JP2014189563A - Tacky sheet, film for forming protective film, composite sheet for forming protective film, and marking method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tacky sheet, etc. unlikely to entail, in a laminated state where a tacky sheet is pasted onto the side of one given surface of a processing target member or the protective film side, etc. thereof, inconveniences originating from contaminants generated on an occasion for marking the rear surface of the processing target member or the protective film, etc. thereof by applying a laser beam from the tacky sheet side; and a marking method.SOLUTION: In a tacky sheet 1 including a substrate 2 and a tackifier layer 3, the principal surface 1A of the tacky sheet 1 on the tackifier layer 3 side possesses, at least as a partial region, a first uneven surface region 1a consisting of an uneven surface. At the time of the use of the tacky sheet 1, one given surface of an adhesion target targeted for laser marking is laminated atop the tacky sheet 1 so as to cover the first uneven surface region 1a partially or entirely. At least a portion of the first recessed segment of the first uneven surface region 1a demarcates the principal surface 1A and a first gap portion without being contacted with the one given surface of the adhesion target so as to embody a diffusion route for contaminants generated on a laser marking occasion.

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, a protective film-forming film capable of forming a protective film, and a pressure-sensitive adhesive sheet and a protective film-forming film, It is related with the composite sheet for protective film formation provided with. Specifically, a process for separating a workpiece such as a semiconductor substrate into a piece, in particular, a dicing process for manufacturing a semiconductor device mounted by a so-called face down method (cutting using a rotary blade or a laser) In some cases, it may be processed, and in other cases, the processed member may be locally modified and broken, such as in stestle dicing.) Adhesive sheets used for), for forming a protective film attached to an adhesive sheet when used The present invention relates to a film and a composite sheet for forming a protective film in which the above-mentioned pressure-sensitive adhesive sheet and a protective film-forming film are laminated. The present invention also relates to a marking method using any one of the pressure-sensitive adhesive sheet and the protective film-forming composite sheet. Furthermore, the present invention also relates to a method for manufacturing a chip having a marking.

  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 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 semiconductor chip may be exposed.

  For this reason, a hard organic film (hereinafter referred to as “protective film”) is often formed on the back surface side in order to protect the semiconductor chip. The protective film is printed in order to display the product number of the semiconductor chip. As a marking method, a laser marking method is generally used in which a protective film is irradiated with laser light, the surface of the protective film is scraped off, and letters are formed.

  When marking with a laser beam, unless the surface to be marked is flat, the laser beam is not focused and good marking properties cannot be obtained. However, as a result of thinning of the wafer, the wafer is warped, the distance between the laser light source and the printing part is not constant, and it becomes difficult to focus the laser beam, marking performance is deteriorated, and printing cannot be performed. ing. The cause of the warpage of the wafer is considered to be that the film itself shrinks when the protective film is formed and the wafer is deformed by the shrinkage force in addition to the thinning of the wafer itself.

  In order to correct the warpage of the wafer on which the protective film is formed, in Patent Document 1, an adhesive sheet is attached to the wafer with the protective film, the outer periphery of the adhesive sheet is fixed with a ring frame, and then marking is performed with laser light. A process has been proposed. In this method, the protective film side of a wafer with a protective film is attached to an adhesive sheet, and marking is performed by irradiating a laser beam from the adhesive sheet side. According to this method, since the warpage of the wafer is corrected by the adhesive sheet, the wafer is maintained flat and the marking performance using laser light is improved.

JP 2006-140348 A

  Here, in the method of Patent Document 1, the protective film side of the wafer with the protective film is attached to the adhesive sheet, and marking is performed by irradiating laser light from the adhesive sheet side. In this method, the laser beam passes through the adhesive sheet, and the laser beam is marked by scraping off the surface of the protective film. At this time, a thermal decomposition product of the protective film is released from the surface of the protective film.

  Some of these pyrolysates, for example, gas phase substances, may accumulate at the interface between the protective film and the pressure-sensitive adhesive sheet, solidify again, and remain as contaminants on the surface of the protective film that has been laser-marked. If such contaminants remain, the laser-marked image (characters, graphics, etc.) will be difficult to identify when it is attempted to recognize the image using a CCD or the like due to the remaining contaminants. May occur. Moreover, such contaminants may impair the function of the resulting semiconductor device.

  In addition, the above-mentioned problems also occur when the back side of a semiconductor wafer is attached to an adhesive sheet, and marking is performed by direct laser irradiation from the adhesive sheet side to the back side of the wafer. In some cases, the wafer material sublimates into gas and fine fragments (debris) are generated, which reattach to the wafer and impair the performance of the wafer.

  The present invention has been made in view of the prior art as described above, and is a pressure-sensitive adhesive sheet directly on one surface of a member to be processed such as the back surface of a semiconductor wafer, or through a protective film-forming film or protective film. In the laminated state with affixed, when marking on the back surface of the processed member or the protective film forming film or protective film by irradiating the laser beam from the adhesive sheet side, the processed member such as a wafer or the protective film forming film Alternatively, a substance generated from a protective film, which efficiently removes a contaminating substance that may adhere to the surface of a laser-marked member such as the above-described workpiece and contaminate it, thereby reducing the marking suitability. , Pressure-sensitive adhesive sheet, protective film-forming film, and protective film-forming composite sheet that can prevent contamination of products manufactured from workpieces such as semiconductor devices As well as an object to provide a marking method using these sheets or films.

  In order to achieve the above object, the present inventors have examined a surface of a workpiece to be processed or a path for diffusing a pollutant generated when marking a protective film-forming film or protective film. Contaminants remain on one surface of the workpiece or the surface of the protective film by preliminarily providing it on one surface of the member or a gap defined by the protective film-forming film or protective film and the adhesive sheet. The knowledge that it is possible to reduce the possibility to do.

  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 of the base material, the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive sheet. The main surface on the agent layer side has a first uneven surface area composed of an uneven surface as at least a part of the main surface, and when the pressure-sensitive adhesive sheet is used, the adherend that is the object of laser marking is used. One surface is laminated on the pressure-sensitive adhesive sheet so as to cover a part or all of the first uneven surface region, and one surface of the adherend and the first uneven surface region are opposed to each other. The at least part of the concave portion located in the region covered with one surface of the adherend among the concave portions of the first uneven surface region is disposed on one surface of the adherend. The main surface and the gap are defined without contacting the gap, and the gap is generated during laser marking. It is the diffusion path of the contaminating substances to provide a pressure-sensitive adhesive sheet characterized by (invention 1).

  Second, the present invention is a protective film-forming film that can be cured to form a protective film, wherein one main surface of the protective film-forming film is at least a part of the main surface, The second uneven surface area is formed of an uneven surface, and the second uneven surface area can be marked with a laser beam. When the protective film-forming film is used, one of the base material and the base material is used. The pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer laminated on the surface is formed with the protective film such that the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet covers part or all of the second uneven surface area. In the state where the second uneven surface area of the protective film-forming film and the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet are opposed to each other, Of the concave portion of the surface region, the adhesive of the adhesive sheet At least a part of the recess located in the region covered by the main surface on the layer side does not contact the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet, and defines the main surface and a void portion, and the void portion Provides a protective film-forming film characterized in that it serves as a diffusion path for pollutants generated during laser marking (Invention 2).

  In the said invention (invention 2), it is preferable that the said 2nd uneven surface area | region has a part which touches the outer periphery of the said film for protective film formation by planar view (invention 3).

  3rdly, this invention is equipped with the base material and the adhesive layer laminated | stacked on one main surface of the said base material, The main surface at the side of the said adhesive layer is at least one part of the said main surface. A protective sheet-forming composite sheet comprising a pressure-sensitive adhesive sheet having a first uneven surface area composed of an uneven surface as an area, and a protective film-forming film that can be cured to form a protective film, wherein the protective film is formed The protective film-forming film is laminated on the pressure-sensitive adhesive sheet so that one main surface of the film for film covers part or all of the first uneven surface area, and the concave portion of the first uneven surface area Among these, at least a part of the recess located in the region covered with one main surface of the protective film-forming film does not contact one main surface of the protective film-forming film and the main surface and the gap The voids are dirt generated during laser marking. To provide a composite sheet for forming a protective film, characterized in that the diffusion path of sex material (Invention 4).

  Fourthly, the present invention provides 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 a protective film-forming film according to the above inventions (inventions 2 and 3). The protective film-forming composite sheet includes the protective film-forming film, such that a main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side covers part or all of the second uneven surface area. The pressure-sensitive adhesive sheet is laminated, and at least part of the concave portion located in a region covered by the main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side of the second concave-convex surface region is the pressure-sensitive adhesive sheet. The protective film is characterized in that it does not contact the main surface of the pressure-sensitive adhesive layer side and defines the main surface and a gap, and the gap serves as a diffusion path for a pollutant generated during laser marking. A composite sheet for forming is provided (Invention 5).

  In the said invention (invention 5), the said adhesive sheet is an adhesive sheet which concerns on the said invention (invention 1), Comprising: At least one part of the said 1st uneven surface area | region opposes the said 2nd uneven surface area | region. It is preferable that they are located (Invention 6).

  In the above inventions (Inventions 4 to 6), in the gap portion, in a plan view, a region to be attached to a workpiece when used on the principal surface on the side distal to the base material of the protective film-forming composite sheet At least a part of the in-region gap portion located in the processing region is a region other than the processing region in the main surface on the side distal to the base material of the composite sheet for protective film formation in a plan view. It is preferable to communicate with the outer space located in the processing region (Invention 7).

  In the said invention (invention 7), the said outside space | gap part has an opening part which uses the said space | gap part as an open system, The peripheral part of the said opening part is the main surface by the side of the said adhesive layer of the said adhesive sheet, The said It is preferable to be located on at least one of the side surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the side surface of the protective film-forming film (Invention 8).

  In the above inventions (Inventions 5 to 8), a jig laminated in a region other than a region to be pasted on a workpiece at the time of use on a main surface distal to the base material of the composite sheet for forming a protective film It is preferable to further include an adhesive layer (Invention 9).

  In the said invention (invention 9), it is preferable that the main surface proximal to the said adhesive sheet of the said jig | tool adhesion layer is affixed on the main surface of the said adhesive sheet in an at least 1 area | region (invention 10).

