in particular about the thickness of the peeling sheet 5, Usually, it is about 20 micrometers or more and 250 micrometers or less.

2. Adhesive Roll The laminate including the adhesive sheet 1 according to the present embodiment is preferably a long body because continuous work is possible and workability is improved. It is preferable from the viewpoint of easy storage that the long body is wound in the longitudinal direction to form a wound body, that is, an adhesive roll.

  The adhesive sheet 1 itself is an elongated body, and the elongated body may be cut from the elongated body as necessary to have a shape for use in a dicing process. In this case, the elongate body includes a plurality of energy ray transmission regions 1a that are separated in the elongate direction. This elongate body may be comprised only from the adhesive sheet 1. FIG. In this case, from the viewpoint of enhancing the feeding property of the pressure-sensitive adhesive sheet 1 when the pressure-sensitive adhesive sheet 1 is used as a pressure-sensitive adhesive roll, the surface 1B on the base material 2 side of the pressure-sensitive adhesive sheet 1 is preferably a peelable surface having peelability. Alternatively, the long body may be a laminate of the pressure-sensitive adhesive sheet 1 and the release sheet 5 bonded so that the release surface 5A faces the surface 1A on the pressure-sensitive adhesive layer 3 side. In this case, the surface 1B on the base material 2 side of the pressure-sensitive adhesive sheet 1 may not be a release surface.

  When the above-mentioned long body is used for the dicing step in advance, a plurality of the long release sheets 5 and the release sheet 5 are arranged in the longitudinal direction while being separated from each other on the release surface 5A of the release sheet 5. The structure provided with the adhesive sheet 1 cut-processed in the shape may be sufficient. In this case, the pressure-sensitive adhesive sheet 1 is laminated so that the surface 1A on the pressure-sensitive adhesive layer 3 side faces the release surface 5A of the release sheet 5.

3. Manufacturing method of adhesive sheet The manufacturing method of the adhesive sheet 1 will not be specifically limited if the adhesive layer 3 can be laminated | stacked on one main surface of the base material 2. FIG. For example, the above-mentioned coating solution for forming an adhesive layer is applied on one main surface of the substrate 2 by a die coater, curtain coater, spray coater, slit coater, knife coater, etc. to form a coating film. And the adhesive layer 3 can be formed by drying the coating film on the said one main surface. The properties of the coating composition are not particularly limited as long as it can be applied. The composition for forming the pressure-sensitive adhesive layer 3 may be contained as a solute, or may be contained as a dispersoid. There is also.

  When the coating composition contains a cross-linking agent (δ), the acrylic weight in the coating film can be changed by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. The cross-linking reaction between the coalescence (α) and the cross-linking agent (δ) may be advanced to form a cross-linked structure in the pressure-sensitive adhesive layer 3 at a desired density. In order to make this crosslinking reaction sufficiently proceed, after the pressure-sensitive adhesive layer 3 is laminated on the substrate 2 by the above-described method or the like, the obtained pressure-sensitive adhesive sheet 1 is placed in an environment of, for example, 23 ° C. and relative humidity 50%. Curing may be performed such as standing for days.

  As another example of the method for producing the pressure-sensitive adhesive sheet 1 according to this embodiment, the above-mentioned pressure-sensitive adhesive layer-forming coating solution is applied onto the release surface 5A of the above-described release sheet 5 to form a coating film, which is then dried. Then, a laminate composed of the pressure-sensitive adhesive layer 3 and the release sheet 5 is formed, and the surface opposite to the surface facing the release sheet 5 in the pressure-sensitive adhesive layer 3 of the laminate is used as one main surface of the substrate 2. A laminated body of the pressure-sensitive adhesive sheet 1 and the release sheet 5 may be obtained by sticking. The release sheet 5 in this laminate may be peeled off as a process material, or may protect the pressure-sensitive adhesive layer 3 until the protective film-forming film is formed on the surface 1A on the pressure-sensitive adhesive layer 3 side. .

  The pressure-sensitive adhesive sheet 1 thus obtained may be a finished product as it is, or a pressure-sensitive adhesive positioned in the energy ray transmission region 1a by irradiating energy rays from the surface 1B side of the pressure-sensitive adhesive sheet 1 on the substrate 2 side. The polymerization reaction of the components contained in the layer 3 may be advanced. In the present specification, the pressure-sensitive adhesive sheet 1 including the pressure-sensitive adhesive layer 3 in which the polymerization reaction has partially proceeded in this way may be referred to as “post-irradiation pressure-sensitive adhesive sheet”.

4). Protective film forming film The pressure-sensitive adhesive sheet 1 according to the present embodiment is not used alone, and a protective film-forming film 4 described below is laminated on the main surface 1A on the pressure-sensitive adhesive layer 3 side. It is used as the composite sheet 10 for forming a protective film. In addition, the adhesive sheet 1 with which the composite sheet 10 for protective film formation is in the state of an adhesive sheet after irradiation. Hereinafter, the protective film-forming film 4 will be described in detail.

As long as the protective film-forming film 4 fulfills the following functions, its configuration (structure, composition, etc.) is not particularly limited.
(Function 1) It is possible to form a protective film for protecting the surface of the workpiece W on which the protective film forming film 4 is laminated. (Function 2) The protective film forming film 4 or a protective film formed from this (this book) In the specification, these may be collectively referred to as “protective film or the like.”) When the material is disposed between the workpiece W and the pressure-sensitive adhesive sheet 1 and subjected to a dicing process, the workpiece W and the protection are protected. Peeling between the film and the like and peeling between the protective film and the adhesive sheet 1 are less likely to occur (Function 3) In the pickup process performed after the dicing process, between the workpiece W and the protective film or the like Peeling occurs between the protective film or the like and the pressure sensitive adhesive sheet 1 in preference to peeling at (Function 4) Opposite of the surface facing the workpiece W in the protective film formed from the protective film forming film 4 Laser marking on side Etc. When performing the marking by, can form a mark having excellent visibility

  Hereinafter, the protective film-forming film 4 is obtained by curing a composition for forming the protective film 4 (also referred to as “protective film-forming composition” in the present specification). Specifically, The protective film-forming film 4 will be described by taking as an example the case of a film having (1) sheet shape maintainability, (2) initial adhesiveness, and (3) curability.