  In the said invention (invention 9 and 10), it is preferable that the main surface proximal to the said adhesive sheet of the said jig | tool adhesion layer is affixed on the main surface of the said film for protective film formation in at least 1 area | region (invention). 11).

  Fifth, in the present invention, the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet according to the above-mentioned invention (invention 1) stretched on the ring frame is in a laminated state in which it is stuck to one surface of the workpiece. The present invention provides a marking method characterized by irradiating a laser beam from the pressure-sensitive adhesive sheet side to mark one surface of the workpiece (Invention 12).

  Sixth, the present invention provides that the main surface of the protective film-forming film included in the protective film-forming composite sheet according to the invention (inventions 4 to 11) stretched on the ring frame is a workpiece to be processed. There is provided a marking method characterized in that, in a laminated state attached to one surface, laser beam is irradiated from the protective film forming composite sheet side to mark the other main surface of the protective film forming film. (Invention 13).

  7thly, this invention is obtained by hardening | curing the said film for protective film formation with which the composite sheet for protective film formation which concerns on the said invention (invention 4 to 11) stretched around the ring frame is used as a protective film. In the laminated state in which one main surface of the protective film is fixed to one surface of the member to be processed, in the protective film-containing composite sheet to be applied, laser light is irradiated from the protective film-forming composite sheet side, A marking method characterized by marking on the other main surface of the protective film (Invention 14).

  In the present invention, the pressure-sensitive adhesive sheet is applied to a workpiece to be processed such as a semiconductor wafer to which a pressure-sensitive adhesive sheet is attached, a protective film-forming film disposed opposite to the pressure-sensitive adhesive sheet, or a protective film formed from the film. By diffusing the pollutant generated when marking by irradiating the laser beam through the diffusion path of the pollutant consisting of a gap provided in advance, the marked part and / or its vicinity It is possible to reduce the possibility that contaminants adhere at a high concentration. Therefore, according to the present invention, a product such as a semiconductor device obtained from a workpiece is reduced in contamination at the time of marking, so that a higher quality product is easily obtained.

It is (a) schematic sectional drawing and (b) schematic perspective view 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 a schematic sectional drawing of the film laminated body for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows notionally the use condition of the film for protective film formation 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 another one Embodiment of this invention. It is a schematic sectional drawing of the composite sheet for protective film formation provided with the interface adhesion adjustment layer based on one Embodiment of this invention. It is a schematic sectional drawing of the composite sheet for protective film formation provided with the adhesive sheet and jig | tool adhesion layer in which the interface adhesion adjustment layer was provided based on one Embodiment of this invention. It is a schematic sectional drawing of the composite sheet for protective film formation provided with the jig | tool adhesion layer based on another one Embodiment of this invention. It is a schematic perspective view of the composite sheet for protective film formation which concerns on one Embodiment of this invention, a peeling sheet, and a laminated body. It is a schematic perspective view of the lamination | stacking state which comprises the adhesive sheet and a to-be-processed member for demonstrating the marking method which concerns on one Embodiment of this invention. It is a schematic perspective view of the lamination | stacking state containing the composite sheet for protective film formation and a to-be-processed member for demonstrating the marking method which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
1. Adhesive sheet The adhesive sheet 1 which concerns on one Embodiment of this invention is equipped with the base material 2 and the adhesive layer 3 laminated | stacked on one main surface of the base material 2, as FIG.1 (a) shows. The main surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1 (also referred to as “pressure-sensitive adhesive sheet first main surface” in this specification) is an uneven surface as at least a partial region of the pressure-sensitive adhesive sheet first main surface 1A. The first uneven surface area 1a is made of.

(1) Base material 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 or the like performed after the dicing process. Usually, a resin-based material is mainly used. Consists of film as 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, Examples thereof include polyolefin films such as norbornene resin films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; and fluororesin films. Further, modified films such as these crosslinked films and ionomer films are also used. The substrate 2 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.

  A chip with a protective film (details will be described later) formed using the protective film-forming composite sheet 10 according to the present embodiment is a chip with a marking protective film that has been laser-marked. Since it irradiates through the base material 2, it is preferable that the base material 2 is excellent in the transmittance | permeability of a laser beam. The type of laser for laser marking is not particularly limited. For example, lasers having wavelengths such as 532 nm and 1064 nm are exemplified. From the viewpoint of excellent laser light transmittance, preferred examples of the film constituting the substrate 2 include an ethylene copolymer film, a polyolefin film, and a polyvinyl chloride film.

More preferably, the film constituting the substrate 2 comprises at least one of an ethylene copolymer film and a polyolefin film.
It is easy to control the mechanical properties of an ethylene copolymer film in a wide range by changing the copolymerization ratio of monomers constituting the ethylene copolymer film. For this reason, the base material 2 provided with the ethylene-based copolymer film easily satisfies the mechanical characteristics required as the base material of the dicing sheet when the protective film-forming composite sheet 10 according to this embodiment is used as the dicing sheet. 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 this embodiment is used as a dicing sheet, the base material 2, the pressure-sensitive adhesive layer 3, Peeling at the interface is difficult to occur.

  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 2 to the adhesive layer 3). And further distributed on the surface of the pressure-sensitive adhesive layer 3 opposite to the side facing the substrate 2 to reduce the adhesiveness of the pressure-sensitive adhesive layer 3 to the adherend). Since there are few, problems, such as the adhesiveness with respect to the adherend of the adhesive layer 3, fall, are hard to arise. That is, the ethylene copolymer film and the polyolefin film are excellent in chemical stability.

  The base material 2 may contain various additives such as pigments, flame retardants, plasticizers, antistatic agents, lubricants, fillers, and the like in a film mainly composed of the above-described 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 additives is not particularly limited, but the substrate 2 performs a desired function (including the function of transmitting laser light irradiated for laser marking), and is smooth and flexible. Should be kept within the range not to lose.

  In the case where ultraviolet rays are used as the energy rays applied to the pressure-sensitive adhesive layer 3, the base material 2 is preferably permeable to the ultraviolet rays. As will be described later, the pressure-sensitive adhesive layer 3 may be composed of an energy beam polymerization-type pressure-sensitive adhesive composition. When an electron beam is used as the energy beam applied to the pressure-sensitive adhesive layer 3, the substrate 2 is made of an electron beam. It preferably has transparency.

  The main surface (hereinafter also referred to as “base material facing surface”) 2 </ b> A facing the pressure-sensitive adhesive layer 3 of the base material 2 is one or two selected from the group consisting of a carboxyl group and its ions and salts. It is preferred that there be a component having more than one species. The above-mentioned components in the substrate 2 and the components related to the pressure-sensitive adhesive layer 3 (components used for forming the pressure-sensitive adhesive layer 3 such as a component constituting the pressure-sensitive adhesive layer 3 and a crosslinking agent (γ) are exemplified.) Can interact with each other chemically to reduce the possibility of delamination between them. The specific method for making such a component exist in 2 A of base material opposing surfaces is not specifically limited. For example, the base material 2 itself is, for example, an ethylene- (meth) acrylic acid copolymer film, an ionomer resin film, etc., and the resin constituting the base material 2 is selected from the group consisting of carboxyl groups and ions and salts thereof. One or two or more types may be included. As another method for causing the above component to exist on the substrate facing surface 2A, the substrate 2 is, for example, a polyolefin film, and is subjected to corona treatment on the substrate facing surface 2A side, or a primer layer is provided. May be. Various coating films may be provided on the surface of the substrate 2 opposite to the substrate facing surface 2A as long as a desired function can be achieved.

  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.

  The elongation at break of the substrate 2 in the present embodiment is preferably 100% or more, particularly preferably 200% or more and 1000% or less, as a value measured at 23 ° C. and a relative humidity of 50%. 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 the elongation at break of 100% or more is not easily broken during the expanding process after the dicing process, and the chips formed by cutting the workpiece W are easily separated.

  In addition, the tensile stress at 25% strain of the base material 2 in this embodiment is preferably 5 N / 10 mm or more and 15 N / 10 mm or less, and the maximum tensile stress is preferably 15 MPa or more and 50 MPa or less. Here, the tensile stress at the time of 25% strain and the maximum tensile stress are measured by a test according to JIS K7161: 1994. If the tensile stress at 25% strain is less than 5 N / 10 mm or the maximum tensile stress is less than 15 MPa, the protective film-forming composite sheet 10 is attached to the adherend W, and then attached to a jig such as a ring frame. When it is fixed, there is a concern that the base material 2 is soft, so that the slack may occur, and this slack may cause a conveyance error. On the other hand, if the tensile stress at 25% strain exceeds 15 N / 10 mm or the maximum tensile stress exceeds 50 MPa, problems such as peeling of the adhesive sheet 1 from a jig such as a ring frame during the expanding process are likely to occur. Is concerned. The elongation at break, the tensile stress at 25% strain, and the maximum tensile stress are values measured in the longitudinal direction of the original fabric in the substrate 2.

(2) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 1 according to this embodiment can be formed of various conventionally known pressure-sensitive adhesive compositions. The pressure-sensitive adhesive composition is not limited in any way, and for example, a pressure-sensitive adhesive composition such as rubber, acrylic, silicone, or polyvinyl ether is used. Moreover, an energy ray curable type, a heat-foaming type, or a water swelling type pressure-sensitive adhesive composition can also be used.

(2-1) First Irregular Surface Area As shown in FIG. 1 (a), the pressure-sensitive adhesive sheet first main surface 1A is a first uneven surface as at least a part of the main surface 1A. It has an uneven surface area 1a. When the pressure-sensitive adhesive sheet 1 is used, one surface of the adherend that is the object of laser marking is laminated on the pressure-sensitive adhesive sheet 1 so as to cover a part or all of the first uneven surface area 1a. Examples of the adherend include a member to be processed such as a semiconductor wafer, a protective film forming film that can be cured to form a protective film, and a protective film formed by curing the protective film forming film. Hereinafter, as shown in FIG. 2, the adherend is the protective film forming film 4, and the protective film forming composite sheet 10 is configured by the adhesive sheet 1 and the protective film forming film 4. A specific example will be described.

  In this protective film forming composite sheet 10, one main surface (main surface on the side proximal to the adhesive sheet 1) 4 </ b> B of the protective film forming film 4 and the first uneven surface area 1 a are opposed to each other. . In this state, of the recesses (also referred to as “first recesses” in the present specification) located in the first uneven surface region 1a, the region covered with one main surface 4B of the protective film forming film 4 At least a part of the concave portion located at is not in contact with one main surface 4B of the protective film-forming film 4, and defines the main surface 4B and a gap. The defined void portion becomes a diffusion path for the pollutant generated during laser marking. In the present specification, the void portion in which the first concave portion participates in the definition is also referred to as “first void portion”.

  The shape characteristic of the first gap is appropriately set according to the composition and amount of the pollutant generated from the adherend by the laser irradiated for laser marking. Examples of the pollutant include a minute solid such as debris, a minute droplet, and a gas phase material. The shape of the first gap is the shape characteristic of the first concave portion of the first concave / convex surface region 1a in plan view and sectional view, and is one of the adherends to which the first concave / convex surface region 1a adheres. The surface feature (one main surface 4B when the adherend is the protective film-forming film 4 as described above), the shape characteristics in plan view and cross-sectional view, and the adhesive sheet 1 was adhered to the adherend. This is determined depending on the degree of deformation of the first recess.

  The shape feature of the first concave portion of the first uneven surface area 1a is set based on the forming method. For example, when the first uneven surface area 1a made of a satin surface is formed by directly performing shot blasting, etching, or the like on a partial area or the entire area of the first main surface 1A of the adhesive sheet, the first The concave portion is a concave portion having a surface on which a plurality of minute concave portions are present in close proximity at random. On the other hand, when the 1st uneven surface area | region 1a is formed by the method of transcribe | transferring the satin surface formed using methods, such as shot blasting, electric discharge, and etching, a 1st recessed part is a several microprotrusion. Becomes a recess having a surface that is present in close proximity to each other. Or the 1st uneven surface area | region 1a may be formed by the method of transcribe | transferring the surface which has the uneven | corrugated shape formed by machining or plating processing, such as cutting, The transfer frequency may be 1 time and may be multiple times . The shape in plan view of the first uneven surface area 1a formed by the first recess, that is, the pattern is not limited. FIG. 1B shows a case where the first concave portion forms a lattice-like pattern in which a plurality of shapes corresponding to the cutting grooves intersect each other.

  The relationship between the first main surface 1A of the pressure-sensitive adhesive sheet and the first uneven surface region 1a in a plan view is arbitrary. As shown in FIG. 1, a part of the adhesive sheet first main surface 1A may be the first uneven surface area 1a, or the entire area of the adhesive sheet first main surface 1A is the first uneven surface. It may be region 1a. In addition, said relationship can be prescribed | regulated also by whether the 1st uneven surface area | region 1a has a part which touches the outer periphery of the adhesive layer 3. FIG. As shown in FIG. 1, in the pressure-sensitive adhesive sheet 1, the first uneven surface area 1 a does not have a portion in contact with the outer periphery of the pressure-sensitive adhesive layer 3. In this case, when the adherend of the first main surface 1A of the pressure-sensitive adhesive sheet is arranged so as to cover the entire first uneven surface area 1a, the pollutant material generated during the laser marking is discharged to the outside air. Without being diffused into the first gap. On the other hand, when the adherend of the pressure-sensitive adhesive sheet first main surface 1A is arranged so as to cover a part of the first uneven surface area 1a, the first gap has an opening to the outside air. Contaminating substances generated during laser marking can be discharged to the outside air through the first gap. On the other hand, when the first uneven surface area 1a has a portion in contact with the outer periphery of the pressure-sensitive adhesive layer 3, the first gap portion has an opening to the outside air on the side surface of the pressure-sensitive adhesive layer. Regardless of the shape or the arrangement of the adherend on the first main surface 1A of the adhesive sheet, the pollutant generated during the laser marking can be discharged to the outside air through the first gap.

  The relationship in plan view between one surface of the adherend and the first uneven surface region 1a arranged to face the first main surface 1A of the pressure-sensitive adhesive sheet is also arbitrary. All of the first uneven surface region 1a may be included in one surface of the adherend, or the first uneven surface region 1a may include the entire region of one surface of the adherend. Good. In the former case, the pollutant generated by performing laser marking on the adherend diffuses into the first gap, so the local concentration of the pollutant increases and contaminates the adherend. Is suppressed. On the other hand, in the latter case, the pollutant generated by performing laser marking on the adherend can be discharged to the outside air through the first gap.

  As an example of the 1st recessed part of the 1st uneven surface area | region 1a, the case where the shape characteristic in a cross sectional view is 5 micrometers or more and 500 micrometers or less and / or the depth is 0.5 micrometers or more and 5 micrometers or less is mentioned. . When the width of the first recess is excessively narrow or the depth is excessively shallow, the diffusion of the pollutant is insufficient, and the occurrence of local contamination based on the pollutant is suppressed. It may become difficult. On the other hand, when the width of the first recess is excessively wide or the depth is excessively deep, there is a possibility that the variation in the amount of light when the laser light is irradiated becomes large enough to affect the marking.

  The pressure-sensitive adhesive layer 3 included in the pressure-sensitive adhesive sheet 1 according to this embodiment may be composed of an energy beam polymerization-type pressure-sensitive adhesive composition containing a component that causes a polymerization reaction upon irradiation with energy rays. Examples of energy rays for this 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.

  Thus, when the pressure-sensitive adhesive layer 3 is formed from an energy ray polymerization-type pressure-sensitive adhesive composition, and the first uneven surface region is formed by transfer processing, the time to irradiate energy rays The relationship with the timing for performing transfer processing is not particularly limited. From the viewpoint of improving the transfer processability, it may be preferable to perform the transfer process before the irradiation with the energy rays. On the other hand, from the viewpoint of improving the temporal stability of the shape obtained by the transfer (specifically, it is difficult to cause the phenomenon that the uneven portion is flattened over time), It may be preferable to perform transfer processing after irradiation.

  As an example of a pressure-sensitive adhesive composition that can be polymerized by ultraviolet rays, a pressure-sensitive adhesive composition containing an acrylic polymer (α) and an energy ray-polymerizable compound (β) described below, and a cross-linking agent (γ) as necessary. Things.

(2-2) 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 (γ) 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 (γ) that can cross-link the acrylic polymer (α) as described later, acrylic The type of the reactive functional group possessed by the system polymer (α) is not particularly limited, and may be appropriately determined based on the type of the crosslinking agent (γ). For example, when the crosslinking agent (γ) is a polyisocyanate compound, examples of the reactive functional group that the acrylic polymer (α) has include a hydroxyl group, a carboxyl group, and an amino group. Among these, when the crosslinking agent (γ) is a polyisocyanate compound, it is preferable to employ a hydroxyl group highly reactive with an isocyanate group as a 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.

(2-3) 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 (γ), the energy ray polymerizable group is ethylenic from the viewpoint of reducing the possibility of functional overlap with the site where the crosslinking agent (γ) 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) preferably has a molecular weight of 4,000 or less as a weight average molecular weight (Mw). As such an energy ray polymerizable compound (β), a compound composed of one or more kinds selected from the group consisting of monofunctional monomers and polyfunctional monomers having an energy ray polymerizable group and oligomers of these monomers is used. 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. .

  The content of the energy beam polymerizable compound (β) contained in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to this embodiment is 50 masses per 100 parts by mass of the acrylic polymer (α). Part to 300 parts by mass, more preferably 75 parts to 150 parts by mass. 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 of the pressure-sensitive adhesive layer 3 after irradiation with the energy beam to the protective film-forming film 4 and the pressure-sensitive adhesive layer before irradiation with the energy beam The difference with the adhesiveness with respect to film 4 for protective film formation of 3 can fully be ensured.

  As another example of the energy beam polymerizable compound (β), the energy beam polymerizable compound (β) is an acrylic polymer, and has a structural unit having an energy beam polymerizable line group in the main chain or side chain. There are some cases. 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 energy beam polymerizable groups.

  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, 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.

(2-4) Crosslinking agent (γ)
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 (γ) 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 (γ).

  Examples of the crosslinking agent (γ) 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 (γ) 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 (γ), 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 (γ) contained in the composition for forming the pressure-sensitive adhesive layer 3. Specifically, the content of the crosslinking agent (γ) of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 is 5 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (α). 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 this controllability, the content of the crosslinking agent (γ) 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). Particularly preferred. The upper limit of the content of the crosslinking agent (γ) is not particularly limited, but if the content is excessively high, it may be difficult to control the adhesiveness of the pressure-sensitive adhesive layer 3 to a range described later. It is preferable to set it as 50 mass parts or less with respect to 100 mass parts of acrylic polymers ((alpha)), and it is more preferable to set it as 40 mass parts or less.

  When the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 according to this embodiment contains a cross-linking agent (γ), an appropriate cross-linking accelerator is added depending on the type of the cross-linking agent (γ). It is preferable to contain. For example, when the crosslinking agent (γ) 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 a storage elastic modulus adjuster and a photopolymerization initiator in addition to the above components. Further, it may contain various additives such as colorants such as dyes and pigments, flame retardants, and fillers.

  Examples of the storage modulus modifier include tackifier resins and long-chain alkyl acrylic oligomers. The content of the storage elastic modulus modifier is preferably 50 parts by mass or more, and 75 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. It is more preferable that the amount be 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 modulus modifier is 500 parts by mass or less with respect to 100 parts by mass of the acrylic polymer (α). Preferably, the amount is 400 parts by mass or less, and more preferably 350 parts by mass or less.

  In the case where the storage modulus modifier 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 these different types of tackifying resins in combination, the compatibility of the storage modulus modifier 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 adjuster, as well as a hydrogenated rosin ester (C2) and a hydrocarbon resin (C3). The case where at least one of these 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.

  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.

(3) Transmittance The pressure-sensitive adhesive sheet 1 according to this embodiment has a transmittance to the pressure-sensitive adhesive 3 side of 70% or more when a laser beam for marking an adherend is incident from the base material 2 side. Preferably there is. The higher the transmittance is, the more preferable, 80% or more is more preferable, and 90% or more is more preferable.

(4) 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. The viewpoint of appropriately maintaining the adhesiveness to the adherend of the pressure-sensitive adhesive layer 3 (here, in addition to the object to be irradiated with a laser such as the protective film-forming film 4, a jig such as a ring frame). Therefore, the thickness of the pressure-sensitive adhesive layer 3 is preferably 1 μm or more, more preferably 2 μm or more, and particularly 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. preferable.