The protective film-forming film 4 can be provided with (1) sheet shape maintainability and (3) curability by adding a binder component. As the binder component, the polymer component (A) and the curable component ( The first binder component containing B) or the second binder component containing the curable polymer component (AB) having the properties of the component (A) and the component (B) can be used.
In addition, it is a function for temporarily attaching the protective film-forming film 4 to the adherend until curing (2) The initial adhesiveness may be pressure-sensitive adhesiveness and is softened by heat. The property of adhering may be sufficient. (2) The initial adhesiveness is usually controlled by adjusting various properties of the binder component and adjusting the blending amount of the inorganic filler (C) described later.

(First binder component)
The first binder component imparts (1) sheet shape maintaining property and (3) curability to the protective film forming film 4 by containing the polymer component (A) and the curable component (B). In addition, the 1st binder component does not contain a curable polymer component (AB) for the convenience of distinguishing from a 2nd binder component.

(A) Polymer component The polymer component (A) is added to the protective film-forming film 4 mainly for the purpose of imparting (1) sheet shape maintaining property to the protective film-forming film 4.
In order to achieve the above object, the polymer component (A) has a weight average molecular weight (Mw) of usually 20,000 or more, preferably 20,000 to 3,000,000. The value of the weight average molecular weight (Mw) is a value when measured by a gel permeation chromatography method (GPC) method (polystyrene standard). Measured by such a method is, for example, in high-speed GPC device manufactured by Tosoh Corporation "HLC-8120GPC", high-speed column "TSK gurd column H _XL -H", "TSK Gel _{GMH XL",} "TSK Gel G2000 H _XL" (The above, all manufactured by Tosoh Corporation) are connected in this order, and the detector is used as a differential refractometer at a column temperature of 40 ° C. and a liquid feed rate of 1.0 mL / min.
In addition, for convenience to distinguish from the curable polymer (AB) described later, the polymer component (A) does not have a curing functional functional group described later.

  As the polymer component (A), an acrylic polymer, polyester, phenoxy resin (for the purpose of distinguishing from the curable polymer (AB) described later, limited to those having no epoxy group), polycarbonate, polyether, polyurethane Polysiloxane, rubber polymer, etc. can be used. Further, it is an acrylic urethane resin obtained by reacting a urethane prepolymer having an isocyanate group at a molecular terminal with an acrylic polyol which is an acrylic polymer having a hydroxyl group, which is a combination of two or more of these. May be. Furthermore, two or more of these may be used in combination, including a polymer in which two or more are bonded.

(A1) Acrylic polymer As the polymer component (A), an acrylic polymer (A1) is preferably used. The glass transition temperature (Tg) of the acrylic polymer (A1) is preferably in the range of −60 to 50 ° C., more preferably −50 to 40 ° C., and further preferably −40 to 30 ° C. When the glass transition temperature of the acrylic polymer (A1) is high, the probe tack value of the protective film-forming film 4 tends to decrease, and the adhesiveness after curing tends to decrease. Therefore, the glass transition temperature (Tg) of the acrylic polymer (A1) is particularly preferably in the range of −40 to −5 ° C.

  The weight average molecular weight of the acrylic polymer (A1) is preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic polymer (A1) is high, the probe tack value of the protective film-forming film 4 tends to decrease, and the adhesiveness after curing tends to decrease. Accordingly, the weight average molecular weight of the acrylic polymer (A1) is more preferably 600,000 to 1,200,000.

The acrylic polymer (A1) contains (meth) acrylic acid ester in at least a constituent monomer.
As the (meth) acrylic acid ester, an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, etc .; (meth) acrylate having a cyclic skeleton, specifically cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl ( Examples include meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate. Among those exemplified as a monomer having a functional group that reacts by heat, a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an amino group, which will be described later, (meth) acrylic acid ester Can be illustrated.

  A monomer having a hydroxyl group may be used as the monomer constituting the acrylic polymer (A1). When such a monomer is used, when a hydroxyl group is introduced into the acrylic polymer (A1) and the protective film-forming film 4 contains an energy ray-curable component (B2) separately, this and the acrylic polymer (A1). Compatibility with the polymer (A1) is improved. Examples of the monomer having a hydroxyl group include (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxylethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-methylol (meth) acrylamide and the like.

  As the monomer constituting the acrylic polymer (A1), a monomer having a carboxyl group may be used. When such a monomer is used, a carboxyl group is introduced into the acrylic polymer (A1), and the protective film-forming film 4 contains an energy ray-curable component (B2) separately. Compatibility with the acrylic polymer (A1) is improved. Examples of the monomer having a carboxyl group include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. When using an epoxy-based thermosetting component as the curable component (B) described below, the carboxyl group and the epoxy group in the epoxy-based thermosetting component react with each other. The amount used is preferably small.

  As a monomer constituting the acrylic polymer (A1), a monomer having an amino group may be used. Examples of such a monomer include (meth) acrylic acid esters having an amino group such as monoethylamino (meth) acrylate.

  In addition, vinyl acetate, styrene, ethylene, α-olefin, or the like may be used as a monomer constituting the acrylic polymer (A1).

  The acrylic polymer (A1) may be cross-linked. In the crosslinking, the acrylic polymer (A1) before being crosslinked has a crosslinkable functional group such as a hydroxyl group, and the crosslinkable functional group and the crosslinkable group are crosslinked by adding a crosslinker to the protective film forming composition. This is performed by the reaction of the functional group of the agent. By crosslinking the acrylic polymer (A1), the cohesive force of the protective film-forming film 4 can be adjusted.

  Examples of the crosslinking agent include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

  Examples of organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds. Examples thereof include terminal isocyanate urethane prepolymers obtained by reacting with a polyol compound.

  Specifically, as the organic polyvalent isocyanate compound, 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, and lysine isocyanates thereof Examples thereof include polyhydric alcohol adducts.

  Specific examples of organic polyvalent imine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylol. Mention may be made of methane-tri-β-aziridinylpropionate and N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine.

  A crosslinking agent is 0.01-20 mass parts normally with respect to 100 mass parts of acrylic polymers (A1) before bridge | crosslinking, Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-5 mass parts. Used in ratio.

  In the present invention, when the content of the component constituting the protective film-forming film 4 is determined with reference to the content of the polymer component (A), the acrylic polymer in which the polymer component (A) is crosslinked Is the content of the acrylic polymer before being crosslinked.

(A2) Non-acrylic resin In addition, as the polymer component (A), polyester, phenoxy resin (for the purpose of distinguishing from the curable polymer (AB) described later, only those having no epoxy group), polycarbonate, poly One type of non-acrylic resin (A2) selected from ethers, polyurethanes, polysiloxanes, rubber polymers, or a combination of two or more of these may be used, or a combination of two or more types. Such a resin preferably has a weight average molecular weight of 20,000 to 100,000, and more preferably 20,000 to 80,000.

  The glass transition temperature of the non-acrylic resin (A2) is preferably -30 to 150 ° C, more preferably -20 to 120 ° C.

  When using a non-acrylic resin (A2) together with the above-mentioned acrylic polymer (A1), the content of the non-acrylic resin (A2) is not particularly limited. The mass ratio (A2: A1) between the non-acrylic resin (A2) and the acrylic polymer (A1) is usually in the range of 1:99 to 60:40, preferably 1:99 to 30:70.

(B) Curable component The curable component (B) is added to the protective film-forming film 4 mainly for imparting curability to the protective film-forming film 4. As the curable component (B), a thermosetting component (B1) or an energy beam curable component (B2) can be used. Moreover, you may use combining these. The thermosetting component (B1) contains at least a compound having a functional group that reacts by heating. The energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts by irradiation with energy rays, and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams. Curing is realized by the functional groups of these curable components reacting to form a three-dimensional network structure. Since the curable component (B) is used in combination with the polymer component (A), its weight average molecular weight (Mw) is usually from the viewpoint of suppressing the viscosity of the composition for forming a protective film and improving the handleability. Is 10,000 or less, and preferably 100 to 10,000.

(B1) Thermosetting component As the thermosetting component, for example, an epoxy thermosetting component is preferable.
The epoxy thermosetting component preferably contains a compound (B11) having an epoxy group and a combination of a compound (B11) having an epoxy group and a thermosetting agent (B12).

(B11) Compound having an epoxy group As the compound (B11) having an epoxy group (hereinafter sometimes referred to as “epoxy compound (B11)”), a conventionally known compound can be used. Specifically, polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as epoxy resins and phenylene skeleton type epoxy resins. These can be used individually by 1 type or in combination of 2 or more types.

  When the epoxy compound (B11) is used, the protective film-forming film 4 preferably contains 1 to 1,500 parts by mass of the epoxy compound (B11) with respect to 100 parts by mass of the polymer component (A). More preferably, it is contained in 3 to 1,200 parts by mass. When there are few epoxy compounds (B11), there exists a tendency for the adhesiveness after hardening of the film 4 for protective film formation to fall. Further, when only the epoxy compound (B11) that is solid at room temperature is used, if the epoxy compound (B11) is small, that is, if the polymer component (A) is relatively large, the protective film is formed. The probe tack value of the film 4 tends to increase. The normal temperature indicates 25 ° C., and the same applies hereinafter.

  Since there exists such a tendency, when using only what is a solid at normal temperature as an epoxy compound (B11), an epoxy compound (B11) is 70-150 with respect to 100 mass parts of polymer components (A). It is particularly preferable that a part by mass is included.

(B12) Thermosetting agent The thermosetting agent (B12) functions as a curing agent for the epoxy compound (B11). A preferable thermosetting agent includes a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Of these, phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, and phenolic hydroxyl groups and amino groups are more preferable.

  Specific examples of the phenolic curing agent include polyfunctional phenolic resin, biphenol, novolac type phenolic resin, dicyclopentadiene type phenolic resin, zylock type phenolic resin, and aralkylphenolic resin. A specific example of the amine curing agent is DICY (dicyandiamide). These can be used individually by 1 type or in mixture of 2 or more types.

  It is preferable that it is 0.1-500 mass parts with respect to 100 mass parts of epoxy compounds (B11), and, as for content of a thermosetting agent (B12), it is more preferable that it is 1-200 mass parts. When there is little content of a thermosetting agent, there exists a tendency for the adhesiveness after hardening to fall.

(B13) Curing accelerator The curing accelerator (B13) may be used to adjust the rate of thermal curing of the protective film-forming film 4. The curing accelerator (B13) is particularly preferably used when an epoxy thermosetting component is used as the thermosetting component (B1).

  Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate. These can be used individually by 1 type or in mixture of 2 or more types.

  The curing accelerator (B13) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). Included in the amount of. By containing the curing accelerator (B13) in an amount within the above range, it has excellent adhesiveness even when exposed to high temperatures and high humidity, and has high reliability even when exposed to severe reflow conditions. Can be achieved. By adding the curing accelerator (B13), the adhesiveness after curing of the protective film-forming film 4 can be improved. Such an action becomes stronger as the content of the curing accelerator (B13) increases.

(B2) Energy ray-curable component The protective film-forming film 4 contains an energy ray-curable component, so that the protective film-forming film 4 can be cured without performing a heat-curing step that requires a large amount of energy and a long time. It can be carried out. Thereby, the manufacturing cost can be reduced.

  As the energy ray-curable component, the compound (B21) having a functional group that reacts by irradiation with energy rays may be used alone, but the compound (B21) having a functional group that reacts by irradiation with energy rays and a photopolymerization initiator ( It is preferable to use a combination of B22).

(B21) Compound having a functional group that reacts upon irradiation with energy rays Compound (B21) having a functional group that reacts upon irradiation with energy rays (hereinafter sometimes referred to as “energy ray-reactive compound (B21)”) is specific. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate Examples include acrylate compounds such as acrylates, oligoester acrylates, urethane acrylate oligomers, epoxy acrylates, polyether acrylates, and esters. An acrylate compound having a polymerized structure such as an acrylate compound such as a taconic acid oligomer, which has a relatively low molecular weight. Such a compound has at least one polymerizable double bond in the molecule.