2. Protective film-forming film The protective film-forming film according to one embodiment of the present invention has a shape feature to be described later on at least one main surface. As shown in FIG. 2, the protective film-forming film 4 is laminated on the pressure-sensitive adhesive sheet first main surface 1 </ b> A and becomes one element constituting the protective film-forming composite sheet 10. As shown in FIG. 3, the protective film forming film 4 may be distributed or stored, for example, as a protective film forming film laminate 40 sandwiched between two release sheets 41 and 42.

Hereinafter, the protective film-forming film 4 will be described in detail.
The protective film-forming film 4 fulfills the following functions as basic functions.
(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, the protective film forming film 4 and the protective film may be collectively referred to as “protective film or the like.” When the protective film forming film 4 is disposed between the workpiece W and the pressure-sensitive adhesive sheet 1 and subjected to the dicing process. In addition, peeling between the workpiece W and the protective film or the like and peeling between the protective film or the like and the adhesive sheet 1 are less likely to occur (Function 3) In the pickup process performed after the dicing process, Peeling occurs between the protective film and the adhesive sheet 1 in preference to peeling between the protective film and the protective film (Function 4) The opposite side of the surface facing the workpiece W such as the protective film Engraved on the surface with laser marking etc. By performing the, it can form a protective film having a mark having excellent visibility

(1) Second uneven surface region As shown in FIG. 3, the protective film forming film 4 according to this embodiment has one main surface 4 </ b> B of the protective film forming film 4 (close to the pressure-sensitive adhesive sheet 1 when used). The main surface located on the lower side has a second uneven surface area 4a made of an uneven surface as at least a part of the main surface 4B. This 2nd uneven surface area | region 4a is comprised so that marking can be performed with a laser beam. The formation method of the 2nd uneven surface area | region 4a is not specifically limited. Similar to the method of forming the first uneven surface area 1a, the uneven surface formed by using a physical method such as cutting or shot blasting, a chemical method such as etching or plating, or the like is transferred. Is given as a typical example.

  When the protective film forming film 4 is used, as shown in FIG. 4, the pressure sensitive adhesive sheet 1 and the protective film forming film 4 have a pressure sensitive adhesive sheet first main surface 1 </ b> A that is one of the protective film forming films 4. The protective sheet forming composite sheet 10 is configured by being laminated so as to cover a part or all of the second uneven surface area 4a on the main surface 4. In FIG. 4, the case where 1 A of adhesive sheet 1st main surfaces cover the whole 2nd uneven | corrugated surface area | region 4a is illustrated. That is, in the plan view, the pressure-sensitive adhesive sheet first main surface 1A is wider than the second uneven surface area 4a. The relationship in plan view between the pressure-sensitive adhesive sheet first main surface 1A and the second uneven surface area 4a is not particularly limited. For example, as shown in FIG. The pressure-sensitive adhesive sheet 1 and the protective film-forming film 4 may be laminated so that the two uneven surface areas 4a face each other.

  The relationship between the region 1b where the protective film forming film 4 is laminated on the first main surface 1A of the adhesive sheet and the first main surface 1A of the adhesive sheet is not particularly limited. As shown in FIG. 4, the region 1b may be a partial region of the main surface 1A, or the entire region of the main surface 1A is the region 1b, and the protective film-forming film 4 is the first main sheet of the adhesive sheet. You may arrange | position so that the whole surface 1A may be covered (FIG. 5).

  In the state where the second uneven surface area 4a of the protective film-forming film 4 laminated on the adhesive sheet 1 and the first main surface 1A of the adhesive sheet face each other, the concave portion ( In this specification, it is also referred to as “second recess”), and at least part of the recess located in the region covered with the first main surface 1A of the adhesive sheet does not contact the first main surface 1A of the adhesive sheet. The main surface 1A and a gap are defined. The defined void portion becomes a diffusion path of the pollutant generated during laser marking. In the present specification, the void portion in which the second concave portion participates in the definition is also referred to as “second void portion”. The shape feature of the second gap portion has the same feature as the shape feature of the first gap portion formed by involving the first recess of the first uneven surface area 1a.

  The second gap has the following characteristics. That is, the second uneven surface area 4a may have a portion that contacts the outer periphery of the protective film-forming film 4 in plan view. In this case, the second gap portion is not a closed space, and a part of the second gap portion defined by the second recess portion in contact with the outer peripheral portion is an opening of the second gap portion. Part. In this case, it is possible to discharge the pollutant generated by the laser light irradiation through the opening.

(2) Composition 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 composition and the like of the protective film-forming film 4 will be described by taking as an example a film having (1) sheet shape maintaining property, (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 various characteristics of the binder component, adjustment of the blending amount of the filler (C) such as an inorganic filler described later, and the like.

(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). The measurement by such a method is performed, for example, on a high-speed GPC device “HLC-8120GPC” manufactured by Tosoh Corporation, a high-speed column “TSK gold column HXL-H”, “TSK Gel GMHXL”, “TSK Gel G2000 HXL” (or more, 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 polymerizable structure such as an acrylate compound such as a taconic acid oligomer and having a relatively low molecular weight can be used. 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) Filler The protective film-forming film 4 may contain a filler (C) such as an inorganic filler. Hereinafter, a case where the filler (C) is an inorganic filler will be described as a specific example. By blending the inorganic filler as the filler (C) in the protective film-forming film 4, it becomes possible to adjust the thermal expansion coefficient of the cured protective film and protect the workpiece W after curing. By optimizing the thermal expansion coefficient of the film, 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 as the filler (C) is exposed at the portion scraped off by the laser beam, and the reflected light diffuses to exhibit a color close to white. Thereby, when the film 4 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 inorganic filler as the filler (C) can be used alone or in admixture of two or more.

  The content of the filler (C) such as an inorganic filler is not particularly limited. When the content is excessively large, the adhesiveness to the workpiece W decreases, and when it is excessively small, it is difficult to obtain the effect of increasing the visibility of the marking portion by containing an inorganic filler, and filling What is necessary is just to set suitably considering the composition of material (C). Usually, the content of the filler (C) is preferably 30% by mass or more and more preferably 50 to 80% by mass as a proportion of the total solid content constituting the protective film-forming film 4. It is particularly preferably 60 to 80% by mass. Moreover, when the base material 2 contains a filler (C) such as an inorganic filler, the mass of the total solid content of the protective film-forming film 4 of the filler (C) contained in the protective film-forming film 4 It is preferable that the ratio occupied in is larger than the ratio occupied in the mass of the total solid content of the base material 2 of the filler contained in the base material 2.

(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. In addition, when the protective film is engraved 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 etc. is printed on the surface of the protective film by the laser marking method (a method in which the surface of the protective film 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 A 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, adhered and / or protected to an adherend of a protective film-forming film. It may be used to improve the cohesiveness of the 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) are 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.

(3) Thickness The thickness of the protective film-forming film 4 is not particularly limited. Usually, it is preferably in the range of 3 μm or more and 300 μm or less. From the viewpoint that the protective film formed from the protective film-forming film 4 functions properly, from the viewpoint of increasing productivity, from the viewpoint of increasing economy, the protective film is formed. The thickness of the film 4 is more preferably 5 μm or more and 250 μm or less, and particularly preferably 7 μm or more and 200 μm or less.

3. Protective film-forming composite sheet (1) void portion As shown in FIG. 2, the protective film-forming composite sheet 10 according to one embodiment of the present invention has the above-described first uneven surface area 1a on one main surface. By providing at least one of the pressure-sensitive adhesive sheet 1 having 1A and the protective film-forming film 4 having the second uneven surface region 4a on one main surface 4B, the diffusion path of the pollutant generated during laser marking and It has a void portion.

With respect to the components that define the voids of the composite sheet 10 for forming a protective film, the following cases can be cited.
(1-1) When only having the 1st uneven surface area When the protective film forming composite sheet 10 has only the 1st uneven surface area 1a, the protective film forming film bonded to the adhesive sheet 1 4 does not have the second uneven surface area 4a. The protective film-forming film so that the main surface 4B of one of the protective film-forming films 4 (the side facing the pressure-sensitive adhesive layer 3) covers part or all of the first uneven surface area 1a of the pressure-sensitive adhesive sheet 1. 4 and the adhesive sheet 1 are laminated. In other words, the outer periphery of one main surface 4B of the protective film forming film 4 may be entirely opposed to the first uneven surface region 1a, and a part of the outer periphery may be the first uneven surface. It may be opposed to the surface region 1a, or the entire outer periphery thereof may not be opposed to the first uneven surface region 1a. In the configuration shown in FIG. 2, the entire outer periphery of one main surface 4B of the protective film-forming film 4 is opposed to the first uneven surface area 1a.

  In the protective film-forming composite sheet 10 obtained in this way, the concave portion located in the region 1b covered with the one main surface 4B of the protective film-forming film 4 among the first concave portions of the first concave-convex surface region 1a. At least a part of the main surface 4B of the protective film forming film 4 does not come into contact with the main surface 4B and defines a first gap. The defined void portion becomes a diffusion path for the pollutant generated during laser marking.

(1-2) In the case of having only the second uneven surface region When the protective film forming composite sheet 10 has only the second uneven surface region 4a, the adhesive sheet to be bonded to the protective film forming film 4 1 does not have the 1st uneven surface area | region 1a. The protective film-forming film 4 and the pressure-sensitive adhesive sheet 1 are laminated so that the pressure-sensitive adhesive sheet first main surface 1A of the pressure-sensitive adhesive sheet 1 covers part or all of the second uneven surface area 4a of the protective film-forming film 4. Is done. In other words, the outer periphery of the pressure-sensitive adhesive sheet first main surface 1A of the pressure-sensitive adhesive sheet 1 may all face the second uneven surface area 4a, or a part of the outer periphery may be the second uneven surface. It may be opposed to the region 4a, or the outer periphery thereof may not have a portion facing the second uneven surface region 4a. 3 and 4, there is no portion facing the second uneven surface area 4 a on the outer periphery of the pressure-sensitive adhesive sheet first main surface 1 </ b> A of the pressure-sensitive adhesive sheet 1. In the configuration shown in FIG. 5, the outer periphery of the pressure-sensitive adhesive sheet first main surface 1 </ b> A of the pressure-sensitive adhesive sheet 1 is entirely opposed to the second uneven surface area 4 a.

  In the protective film-forming composite sheet 10 obtained in this way, at least a part of the recesses located in the region covered with the adhesive sheet first main surface 1A among the second recesses of the second uneven surface region 4a, Without contacting the first main surface 1A of the pressure-sensitive adhesive sheet, the first main surface 1A of the pressure-sensitive adhesive sheet and the second gap are defined. The defined void portion becomes a diffusion path for the pollutant generated during laser marking.

(1-3) When having the first uneven surface area and the second uneven surface area When the adhesive sheet 1 according to the present embodiment and the protective film forming film 4 according to the present embodiment are laminated, A first gap and a second gap are defined. The defined voids serve as a diffusion path for the pollutant that these voids generate during laser marking. In this case, the positional relationship between the second gap and the first gap in plan view is not particularly limited. In a plan view, the region where the second gap is formed and the region where the first gap is formed may overlap or may be independent. When these regions overlap, there may be a portion where the first gap and the second gap are integrated.

  Here, a void portion (may be composed of a first void portion, may be composed of a second void portion, or is composed of a first void portion and a second void portion) Is defined in relation to a processing area that is an area that is affixed to the workpiece W during use on the main surface 10A distal to the base material 2 of the composite sheet 10 for forming a protective film. Also good. Specifically, the void portion is an inner void portion that is a void portion located in the processing region in plan view, and processing in the main surface 10A distal to the base material 2 of the protective film-forming composite sheet 10 in plan view. You may prescribe | regulate a space | gap part by the relationship with the outside space | gap part located in the non-processed area | region which is areas other than an area | region. The intra-region gap portion may be locally increased in concentration of the pollutant when the laser beam is irradiated to perform laser marking. It is preferred that the contaminating substances present are capable of diffusing into the voids outside the zone.

  Furthermore, you may make the shape of a space | gap part different in a space | gap part inside a region and a space | gap part outside a region. Since there is a possibility that the laser beam is irradiated to the intra-region gap, the width of the concave portion defining the intra-region gap is narrow and the depth thereof is set so that the laser beam is less likely to be scattered based on the intra-region gap. In some cases, shallowness is preferred. On the other hand, since it is not necessary to consider the influence due to the scattering of the laser light, it is difficult for the out-of-region gap to be widened or deepened. Therefore, the recesses that define the inner gaps are narrowed or reduced in depth, while the recesses that define the outer gaps are increased in width or depth. For example, the pollutant material generated in the inner space may be easily diffused into the outer space.

  The out-of-area gap portion may have an opening having the gap portion as an open system. In this case, the peripheral edge of the opening is located on at least one of the pressure-sensitive adhesive sheet first main surface 1 </ b> A, the side surface of the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 1, and the side surface of the protective film forming film 4. In this way, when the opening is provided and the gap is an open system, the pollutant in the inner gap generated by the laser light irradiation diffuses to the outer gap, and further from the opening to the outside of the gap. It becomes possible to be discharged.

(2) Other components (2-1) Interfacial adhesion adjusting layer As shown in FIG. 6, the pressure-sensitive adhesive sheet 1 according to this embodiment is a partial region 1 c of the main surface 1 </ b> A on the pressure-sensitive adhesive layer 3 side. An interfacial adhesion adjusting layer 5 may be provided as an element constituting the. In the pressure-sensitive adhesive sheet 1 according to this embodiment, the interface adhesive layer 5 is positioned as one element of the pressure-sensitive adhesive layer 3. The shape of the interfacial adhesive layer 5 in plan view is a shape corresponding to the shape of the protective film forming film 4 in plan view, and the interfacial adhesive layer 5 forms the protective film on the first main surface 1A of the adhesive sheet 1 of the adhesive sheet 1. The adhesiveness to the film 4 can be controlled to facilitate picking up a chip provided with a protective film or the like on one surface thereof. In addition, in the area | region where the film 4 for protective film formation in the adhesive sheet 1st main surface 1A of the adhesive sheet 1 is surrounded and the film 4 for protective film formation is not laminated | stacked, the adhesive sheet 1 or the jig | tool mentioned later Due to the sufficient adhesiveness of the adhesive layer 6, the protective film-forming composite sheet 10 can be adhered to a jig.

  The interface adhesion adjusting layer 5 may be a predetermined film or an interface adhesion adjusting pressure-sensitive adhesive layer. The interfacial adhesion-adjusting pressure-sensitive adhesive layer is preferably a layer obtained by previously irradiating an energy ray-curable pressure-sensitive adhesive and curing it. The interfacial adhesion adjusting layer 5 may be the pressure-sensitive adhesive layer 3 manufactured by a common method, and may be processed so as to have different properties from other parts. For example, the pressure-sensitive adhesive layer 3 is formed from a pressure-sensitive adhesive composition containing the aforementioned acrylic polymer (α) and the like, and irradiation is performed to advance the polymerization reaction of the components contained in the pressure-sensitive adhesive composition. Since the irradiation amount of the energy beam is relatively large, the degree of progress of the polymerization reaction may be relatively high, and as a result, it may be a portion where the adhesiveness is lowered. Alternatively, it may be a region of the surface of the pressure-sensitive adhesive layer 3 on the side farther from the base material 2 and roughened than the other region, resulting in a decrease in the adhesiveness. . Since the laser for laser marking is irradiated through the interfacial adhesion adjusting layer 5, the interfacial adhesion adjusting layer 5 is preferably excellent in laser light transmittance.

  The relationship in plan view between the region 1c, which is a surface composed of the interface adhesion adjusting layer 5, and the pressure-sensitive adhesive sheet first main surface 1A is not particularly limited. As shown in FIG. 6, the region 1 c may be a partial region of the adhesive sheet first main surface 1 </ b> A, or the entire region of the adhesive sheet first main surface 1 </ b> A is the region 1 c, The surface on the side farther from the base material 2 may be a surface entirely composed of the interface adhesion adjusting layer 5.

  The relationship in plan view between the region 1c, which is a surface formed of the interface adhesion adjusting layer 5, and the region 1b on which the protective film forming film 4 is laminated is not particularly limited. As shown in FIG. 6, the region 1 b may be a partial region of the region 1 c, or the entire region 1 c may be the region 1 b, and the protective film forming film 4 may be a surface formed of the interface adhesion adjusting layer 5. It may be arranged so as to cover the entire surface.

(2-2) Jig Adhesive Layer As shown in FIG. 7, the protective film-forming composite sheet 10 according to the present embodiment has a main surface 10 </ b> A on the protective film-forming film 4 side of the protective film-forming composite sheet 10. May be further provided with a jig adhesive layer 6 laminated on a region 10b that is a partial region of the main surface 10A and is proximal to the outer periphery of the main surface 10A. The jig adhesive layer 6 is for fixing a jig such as a ring frame to the adhesive sheet 1. 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.

  As described above, when the pressure-sensitive adhesive sheet 1 includes the interface adhesion adjusting layer 5, as shown in FIG. 7, the region 10b where the jig adhesion layer 6 is provided is a protective film of the composite sheet 10 for forming a protective film. It is a partial region of the main surface 10A on the forming film 4 side, and is positioned so as not to overlap with the region 1c provided with the interface adhesion adjusting layer 5 in the first main surface 1A of the pressure-sensitive adhesive sheet in a plan view. Also good.

  The relationship between the region 1b where the protective film forming film 4 is laminated on the first main surface 1A of the pressure-sensitive adhesive sheet and the region 10b where the jig adhesive layer 6 is provided is not particularly limited. As shown in FIG. 7, it is not necessary to have a region overlapping in plan view, or it is possible to have a region overlapping in plan view as shown in FIG. That is, the main surface proximal to the pressure-sensitive adhesive sheet 1 of the jig adhesive layer 6 may be attached to the main surface 1A of the pressure-sensitive adhesive sheet 1 in at least one region, or the other surface of the protective film-forming film 4 You may affix on 4A of main surfaces (the main surface stuck on the to-be-processed member W at the time of use, and also as "the 1st film main surface" in this specification).

(2-3) Peeling Sheet The protective film-forming composite sheet 10 according to the present embodiment is, as shown in FIG. 9, for the purpose of protecting the main surface 10A on the protective film-forming film 4 side. The release surface 20A of the release sheet 20 may be bonded to the surface 10A. The configuration of the release sheet 20 is arbitrary, and examples include a support member such as 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 20, Usually, it is about 20 micrometers or more and 250 micrometers or less.

(3) Protective film-forming composite sheet-peeling sheet laminate When the release sheet 20 is bonded to the protective film-forming composite sheet 10 according to this embodiment as shown in FIG. The protective film-forming composite sheet-release sheet laminate (also referred to as “PR laminate” in this specification) 100 may be stored. As a specific configuration of the PR laminate 100, a plurality of composite sheets 10 for forming a protective film processed into a predetermined shape are disposed on a long release sheet 20 while being separated from each other in the longitudinal direction of the release sheet 20. Thus, a configuration in which the PR laminate 100 is a long body as a whole is exemplified. In the case of such a configuration, the long body is rolled up to form a wound body, and the PR laminated body 100 is unwound from the wound body as necessary to form a protective film-forming composite sheet from the release sheet 20. 10 can be peeled off and used.

4). Manufacturing method of adhesive sheet The manufacturing method of the adhesive sheet 1 which concerns on this embodiment is the process of providing the uneven | corrugated shape for the 1st uneven surface area | regions 1a on the one surface of the adhesive layer 3, and the adhesive layer 3. Including a step of laminating on one surface of the substrate 2. These steps may be independent, or may be common and the formation of unevenness and lamination may be performed simultaneously.

  If an example of the manufacturing method of the adhesive sheet 1 is given, on the one main surface of the base material 2, the above-mentioned coating liquid for adhesive layer formation will be applied by a die coater, curtain coater, spray coater, slit coater, knife coater, etc. The pressure-sensitive adhesive layer 3 can be formed by coating to form a coating film and drying the coating film on one main surface of the substrate 2. The adhesive layer forming coating liquid is not particularly limited in its properties as long as it can be applied, and may contain a component for forming the adhesive layer 3 as a solute or a dispersoid. There is also a case.