  When the energy ray reactive compound (B21) is used, the energy ray reactive compound (B21) is preferably 1 to 1, with respect to 100 parts by mass of the polymer component (A). 500 parts by mass are contained, more preferably 3 to 1,200 parts by mass.

(B22) Photopolymerization initiator By combining the energy ray-reactive compound (B21) with the photopolymerization initiator (B22), the polymerization curing time can be shortened and the amount of light irradiation can be reduced.

  Specific examples of such a photopolymerization initiator (B22) include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. 2,4-diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and β -Chloranthraquinone and the like. A photoinitiator (B22) can be used individually by 1 type or in combination of 2 or more types.

  The blending ratio of the photopolymerization initiator (B22) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the energy ray reactive compound (B21). . If the blending ratio of the photopolymerization initiator (B22) is less than 0.1 parts by mass, sufficient curability may not be obtained due to insufficient photopolymerization, and if it exceeds 10 parts by mass, the residue does not contribute to photopolymerization. May cause a malfunction.

(Second binder component)
The second binder component imparts (1) sheet shape maintaining property and (3) curability to the protective film-forming film 4 by containing the curable polymer component (AB).

(AB) Curable polymer component The curable polymer component is a polymer having a functional functional group. The curing functional group is a functional group that can react with each other to form a three-dimensional network structure, and examples thereof include a functional group that reacts by heating and a functional group that reacts by energy rays.

  The functional functional group may be added to the unit of a continuous structure that becomes the skeleton of the curable polymer (AB) or may be added to the terminal. When the functional functional group is added in the unit of the continuous structure that becomes the skeleton of the curable polymer component (AB), the functional functional group may be added to the side chain or directly to the main chain. You may do it. The weight average molecular weight (Mw) of the curable polymer component (AB) is usually 20,000 or more from the viewpoint of achieving the purpose of imparting (1) sheet shape maintainability to the protective film-forming film 4.

  An example of a functional group that reacts by heating is an epoxy group. Examples of the curable polymer component (AB) having an epoxy group include a high molecular weight epoxy group-containing compound and a phenoxy resin having an epoxy group. High molecular weight epoxy group-containing compounds are disclosed, for example, in JP-A-2001-261789.

  Moreover, it is a polymer similar to the above-mentioned acrylic polymer (A1), which is polymerized using a monomer having an epoxy group as a monomer (epoxy group-containing acrylic polymer). Also good. Examples of such monomers include (meth) acrylic acid esters having a glycidyl group such as glycidyl (meth) acrylate.

  When an epoxy group-containing acrylic polymer is used, the preferred embodiment is the same as that of the acrylic polymer (A1).

  When the curable polymer component (AB) having an epoxy group is used, the thermosetting agent (B12) or the curing accelerator (B13) is used as in the case of using an epoxy thermosetting component as the curable component (B). ) May be used in combination.

  Examples of the functional group that reacts with energy rays include a (meth) acryloyl group. As the curable polymer component (AB) having a functional group that reacts with energy rays, an acrylate compound having a polymer structure such as polyether acrylate, and the like having a high molecular weight can be used.

  In addition, for example, a raw material polymer having a functional group X such as a hydroxyl group in a side chain, a functional group Y that can react with the functional group X (for example, an isocyanate group when the functional group X is a hydroxyl group) and energy beam irradiation Alternatively, a polymer prepared by reacting a low molecular compound having a functional group that reacts with the above may be used.

  In this case, when a raw material polymer corresponds to the above-mentioned acrylic polymer (A), the preferable aspect of the raw material polymer is the same as that of the acrylic polymer (A).

  When the curable polymer component (AB) having a functional group that reacts with energy rays is used, the photopolymerization initiator (B22) may be used in the same manner as when the energy ray curable component (B2) is used. .

  The second binder component may contain the above-described polymer component (A) and curable component (B) in combination with the curable polymer component (AB).

  In addition to the binder component, the protective film-forming film 4 may contain the following components.

(C) Inorganic filler The protective film-forming film 4 may contain an inorganic filler (C). By blending the inorganic filler (C) in the protective film-forming film 4, the thermal expansion coefficient of the cured protective film can be adjusted, and the thermal expansion of the protective film after curing with respect to the workpiece W By optimizing the coefficient, the reliability of a product (hereinafter abbreviated as “product”) formed from the workpiece W such as a semiconductor device can be improved. It is also possible to reduce the hygroscopicity of the protective film after curing.

  Furthermore, by applying laser marking to the protective film, the inorganic filler (C) is exposed in the portion scraped off by the laser light, and the reflected light diffuses to exhibit a color close to white. Thereby, when the film W for protective film formation contains the coloring agent (D) mentioned later, there exists an effect that a contrast difference is obtained by a laser marking part and another part, and printing becomes clear.

  Preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like, beads formed by spheroidizing these, single crystal fibers, glass fibers, and the like. Among these, silica filler and alumina filler are preferable. The said inorganic filler (C) can be used individually or in mixture of 2 or more types.

  The content of the inorganic filler (C) is not particularly limited. When the content is excessively large, the adhesion to the workpiece W is lowered, and when it is excessively small, it is difficult to obtain the effect of increasing the visibility of the marking portion by adding an inorganic filler, and inorganic. What is necessary is just to set suitably in consideration of a composition of a filler (C). Usually, it is preferable that content of an inorganic filler (C) is 50-80 mass% as a ratio which occupies for the mass of the total solid which comprises the film 4 for protective film formation, More preferably, it is 60-80 mass%. is there.

(D) Colorant Colorant (D) can be blended in the protective film-forming film 4. By blending the colorant, it is possible to prevent the product from malfunctioning due to infrared rays or the like generated from devices arranged around the product when a product such as a semiconductor device is incorporated into the device. Further, when a protective film or the like is stamped by means such as laser marking, there is an effect that marks such as characters and symbols can be easily recognized. That is, in products (semiconductor devices, semiconductor chips, etc.) on which a protective film is formed, the product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the protective film surface is scraped off and printed by laser light). When the protective film contains the colorant (D), a sufficient difference in contrast between the portion of the protective film scraped by the laser beam and the portion that is not removed is obtained, and the visibility is improved.