  When the adhesive layer forming coating solution contains a crosslinking agent (γ), the acrylic in the coating film can be changed by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. What is necessary is just to advance the crosslinking reaction of a type | system | group polymer ((alpha)) and a crosslinking agent ((gamma)), and to form a crosslinked structure in the adhesive layer 3 with desired presence 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 a relative humidity of 50%. Curing may be performed such as standing for days.

  There is no particular limitation on the method of imparting the uneven shape to one main surface of the pressure-sensitive adhesive layer 3. A cylindrical body having a concavo-convex shape on its side surface may be rolled on one main surface of the pressure-sensitive adhesive layer 3, and a shape based on the inverted shape of the concavo-convex shape may be formed on one main surface of the pressure-sensitive adhesive layer 3 (rolling). Made). As a transfer process other than rolling, an original plate having a concavo-convex shape on one surface is prepared, and one main surface of the pressure-sensitive adhesive layer is pressed against the surface, and a shape based on the inverted shape of the concavo-convex shape on the surface is adhered. It may be formed on one main surface of the agent layer 3. Alternatively, an uneven shape may be formed by performing processing such as shot blasting, electric discharge, etching, etc. on one surface of the pressure-sensitive adhesive layer 3.

  As another example of the method for producing the pressure-sensitive adhesive sheet 1 according to the present embodiment, a release sheet such as the above-described release sheet 20 (hereinafter, also referred to as “first release sheet”) is prepared, and the above-described release surface is provided on the release surface. An adhesive layer forming coating solution is applied to form a coating film, which is dried to form a laminate composed of the adhesive layer 3 and the first release sheet. You may stick the main surface of a distal side to a 1st peeling sheet to one main surface of the base material 2, and obtain the laminated body which consists of the adhesive sheet 1 and a 1st peeling sheet. The first release sheet in this laminate may be peeled off quickly, or the pressure-sensitive adhesive layer 3 is protected until the protective film-forming film 4 is formed on the surface 1A on the pressure-sensitive adhesive layer 3 side of the pressure-sensitive adhesive sheet 1. You may do it.

  Here, if the peeling surface of said 1st peeling sheet has the inverted shape of the uneven | corrugated shape which one main surface of the adhesive layer 3 should have, the 1st peeling sheet will be peeled from the adhesive layer 3. By making it, a desired uneven | corrugated shape can be provided to one main surface of the adhesive layer 3. FIG. There is no limitation on the method for imparting the inverted shape of the uneven shape to the release surface of the first release sheet. Transfer processing such as rolling may be performed, or removal processing such as shot blasting, electric discharge, and etching may be performed. In the case where the first release sheet is composed of a support member and a release layer, it is preferable to perform shape processing on one main surface of the support member and then form a release layer on the main surface. There is also.

  When the pressure-sensitive adhesive layer 3 is formed by such a method, the pressure-sensitive adhesive layer 3 may be formed so as to have a laminated structure. Specifically, an adhesive layer made of a material that easily transfers the shape of the release surface of the first release sheet is formed on the release surface of the first release sheet, and then such an adhesive layer is formed on the adhesive layer. An adhesive layer made of a material other than the material that can be easily transferred may be formed, and the adhesive layer 3 may be made of a laminate of these layers. By adopting such a method, the material cost may be reduced.

  The pressure-sensitive adhesive sheet 1 obtained in this way may be a finished product as it is, or by subjecting the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 1 to energy ray irradiation or the like, the polymerization reaction of the components contained in the pressure-sensitive adhesive layer 3 May be advanced. In the present specification, the pressure-sensitive adhesive sheet 1 including the pressure-sensitive adhesive layer 3 having undergone the polymerization reaction in this way may be referred to as “post-irradiation pressure-sensitive adhesive sheet”.

  The interfacial adhesion adjusting layer 5 may be formed on the surface on the distal side of the base material 2 on the pressure-sensitive adhesive layer 3 side obtained as described above, or it may be distal to the base material 2 on the pressure-sensitive adhesive layer 3 side. The surface on the side may be the pressure-sensitive adhesive sheet first main surface 1A, and the jig adhesive layer 6 may be laminated on the surface. As a specific example of the forming and laminating method, a layered body that provides the interface adhesion adjusting layer 5 and the jig adhesive layer 6 is laminated on the surface of the pressure-sensitive adhesive layer 3 on the distal side, and the layered body is cut. As described above, there is a method of performing the half-cut from the layered body side to remove unnecessary portions of the layered body to obtain the interface adhesion adjusting layer 5 and the jig adhesion layer 6. Alternatively, a layered body that provides the interfacial adhesion adjusting layer 5 and the jig bonding layer 6 is laminated on the release surface of the release sheet, and the layered body is cut from the layered body side in the laminate of the release sheet and the layered body. Half-cutting is performed to remove unnecessary portions of the layered body, and the layered body side of the laminate of the interface adhesive adjusting layer 5 and the jig adhesive layer 6 and the release sheet as the layered body thus obtained is processed. The method of bonding the surface and the surface on the distal side to the base material 2 of the pressure-sensitive adhesive layer 3 and peeling the release sheet may also be mentioned.

  In said description, although the process of providing uneven | corrugated shape with respect to one main surface of the adhesive layer 3 is performed before irradiation of an energy ray, said shape provision process is performed after an energy ray is irradiated. It may be done.

5. Method for Producing Protective Film Forming Film The method for producing the protective film forming film 4 according to the present embodiment imparts a concavo-convex shape for the second concavo-convex surface region 4 a to one surface of the protective film forming film 4. Process.

  It will be as follows if a specific example of the manufacturing method of the film 4 for protective film formation is given. That is, a protective film-forming composition, which is a composition for forming a protective film-forming film, is prepared, and a release sheet such as the release sheet 41 (hereinafter referred to as “second release sheet”) is peeled off. On the surface, the protective film-forming composition is applied to form a coating film, and the resulting coating film is dried to form a protective film-forming film 4, with the protective film-forming film 4 exposed. The release surface of the release sheet 42 is bonded to the surface to form a laminate in which the protective film-forming film 4 is sandwiched between two release sheets (second release sheet and release sheet 42). Next, this laminated body is half-cut from the second release sheet side so that the second release sheet and the protective film forming film 4 are cut, and unnecessary portions (a part of the second release sheet and the protective film forming) A part of the film 4 is removed, and the shape of one main surface (also referred to as “second film main surface” in this specification) 4B of the protective film-forming film 4 is changed to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 1. The shape corresponds to a partial region 1b of the main surface 1A on the 3 side. In this way, a laminate is obtained in which the protective film-forming film 4 is laminated on the release surface of the release sheet 42 and the second release sheet is further laminated on the film 4.

  Here, the release surface of the second release sheet has an inverted shape of the concavo-convex shape for the second concavo-convex surface region of the protective film-forming film 4, thereby forming the second release sheet of the protective film-forming film 4. A desired uneven shape can be formed on the opposing surfaces. A method for imparting the inverted shape of the uneven shape to the release surface of the second release sheet is not limited, and may be performed in the same manner as the case of providing the uneven shape to the release surface of the first release sheet.

  When the protective film forming film 4 is formed by such a method, the protective film forming film 4 may be formed to have a laminated structure. Specifically, a first layer made of a material that easily transfers the shape of the release surface of the second release sheet is formed on the release surface of the second release sheet, and then, on the first layer, A second layer made of a material other than the material that can be easily transferred may be formed, and the protective film-forming film 4 may be made of a laminate of these layers. By adopting such a method, the material cost may be reduced. For example, if the first layer does not contain a filler or a colorant, the material cost can be reduced, and the transferability of the shape imparted to the release surface of the second release sheet can be improved. is there.

6). Method for Manufacturing Protective Film Forming Composite Sheet A protective film forming composite sheet 10 according to the present embodiment uses at least one of the pressure-sensitive adhesive sheet 1 according to the present embodiment and the protective film forming film 4 according to the present embodiment. Manufacturing by bonding the main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side and one surface of the protective film-forming film (the surface having the region when the second uneven surface region is provided). Can do.

7). Marking Method The marking method according to some embodiments of the present invention will be described below.

(First marking method)
In the marking method according to an embodiment of the present invention (also referred to as “first marking method” in the present specification), first, as shown in FIG. 10, an adhesive having the first uneven surface area 1 a described above. The sheet first main surface 1A is stretched on the ring frame R and attached to one surface WA of the workpiece W such as a semiconductor wafer to form a laminated state. In this laminated state, laser light is irradiated from the pressure-sensitive adhesive sheet 1 side to mark one surface WA of the workpiece.

  In the case of the first marking method, even if a pollutant material is generated due to the marking formed on one surface WA of the workpiece W, the pollutant material is generated based on the first uneven surface area 1a. It is possible to diffuse through one void. Therefore, according to the first marking method, local contamination caused by the contaminating substance adhering to one surface WA of the workpiece W is unlikely to occur.

(Second marking method)
In a marking method according to another embodiment of the present invention (also referred to as “second marking method” in the present specification), first, as shown in FIG. The protective film forming composite sheet 10 having at least one of the second uneven surface areas 4a is stretched on the ring frame R, and the first film main film 4 of the protective film forming film 4 provided in the protective film forming composite sheet 10 is provided. The surface 4A is affixed to one surface WA of the workpiece W to obtain a laminated state. In this laminated state, protection is performed by irradiating the protective film forming composite sheet 10 side, specifically, by irradiating a laser beam from the base material 2 side, which is the distal side to the workpiece W of the protective film forming composite sheet 10. One main surface (second film main surface) 4B of the film forming film 4 is marked.

  In the case of the second marking method, even if the pollutant material is generated by forming the marking on the second film main surface 4B of the protective film forming film 4, the pollutant material is It is possible to diffuse through a gap formed by at least one of the first gap and the second gap based on at least one of the surface area 1a and the second uneven surface area 4a. Therefore, according to the second marking method, the local contamination due to the contaminating substance adhering to the second film main surface 4B of the protective film forming film 4 is hardly generated. The second marking method is different in marking object from the first marking method. In the first marking method, the workpiece W is marked, and in the second marking method, the protective film forming film 4 is marked. The

(Third marking method)
The marking method according to still another embodiment of the present invention (also referred to as “third marking method” in the present specification) is that the marking target is a protective film formed from the protective film-forming film 4. This is different from the second marking method. Specifically, the protective film in the protective film-containing composite sheet obtained by curing the protective film-forming film 4 provided in the protective film-forming composite sheet 10 stretched on the ring frame R to form a protective film. In the laminated state where one main surface (the main surface on the side distal to the adhesive sheet 1) is fixed to one surface WA of the workpiece W, the composite sheet side for protecting film formation (specifically, the adhesive) Laser light is irradiated from the base material 2 side of the sheet 1 to mark the other main surface of the protective film (main surface on the side proximal to the adhesive sheet 1).

  Since the protective film is formed by curing the protective film-forming film 4, when the protective film-forming film 4 has the second uneven surface region, the protective film also has an uneven surface region corresponding to this region. As a result, a gap corresponding to the second gap is also defined by the adhesive sheet 1 and the protective film. Therefore, even if a pollutant is generated by forming a marking on the main surface of the protective film on the side proximal to the pressure-sensitive adhesive sheet 1, the pollutant is an uneven surface corresponding to the second uneven surface area 4a. It is possible to diffuse through a void portion composed of at least one of a void portion corresponding to the second void portion and the first void portion based on at least one of the region and the first uneven surface area 1a. Therefore, according to the third marking method, the local contamination due to the contaminating substance adhering to the main surface on the side proximal to the adhesive sheet 1 of the protective film is less likely to occur.

8). Method for Producing Marking Chip Hereinafter, a chip formed by separating a workpiece W such as a semiconductor wafer using the pressure-sensitive adhesive sheet 1 and / or the composite sheet 10 for forming a protective film according to the present embodiment, A plurality of manufacturing methods for manufacturing a marking chip, which is a chip having a marking on its main surface (specifically, the main surface opposite to the circuit surface) will be described.

(First manufacturing method)
In the first manufacturing method, a chip to be processed is obtained by dicing the marked workpiece W obtained by performing the first marking method described above, and the workpiece W is separated into pieces. A marking chip having a marking on a surface based on one surface WA of the processed member W is obtained. The specific method of said dicing process is not specifically limited. Cutting with a blade (rotating blade) or laser ablation may be used. In these cases, the form of cutting may be full cut or half cut. Further, the dicing process may be stealth dicing in which the workpiece W is locally modified by laser irradiation and the modified portion is broken by a tensile process. The details of the dicing process are also the same in the second manufacturing method and later described later.

  In the marking chip manufactured by the first manufacturing method, marking is performed on one surface WA of the workpiece W to which the pressure-sensitive adhesive sheet 1 capable of defining the first gap portion is attached. For this reason, the possibility that the surface on which the marking chip has been marked is contaminated with a contaminating substance is reduced. Therefore, according to the first manufacturing method, the resulting marking chip is unlikely to have a problem due to a pollutant.

(Second manufacturing method)
In the second manufacturing method, a protective film formed on the principal surface (second film principal surface) 4B on the side proximal to the pressure-sensitive adhesive sheet 1 obtained by performing the second marking method described above is formed. Dicing is performed on the laminated structure including the protective film-forming composite sheet 10 including the protective film 4 and the processed member W to which the protective film-forming composite sheet 10 is attached. A chip formed in one piece and a small piece of the protective film forming film 4 affixed to a surface based on one surface WA of the workpiece W in the chip (also referred to as “protective film forming film piece” in this specification). A chip with a marking film is obtained.

  In the manufacturing process of the chip of the workpiece W and the chip with the marking film in the chip, the film for forming the protective film provided in the chip with the marking film obtained by the above method is cured and used as the protective film piece. A chip with a marking protective film comprising a protective film piece fixed to the surface that was proximal to the pressure-sensitive adhesive sheet 1 is obtained.

  According to the second manufacturing method, in the step of obtaining the chip with the marking film, the pressure-sensitive adhesive sheet in the protective film-forming film 4 that is a surface that defines at least one of the first gap and the second gap. Marking is performed on the main surface (second film main surface) 4B on the side proximal to 1. Therefore, the pollutant generated by the marking can be diffused through the first gap and / or the second gap. Specifically, when the pressure-sensitive adhesive sheet 1 has a first uneven surface area and the protective film forming film 4 does not have a second uneven surface area, the pollutant is diffused through the first gap. Yes. When the pressure-sensitive adhesive sheet 1 does not have the first uneven surface area 1a and the protective film-forming film 4 has the second uneven surface area 4a, the pollutant can diffuse through the second gap. When the pressure-sensitive adhesive sheet 1 has the first uneven surface area 1a and the protective film forming film 4 has the second uneven surface area 4a, the first void and the void based on the second void. (It may consist of the first gap, may consist of the second gap, or may be a gap formed by the first gap and the second gap). Sexual substances can diffuse.

  Therefore, the surface (the surface based on the second film main surface 4B of the protective film-forming film piece) on which the marking film-attached chip is marked is less likely to be contaminated with a contaminant. Yes. Therefore, according to the second manufacturing method, the resulting chip with the marking protective film is unlikely to be defective due to a pollutant.

  The method for curing the protective film forming film piece is not particularly limited, and a method suitable for the material constituting the protective film forming film piece may be used. When a material that cures by energy rays is contained, ultraviolet rays, electron beams, or the like may be irradiated. When a material that cures by heat is contained, it may be heated at a predetermined temperature for an appropriate time. When it is preferable to perform curing after performing the work for curing, curing may be performed under appropriate conditions (for example, standing for 7 days in an environment of 23 ° C. and 50% relative humidity).

  Curing of the protective film-forming film piece may be performed in a state where the protective film-forming film piece is separated from the pressure-sensitive adhesive sheet 1 or in a state where it is in contact with the pressure-sensitive adhesive sheet 1. That is, the temporal relationship between the step of curing the protective film forming film piece and the pickup step is not limited.

(Third production method)
In the third manufacturing method, first, the protective film on which the main surface (second film main surface) 4B on the side proximal to the adhesive sheet 1 is obtained by performing the second marking method described above. The forming film 4 is cured to form a marked protective film. As a result, a laminated structure including a protective film-containing composite sheet having a marked protective film formed from the protective film-forming composite sheet 10 and a workpiece W to which the protective film-containing composite sheet is attached is obtained. With a marking protective film comprising a chip formed by dividing a workpiece W into pieces and a small piece of a marked protective film fixed to one main surface of the chip by dicing the laminated structure. Get a chip.

  According to the third manufacturing method, in the step of obtaining the chip with the marking film, the pressure-sensitive adhesive sheet in the protective film-forming film 4 which is a surface that defines at least one of the first gap and the second gap. Marking is performed on the main surface (second film main surface) 4B on the side proximal to 1. Therefore, the pollutant generated by the marking can be diffused through the first gap and / or the second gap. Specifically, when the pressure-sensitive adhesive sheet 1 has the first uneven surface area 1a and the protective film-forming film 4 does not have the second uneven surface area 4a, the pollutant substance passes through the first gap. Can spread. When the pressure-sensitive adhesive sheet 1 does not have the first uneven surface area 1a and the protective film-forming film 4 has the second uneven surface area 4a, the pollutant can diffuse through the second gap. When the pressure-sensitive adhesive sheet 1 has the first uneven surface region 1a and the protective film-forming film 4 has the second uneven surface region, the first void portion and the void portion based on the second void portion ( In some cases, the first void portion may be a second void portion, and in other cases, the void portion is formed by the first void portion and the second void portion. Material can diffuse.

  Therefore, the surface (the surface based on the second film main surface 4B of the protective film-forming film piece) on which the marking film-attached chip is marked is less likely to be contaminated with a contaminant. Yes. Therefore, according to the third manufacturing method, the resulting chip with the marking protective film is unlikely to be defective due to a pollutant.

(Fourth manufacturing method)
In the fourth manufacturing method, a laminated structure comprising a protective film-containing composite sheet marked with a protective film and a workpiece W to which the protective film-containing composite sheet adheres, obtained by performing the third marking method described above. Dicing processing is performed on the body to obtain a chip with a marking protective film, which includes a chip of the workpiece W and a small piece of a marked protective film that is fixed to one main surface of the chip.

  According to the fourth manufacturing method, in the step of obtaining the chip with the marking film, the adhesive in the protective film, which is a surface that defines at least one of the first gap and the second gap. Marking is performed on the main surface on the side proximal to the sheet 1. Accordingly, the pollutant generated by the marking can be diffused through the gap corresponding to the first gap and / or the second gap. Specifically, when the pressure-sensitive adhesive sheet 1 has a first uneven surface area and the protective film does not have an uneven surface area corresponding to the second uneven surface area, a pollutant substance passes through the first gap. Can spread. In the case where the pressure-sensitive adhesive sheet 1 does not have the first uneven surface region 1a and the protection has the uneven surface region corresponding to the second uneven surface region 4a, it is contaminated through the void corresponding to the second void. Material can diffuse. When the pressure-sensitive adhesive sheet 1 has the first uneven surface region 1a and the protective film has the uneven surface region corresponding to the second uneven surface region 4a, it corresponds to the first void portion and the second void portion. A void portion based on the void portion (which may be composed of a first void portion or a void portion corresponding to the second void portion, or corresponding to the first void portion and the second void portion) Contaminants may diffuse through the voids that are created by the gaps that form).

  Therefore, the possibility that the surface of the chip with the marking protective film marked (the surface facing the adhesive sheet 1 of the protective film piece) is contaminated with a contaminant is reduced. Therefore, according to the fourth manufacturing method, the resulting chip with the marking protective film is unlikely to have a problem due to a contaminating substance.

(Fifth manufacturing method)
In the fifth manufacturing method, first, a laminated structure including an adhesive sheet 1 stretched on a ring frame and a workpiece W in which an adhesive sheet first main surface 1A is laminated on one surface WA. Get. Next, the laminated structure is diced from the workpiece W side to divide the workpiece W into pieces, thereby forming a plurality of chips, and an adhesive sheet on each surface of the plurality of chips. Let it be a laminated state with 1 attached. Subsequently, laser light is irradiated from the pressure-sensitive adhesive sheet 1 side (that is, the base material 2 side of the pressure-sensitive adhesive sheet 1), and marking is performed on one surface of the above chip to obtain a marking chip.

  In the marking chip manufactured by the fifth manufacturing method, marking is performed on one surface WA of the workpiece W to which the pressure-sensitive adhesive sheet 1 capable of defining the first gap portion is attached. For this reason, the possibility that the surface on which the marking chip has been marked is contaminated with a contaminating substance is reduced. Therefore, according to the fifth manufacturing method, the obtained marking chip is unlikely to have a problem due to a pollutant.