  As the colorant, organic or inorganic pigments and dyes are used. Among these, black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties. Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto. Carbon black is particularly preferable from the viewpoint of increasing the reliability of products such as semiconductor devices. A coloring agent (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending amount of the colorant (D) is preferably 0.1 to 35 parts by mass, more preferably 0.5 to 25 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming film 4. Especially preferably, it is 1-15 mass parts.

(E) Coupling agent The coupling agent (E) having a functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group is bonded to the adherend of the protective film-forming film 4, adhesiveness and / or It may be used to improve the cohesiveness of the protective film. Moreover, the water resistance can be improved by using a coupling agent (E), without impairing the heat resistance of the protective film obtained by hardening | curing the film 4 for protective film formation. Examples of such coupling agents include titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like. Of these, silane coupling agents are preferred.

  As the silane coupling agent, the functional group that reacts with the organic functional group is a group that reacts with the functional group of the polymer component (A), the curable component (B), the curable polymer component (AB), and the like. Some silane coupling agents are preferably used.

Examples of such silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacryloxy). Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltri Methoxysilane , Methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. These can be used individually by 1 type or in mixture of 2 or more types.

  A silane coupling agent is 0.1-20 mass parts normally with respect to a total of 100 mass parts of a polymer component (A), a curable component (B), and a curable polymer component (AB), Preferably it is 0.00. 2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass. If the content of the silane coupling agent is less than 0.1 parts by mass, the above effect may not be obtained, and if it exceeds 20 parts by mass, it may cause outgassing.

(F) Release agent A release agent may be added to adjust the adhesion of the protective film-forming film 4 to the surface of the workpiece W and the adhesion to the pressure-sensitive adhesive layer 3. Examples of the release agent include silicone compounds such as polydimethylsiloxane, polyphenylmethylsiloxane, and polydiphenylsiloxane, and fluorine compounds.

Among these, a silicone compound is preferable, and an organopolysiloxane having an aromatic ring-containing group as a side chain and a kinematic viscosity at 25 ° C. of 50 to 100,000 mm ² / s is more preferable. Polysiloxane is a compound in which a plurality of unit structures represented by —Si (X) ₂ —O— (X represents a side chain) is connected, and the number of unit structures is not particularly limited, but usually 3 or more. It is. The kinematic viscosity value can be controlled by increasing or decreasing the number of unit structures.

  The silicone compound lowers the adhesion with the support by the siloxane portion of the organopolysiloxane and has a high lipid solubility by having the above aromatic ring-containing group in the side chain, and other components in the composition for forming a protective film High compatibility with. In addition, the curing component (B) in the composition for forming a protective film often has an aromatic ring as a constituent component, and in such a case, the compatibility of the silicone compound with the aromatic ring-containing group further increases. .

  The aromatic ring-containing group is an aromatic ring-containing group, and examples thereof include a phenyl group and an aralkyl group. The term “aralkyl group” as used herein means that the alkyl part is linear or branched, the alkyl part preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and the aryl part preferably has carbon atoms. It is an aralkyl group that is 6 to 10, more preferably 6. Preferable examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylisopropyl group. The aromatic ring-containing group is preferably an aralkyl group.

(G) General-purpose additive In addition to the above, various additives may be added to the protective film-forming film 4 as necessary. Examples of various additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, and the like.

  The thickness of the protective film-forming film 4 is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, and particularly preferably 7 to 200 μm.

  The optical characteristics of the protective film-forming film 4 are not particularly limited. The maximum transmittance in the wavelength range of 300 to 1,200 nm in the protective film formed from the protective film-forming film 4 is preferably 20% or less, more preferably 0 to 15%, and 0 % Is more preferably 10% or less, and particularly preferably 0.001 to 8%. In the present specification, the maximum transmittance of the protective film refers to the total thickness of the protective film having a thickness of 25 μm at 300 to 1,200 nm using a UV-vis spectrum inspection apparatus (for example, manufactured by Shimadzu Corporation). When the light transmittance is measured, it means the highest value of transmittance.

  As described above, when the protective film is difficult to transmit the visible light wavelength region and / or the infrared wavelength region, effects such as prevention of malfunction caused by infrared of a product such as a semiconductor device and an improvement in printing visibility are obtained. It is done. The optical properties of the protective film can be adjusted by the colorant (D) as a component contained in the protective film-forming film 4.

5. Protective film forming composite sheet A protective film forming composite sheet 10 according to the present embodiment is a pressure-sensitive adhesive sheet (in a state of a post-irradiation pressure-sensitive adhesive sheet) 1 according to the above-described present embodiment, and a pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 1. And a protective film-forming film 4 laminated on at least one region of the three-side main surface 1A.

  The adhesive sheet 1 included in the protective film-forming composite sheet 10 according to the present embodiment includes the mask layer 21 as described above, and the protective film region 1b of the adhesive sheet 1 includes the energy ray transmitting region 1a. For this reason, in the surface opposite to the surface facing the base material 2 of the pressure-sensitive adhesive layer 3, the region that is the protective film region 1 b but is not the energy ray transmitting region 1 a, that is, the peripheral portion of the protective film forming film 4. The adhesiveness of the pressure-sensitive adhesive layer 3 adhered to 4a to the protective film-forming film 4 is higher than the adhesiveness of the pressure-sensitive adhesive layer 3 located in the energy ray transmitting region 1a to the protective film-forming film 4. For this reason, the protective film-forming film 4 provided in the protective film-forming composite sheet 10 according to the present embodiment is relatively strongly in close contact with the adhesive sheet 1 at the peripheral edge 4a.

  In the composite sheet 10 for forming a protective film according to this embodiment, the release surface of the release sheet is bonded to the surface on the protective film forming film 4 side, and the workpiece W is an adhesive sheet of the protective film forming film 4. 1 is affixed to a surface opposite to the surface opposite to 1 or a surface on the protective film forming film 4 side of the protective film forming composite sheet 10 other than the region formed by the surface of the protective film forming film 4 The surface on the protective film forming film 4 side of the protective film forming composite sheet 10 may be protected until a jig such as a ring frame is disposed on the surface of the region 1Aa.

  The region 1Aa where the jig is disposed may be configured from the surface of the pressure-sensitive adhesive layer 3, or the jig adhesive layer may be laminated on the surface of the pressure-sensitive adhesive layer 3. It is as follows.

  The shape of the protective film-forming composite sheet 10 according to the present embodiment may be a shape corresponding to one workpiece W or a shape corresponding to a plurality of workpieces W. In the case of a shape corresponding to a plurality of workpieces W, the protective film-forming composite sheet 10 is a long body, and includes a plurality of protective film-forming films 4 separated in the longitudinal direction. It is preferable from the viewpoint of realizing continuous work. Even when the shape of the protective film-forming composite sheet 10 is a shape corresponding to one workpiece W, a plurality of protective film-forming composite sheets 10 are formed on the release surface of the release sheet made of a long body. It is preferable to arrange | position in the elongate direction of a peeling sheet, mutually separating. In this case, the protective film-forming composite sheet 10 is laminated so that the surface on the protective film-forming film 4 side faces the release surface of the release sheet.

  As described above, when the laminated body including the composite sheet 10 for forming a protective film is a long body as a whole, the laminated body is wound up in the long direction until it is used. It is preferable from the viewpoint of improving the storage easiness.

6). Method for Producing Protective Film-Forming Composite Sheet The method for producing protective film-forming composite sheet 10 is not particularly limited, but is preferably produced by the following production method.

  First, the adhesive sheet 1 which concerns on this embodiment is prepared, an energy ray is contained in the adhesive layer 3 located in the energy-beam permeable area | region 1a by irradiating an energy ray from the surface 1B side of the base material 2 side. The polymerization reaction of the component that causes the polymerization reaction by the irradiation is performed. As a result, the pressure-sensitive adhesive sheet 1 becomes a pressure-sensitive adhesive sheet after irradiation, and the pressure-sensitive adhesive property of the pressure-sensitive adhesive layer 3 located in the energy ray transmission region 1a with respect to the protective film-forming film 4 is on the surface 1A of the pressure-sensitive adhesive sheet 1 on the pressure-sensitive adhesive layer 3 side. It will be in the state which fell rather than the adhesiveness with respect to the film 4 for protective film formation of the adhesive layer 3 located in area | regions other than the energy ray transmission area | region 1a.

  Separately, a protective film-forming composition is prepared, and the protective film-forming composition is applied onto the release surface of the release sheet to form a coating film. A laminate with the protective film-forming film 4 is formed. Next, this laminate is half-cut so that the protective film forming film 4 is cut from the protective film forming film 4 side to remove unnecessary portions (a part of the protective film forming film 4), and the protective film The shape of the film 4 for formation is made into the shape corresponding to the area | region 1b for protective films of the adhesive sheet 1. FIG.

  The surface on the protective film forming film 4 side in the laminate comprising the release sheet and the protective film forming film 4 having a shape corresponding to the protective film region 1b thus obtained, and the pressure sensitive adhesive layer 3 side of the post-irradiation pressure sensitive adhesive sheet 1 The surface 1A is bonded so that the protective film-forming film 4 is in contact with the protective film region 1b.

  The post-irradiation pressure-sensitive adhesive sheet 1 is a post-irradiation pressure-sensitive adhesive sheet 1 from the post-irradiation pressure-sensitive adhesive sheet 1 side. The protective film forming composite sheet 10 processed into a predetermined shape is laminated on the release sheet by half-cutting so as to be cut and removing unnecessary portions (part of the post-irradiation pressure-sensitive adhesive sheet 1). A laminate is obtained. In addition, the peeling sheet with which this laminated body is provided peels in use.

7). Manufacturing Method of Chip with Protective Film Hereinafter, the protective film forming film 4 side surface of the protective film forming composite sheet 10 is attached to one surface of the workpiece W, and the protective film forming composite sheet 10 is attached. By separating the workpiece W into individual pieces and curing the protective film-forming film 4 when the protective film-forming film 4 is adhered to the surface of the workpiece W, a protective film is obtained. A method for manufacturing a chip with a protective film that obtains a chip with a protective film including a chip-shaped member obtained by separating the processed member W and a protective film laminated on one surface of the chip-shaped member will be described.

  First, a predetermined region on the surface on the protective film forming film 4 side of the protective film forming composite sheet 10, specifically, the surface 1A on the pressure sensitive adhesive layer 3 side of the adhesive sheet 1 provided in the protective film forming composite sheet 10. A region corresponding to the region 1c for the workpiece is attached to one surface of the workpiece W. The type of the workpiece W is not particularly limited, but is usually a semiconductor substrate such as a silicon wafer, and the surface on which the circuit is not formed, that is, the back surface is the deposition surface. If necessary, a jig such as a ring frame is arranged in a region 1Aa which is a part of the surface on the protective film forming film 4 side of the protective film forming composite sheet 10 and is formed of other than the protective film forming film 4. Also good.

  Next, the protective film forming film 4 provided in the protective film forming composite sheet 10 in the laminated structure of the workpiece W and the protective film forming composite sheet 10 (further provided with a jig) may be cured. Let it be a protective film. Hereinafter, the protective film-forming composite sheet 10 in which the protective film-forming film 4 becomes a protective film is also referred to as a “protective film-containing composite sheet”. The curing conditions for the protective film-forming film 4 are appropriately set according to the composition of the protective film-forming film 4. When it contains a thermosetting component, it is cured by heating (for example, 130 ° C., 2 hours). When a component that is cured by energy rays is contained, the protective film-forming film 4 is cured by irradiating energy rays such as ultraviolet rays through the pressure-sensitive adhesive sheet 1.

The laminate of the workpiece and the protective film-containing composite sheet obtained through the above-described curing process is placed on a dicing table for performing dicing and fixed. At this time, the protective film-containing composite sheet can be caused to function as a dicing sheet by placing the protective film-containing composite sheet so that the surface of the protective film-containing composite sheet on the substrate 2 side is in contact with the dicing table. The kind of this dicing process is not limited. The blade dicing which cuts using a rotary blade may be sufficient, and the laser dicing which uses a laser beam may be sufficient. In the case of laser dicing, ablation processing, which is removal processing of the workpiece, may be performed, or a deteriorated layer is formed inside the workpiece (specifically, a wafer made of a silicon-based material). It may be stealth dicing that changes the mechanical properties (particularly breakability). That is, the workpiece member W may be separated into pieces by cutting the workpiece member W using a rotary blade or laser light (full cutting may be mentioned as a specific example). May be performed. As a specific example of the fracture of the workpiece W, there is a fracture based on applying a tensile force to the workpiece W by extending the pressure-sensitive adhesive sheet 1 in the expanding step. Moreover, the workpiece W may be separated into pieces by a combination of cutting with laser light (groove processing by half cut) and breaking (braking) as in scribing.
Hereinafter, a case where dicing processing by blade dicing is performed will be described first as a specific example.

  Dicing processing by blade dicing is performed on the workpiece W fixed on the dicing table, and a structure in which a plurality of chips are arranged on the adhesive sheet 1 through a protective film is obtained. At that time, the protective film included in the protective film-containing composite sheet is also cut at the same time.

  Here, as described above, since the protective film forming film 4 is relatively strongly adhered to the adhesive layer 3 of the pressure sensitive adhesive sheet 1 at the peripheral edge 4a, the protective film forming film positioned at the peripheral edge 4a is formed. Even if the protective film formed by curing the protective film 4 is separated into pieces by dicing, a part of the separated protective film (small piece) is peeled off from the adhesive layer 3 and scattered, Chip scattering, in which the laminate of the small pieces of the protective film and the chip-like member peels off from the pressure-sensitive adhesive layer 3 and hardly scatters, is less likely to occur.

  When the dicing process is thus completed, an expanding process for expanding the adhesive sheet 1 is performed, and the chip-like members on the adhesive sheet 1 are separated from each other. Subsequently, by pressing a pin from the base material 2 side of the pressure-sensitive adhesive sheet 1 to extrude a laminated body of a small piece of a protective film and a chip-like member, and performing a pick-up step of picking up this with a collet, the above-mentioned The laminate is obtained as a chip with a protective film. Here, as described above, the pressure-sensitive adhesive layer 3 included in the pressure-sensitive adhesive sheet 1 according to the present embodiment is opposed to the protective film-forming film 4 at a portion facing the portion other than the peripheral edge 4 a of the protective film-forming film 4. Therefore, when picking up, the protective film forming film 4 is easily cured and the adhesive layer 3 is easily peeled off, and only the chip is picked up. Defects are less likely to occur.

  In the above description, the protective film-forming film 4 is cured before the dicing step, but the curing time is not limited thereto. Curing may be performed before the dicing process is started after the laminated structure of the workpiece W and the protective film forming composite sheet 10 is placed on the dicing table, and the picking process after the dicing process is performed. You may perform in either of the period until it starts. Or after picking up the laminated body of the small piece of the film 4 for protective film formation and a chip-shaped member, you may harden the small piece of the film 4 for protective film formation in the laminated body.

  When the dicing process is performed by laser dicing, the protective film or the like may be separated into pieces by the laser, or the protective film or the like is separated into pieces when the workpiece W is separated in the expanding process. Sometimes it is done. In the latter case, when the pressure-sensitive adhesive layer 3 is too low in adhesion to the protective film or the like, the protective film or the like is peeled off from the pressure-sensitive adhesive layer 3 due to the impact caused by the separation of the workpiece W. Therefore, as in the protective film-containing composite sheet 10 according to the present embodiment, the adhesive layer 3 is set to have high adhesiveness to the protective film and the like attached to the chip-like member. The possibility of film scattering and chip scattering in the expanding process is reduced, which is particularly preferable.

  As described above, the method for manufacturing a chip with a protective film according to the present embodiment hardly causes film scattering or chip scattering. For this reason, the yield is unlikely to decrease in the dicing process of dividing the workpiece W into a plurality of chips. Therefore, the chip with the protective film obtained by the manufacturing method according to the present embodiment using the composite sheet 10 for forming a protective film according to the present embodiment tends to be advantageous in cost. In addition, chip scattering may cause problems such as chipping in other chips manufactured in the same lot due to collision of not only the scattered chips but also the chips that are not scattered. Therefore, the chip with the protective film manufactured by the manufacturing method according to the present embodiment is less likely to have such a problem and is excellent in quality.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  The composite sheet for forming a protective film according to the present invention is suitably used as a sheet for obtaining a chip with a protective film from a plate-shaped workpiece such as a semiconductor wafer.

DESCRIPTION OF SYMBOLS 1 ... Adhesive sheet 1A ... Main surface 1Aa of the adhesive sheet 1 and the adhesive layer 3 side of the adhesive sheet 1 ... The jig | tool for hold | maintaining the laminated body which consists of the composite sheet 10 for protective film formation, and the to-be-processed member W is arrange | positioned Area 1B ... main surface 1a opposite to the main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1 ... energy ray transmitting area 1b ... area 1c for protective film ... area 2 for workpiece ... base material 2A ... base One main surface 2B of the material 2 ... the other main surface 21 of the substrate 2 ... a mask layer 22 ... a substrate main portion 22A ... a surface 3 facing the adhesive layer 3 of the substrate main portion 22 ... an adhesive layer 3a ... Part 3b located in the mask layer region in the pressure-sensitive adhesive layer 3 ... Part 4 located in the non-mask layer region in the pressure-sensitive adhesive layer 3 ... Film 4a for protective film formation ... Peripheral part 4b of the film 4 for protective film formation ... Protective film formation Part 5 of the film 4 other than the peripheral edge 4a ... peeling sheet 5A ... peeling Release surface 10 ... composite sheet W for forming a protective film sheet 5 ... workpiece Wa ... peripheral portion of the workpiece W

Claims (18)

A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface side of the base material,
The pressure-sensitive adhesive sheet is one of the constituent elements of a protective film-forming composite sheet comprising a protective film-forming film laminated on at least one region of a main surface of the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet. As one, it can be used when dicing the workpiece,
The base material is provided inside the base material in the thickness direction, and reduces the transmittance of the energy rays irradiated from the other main surface side of the base material to the one main surface side of the base material. Having a mask layer,
The pressure-sensitive adhesive layer contains a component that causes a polymerization reaction upon irradiation with energy rays, and the adhesiveness to the protective film-forming film can be reduced by the polymerization reaction of the component,
It is a region surrounded by a mask layer region that is a region where the mask layer is present in a plan view on a main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side, and on the pressure-sensitive adhesive layer-side main surface of the pressure-sensitive adhesive sheet The adhesive layer of the pressure-sensitive adhesive sheet is an energy ray transmission region which is a part or all of a non-mask layer region which is a region other than the mask layer region, and which is a region where the adhesive layer is to be irradiated with energy rays. A pressure-sensitive adhesive sheet comprising a protective film region which is a region where the protective film-forming film on the main surface on the agent layer side is laminated in use. The pressure-sensitive adhesive sheet, from the main surface side of the substrate side, there is the energy ray is irradiated to the adhesive layer located on the energy ray transmissive areas,
The adhesiveness of the pressure-sensitive adhesive layer located in the energy ray transmitting region to the protective film-forming film is lower than the adhesiveness of the pressure-sensitive adhesive layer located in the mask layer region to the protective film-forming film. The pressure-sensitive adhesive sheet according to 1. At least a part of a region where a jig for holding the laminate composed of the composite sheet for forming a protective film and the workpiece on the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet is arranged, consisting mask layer region, the pressure-sensitive adhesive sheet according to claim 1 or 2. The mask layer is composed of a material that blocks the transmission of the one main surface side of the base material of the energy ray emitted from the other main surface side of the substrate, any one of claims 1 3 The pressure-sensitive adhesive sheet described in 1. The pressure-sensitive adhesive sheet according to any one of claims 1 to 4 , wherein the pressure-sensitive adhesive sheet is a long body, and includes a plurality of the energy ray transmission regions separated in a longitudinal direction. An adhesive roll formed by rolling up the adhesive sheet according to claim 5 in the longitudinal direction. The pressure-sensitive adhesive sheet according to any one of claims 2 to 4 , and a protective film-forming film laminated on the protective film region on the main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side. A composite sheet for forming a protective film. The composite sheet for forming a protective film according to claim 7 , wherein the composite sheet for forming a protective film is a long body, and includes a plurality of films for forming the protective film that are separated in the longitudinal direction. A wound body of the protective film-forming composite sheet obtained by winding the protective film-forming composite sheet according to claim 8 in the longitudinal direction. Comprising a release sheet long, and a pressure-sensitive adhesive sheet described in any one of 4 claim 1 in which a plurality arranged in a longitudinal direction of the release sheet apart while each other on a release surface of the release sheet ,
The said adhesive sheet is laminated | stacked so that the surface by the side of the said adhesive layer may oppose the peeling surface of the said peeling sheet. A laminated body wound by winding the laminated body according to claim 10 in the longitudinal direction. A long release sheet, and a protective sheet-forming composite sheet according to claim 7 , wherein a plurality of the release sheets are arranged in the longitudinal direction of the release sheet while being separated from each other on the release surface of the release sheet,
The composite sheet for forming a protective film is laminated such that the surface on the protective film-forming film side faces the release surface of the release sheet. A wound body of a laminated body obtained by winding the laminated body according to claim 12 in a longitudinal direction. A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface side of the base material, and a protective film on the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet the composite sheet for forming a protective film having a protective film forming film, the surface of the protective film forming film side affixed to one surface of the workpiece, the protective film forming composite sheet is adhered the object The processed member is separated into individual pieces, and the protective film-forming film is cured to form a protective film when the protective film-forming film is adhered to the surface of the processed member. A method for producing a chip with a protective film, which obtains a chip with a protective film comprising a chip-shaped member formed by separating the member and the protective film laminated on one surface of the chip-shaped member ,
The base material is provided inside the base material in the thickness direction, and reduces the transmittance of the energy rays irradiated from the other main surface side of the base material to the one main surface side of the base material. Having a mask layer,
The pressure-sensitive adhesive layer contains a component that causes a polymerization reaction upon irradiation with energy rays, and the adhesiveness to the protective film-forming film can be reduced by the polymerization reaction of the component,
It is a region surrounded by a mask layer region that is a region where the mask layer is present in a plan view on a main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side, and on the pressure-sensitive adhesive layer-side main surface of the pressure-sensitive adhesive sheet The adhesive layer of the pressure-sensitive adhesive sheet is an energy ray transmission region which is a part or all of a non-mask layer region which is a region other than the mask layer region, and which is a region where the adhesive layer is to be irradiated with energy rays. The protective film region, which is a region where the protective film-forming film on the main surface on the agent layer side is laminated in use, includes:
The pressure-sensitive adhesive sheet is obtained by irradiating the pressure-sensitive adhesive layer located in the energy ray transmission region with energy rays from the main surface side on the base material side,
The adhesiveness of the pressure-sensitive adhesive layer located in the energy ray transmission region to the protective film-forming film is lower than the adhesiveness of the pressure-sensitive adhesive layer located in the mask layer region to the protective film-forming film,
Manufacturing method of chip with protective film . For a work member that is a projection region of a region where the work member is disposed on the protective film-forming composite sheet when the protective film-forming composite sheet is used on the main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side The method for manufacturing a chip with a protective film according to claim 14 , wherein the region includes the energy ray transmission region . The method for manufacturing a chip with a protective film according to claim 15 , wherein the region for a member to be processed is included in the region for a protective film . The method for producing a chip with a protective film according to claim 14, wherein the singulation of the workpiece includes cutting of the workpiece. The method for manufacturing a chip with a protective film according to claim 14, wherein the singulation of the workpiece includes breakage of the workpiece.

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