(Sixth manufacturing method)
In the sixth manufacturing method, first, the protective film forming composite sheet 10 stretched on the ring frame, and the first film main surface 4A of the protective film forming film 4 included in the protective film forming composite sheet 10 are A laminated structure including a workpiece W laminated on one surface WA is obtained. Next, dicing processing is performed on the laminated structure from the workpiece W side, and a plurality of chips formed by dividing the workpiece W into individual pieces and one surface of each of the plurality of chips. A plurality of film-attached chips comprising the attached protective film-forming film pieces are formed. As a result, a laminated state in which each of the plurality of film-attached chips is attached to the pressure-sensitive adhesive sheet first main surface 1A is obtained. In this laminated state, a laser beam is irradiated from the pressure-sensitive adhesive sheet 1 side, and marking is performed on the surface of each of the plurality of film-coated chips on the protective film forming film side to obtain a chip with a marking film. The chip for protective film formation of the chip with marking film thus obtained is cured to obtain a chip with marking protective film in which the marked protective film is laminated on one surface of the chip.

  According to the sixth manufacturing method, in the step of obtaining the chip with the marking film, the protective film-forming film 4 (specifically, which is a surface that defines at least one of the first gap and the second gap) Is formed into a protective film-forming film piece by dicing), and marking is performed on the main surface (second film main surface) 4B on the side proximal to the pressure-sensitive adhesive sheet 1. Therefore, the pollutant generated by the marking can be diffused through the first gap and / or the second gap. Specifically, when the pressure-sensitive adhesive sheet 1 has the first uneven surface area 1a and the protective film-forming film 4 does not have the second uneven surface area 4a, the pollutant substance passes through the first gap. Can spread. When the pressure-sensitive adhesive sheet 1 does not have the first uneven surface area 1a and the protective film-forming film 4 has the second uneven surface area 4a, the pollutant can diffuse through the second gap. When the pressure-sensitive adhesive sheet 1 has the first uneven surface region 1a and the protective film-forming film 4 has the second uneven surface region, the first void portion and the void portion based on the second void portion ( In some cases, the first void portion may be a second void portion, and in other cases, the void portion is formed by the first void portion and the second void portion. Material can diffuse.

  Therefore, the surface (the surface based on the second film main surface 4B of the protective film-forming film piece) on which the marking film-attached chip is marked is less likely to be contaminated with a contaminant. Yes. Therefore, according to the sixth manufacturing method, the resulting chip with the marking protective film is unlikely to be defective due to a pollutant.

(Seventh manufacturing method)
In the seventh manufacturing method, first, the protective film forming composite sheet 10 stretched on the ring frame, and the first film main surface 4A of the protective film forming film 4 included in the protective film forming composite sheet 10 are A laminated structure including a workpiece W laminated on one surface WA is obtained. Next, dicing processing is performed on the laminated structure from the workpiece W side, so that a plurality of chips formed by dividing the workpiece W into one piece and one surface of each of the plurality of chips A plurality of film-attached chips formed of a protective film-forming film piece attached to the film. Subsequently, the film pieces for forming a protective film included in the plurality of chips with a film are cured to obtain a plurality of chips with a protective film in which small pieces of the protective film are laminated on one surface of the chip. As a result, a stacked state is obtained in which each of the plurality of chips with protective film is adhered to the first main surface 1A of the pressure-sensitive adhesive sheet. In this laminated state, laser light is irradiated from the pressure-sensitive adhesive sheet 1 side to mark the main surface of each of the plurality of protective film-coated chips on the protective film side to obtain a chip with a marking protective film.

  According to the seventh manufacturing method, in the step of obtaining the chip with the marking film, the protective film (specifically, a surface that defines at least one of the first gap and the second gap corresponding to the second gap) Specifically, the protective film is divided into small pieces, and the main surface on the side proximal to the adhesive sheet 1 is marked. Accordingly, the pollutant generated by the marking can be diffused through the gap corresponding to the first gap and / or the second gap. Specifically, when the pressure-sensitive adhesive sheet 1 has a first uneven surface area and the protective film does not have an uneven surface area corresponding to the second uneven surface area, a pollutant substance passes through the first gap. Can spread. In the case where the pressure-sensitive adhesive sheet 1 does not have the first uneven surface region 1a and the protection has the uneven surface region corresponding to the second uneven surface region 4a, it is contaminated through the void corresponding to the second void. Material can diffuse. When the pressure-sensitive adhesive sheet 1 has the first uneven surface region 1a and the protective film has the uneven surface region corresponding to the second uneven surface region 4a, it corresponds to the first void portion and the second void portion. A void portion based on the void portion (which may be composed of a first void portion or a void portion corresponding to the second void portion, or corresponding to the first void portion and the second void portion) Contaminants may diffuse through the voids that are created by the gaps that form).

  Therefore, the possibility that the surface of the chip with the marking protective film marked (the surface facing the adhesive sheet 1 of the protective film piece) is contaminated with a contaminant is reduced. Therefore, according to the seventh manufacturing method, the resulting chip with the marking protective film is unlikely to be defective due to a pollutant.

  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.

  For example, in the manufacturing method of the above-described marking chip, when the dicing process includes a half cut or a stealth dicing and includes a plurality of operations (half cut or modification, and fracture), the dicing process is performed. During these operations, a protective film may be formed from the laser marking or the protective film-forming film 4.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

Example 1
As an adhesive composition for forming an adhesive layer provided in the adhesive sheet, an acrylic polymer (2-ethylhexyl acrylate / vinyl acetate / hydroxyethyl acrylate = 45/40/15 (mass ratio), weight average molecular weight = about 500,000) ) Is reacted with 80% equivalent of methacryloyloxyethyl acrylate (16 parts by mass with respect to 100 parts by mass of the acrylic polymer) to 100 parts by mass of the energy beam curable polymer, and a photopolymerization initiator (Ciba Specialty Chemicals) Co., Ltd., Irgacure (registered trademark) 184) 3.5 parts by mass, and isocyanate compound (Toyo Ink Manufacturing Co., Ltd., BHS-8515) 1.07 parts by mass (all blending ratio in terms of solid content) An agent composition was obtained.

The above-mentioned pressure-sensitive adhesive composition is applied onto a 100 μm-thick polyethylene film, and the resulting coating film is dried to form a substrate (thickness: 100 μm) and a pressure-sensitive adhesive layer (thickness: 10 μm). An adhesive sheet (total thickness: 110 μm) was obtained. The obtained pressure-sensitive adhesive sheet is irradiated with ultraviolet rays (230 mW / cm ² , 190 mJ / cm ² ) using an ultraviolet irradiation device (Adwill RAD-2000 m / 8, manufactured by Lintec Corporation). The polymerization reaction of the polymerizable component was allowed to proceed.

  An original plate having a surface in which a plurality of grooves having a width of 1 μm are formed at a distance of 2 mm by machining on the surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet thus subjected to polymerization treatment of the pressure-sensitive adhesive layer (hereinafter also referred to as “stripe original plate”). .) Is pressure-contacted to obtain a pressure-sensitive adhesive sheet having a region having a shape based on an inverted shape of the shape formed on the surface of the original plate on the surface on the pressure-sensitive adhesive layer side as a first uneven surface region. It was.

(Example 2)
Acrylic polymer (weight average molecular weight 900,000, glass transition temperature obtained by copolymerizing 55 parts by weight of butyl acrylate, 15 parts by weight of methyl methacrylate, 20 parts by weight of glycidyl methacrylate and 10 parts by weight of 2-hydroxyethyl acrylate) 100 parts by weight of a binder polymer comprising a copolymer at -28 ° C, a mixture of epoxy resins (liquid bisphenol A type epoxy resin (molecular weight about 370, epoxy equivalent 180 to 200 g / eq) 60 parts by weight, solid bisphenol A type epoxy resin (Molecular weight about 1,600, epoxy equivalent 800-900 g / eq) 10 parts by weight, o-cresol novolac type epoxy resin (molecular weight about 1,500-1,800, epoxy equivalent 210-230 g / eq) 30 parts by weight 100 parts by weight of thermosetting component, thermally active latent epoxy Fat curing agent (2.4 parts by weight of dicyandiamide, 2.4 parts by weight of 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2PHZ)), 10 parts by weight of carbon black (average particle size 28 nm), A formulation for forming a film for forming a protective film, comprising 288 parts by weight of fused silica filler (average particle size 8 μm), 32 parts by weight of synthetic silica filler (average particle size 0.5 μm), and a diluent was prepared.

The composition for forming the protective film-forming film is applied onto the release surface of the release sheet, and the resulting coating film is dried (temperature 100 ° C., 1 minute) to protect 20 μm in thickness. A laminate of the film forming film and the release sheet was obtained.
The protective film-forming composite sheet was obtained by pasting the protective film-forming film surface of the laminate on the adhesive layer-side surface of the adhesive sheet produced in Example 1. The protective film-forming film had a shape corresponding to the shape of a 6-inch semiconductor wafer.

(Example 3)
A pressure-sensitive adhesive sheet was obtained by the same production method as in Example 1 except that the width of the groove produced in the stripe original plate was 0.5 μm.

Example 4
A pressure-sensitive adhesive sheet was obtained by the same production method as in Example 1 except that the width of the groove produced in the stripe original plate was changed to 5 μm.

(Example 5)
A pressure-sensitive adhesive sheet was obtained by the same production method as in Example 1 except that the interval between the grooves produced on the stripe original plate was 0.4 mm.

(Example 6)
A pressure-sensitive adhesive sheet was obtained by the same production method as in Example 1 except that the interval between the grooves produced on the stripe original plate was 6.0 mm.

(Example 7)
An adhesive sheet was obtained by the same manufacturing method as in Example 1 (that is, the groove width was 1 μm and the groove interval was 2 mm) except that the pattern formed on the original plate was a lattice pattern.

(Comparative Example 1)
In Example 1, in producing the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer was not pressed against the stripe original plate, and the first uneven surface area was not formed on the pressure-sensitive adhesive sheet first main surface. An adhesive sheet was obtained by the production method.

(Test Example 1) Measurement of transmittance of pressure-sensitive adhesive sheet The pressure-sensitive adhesive sheet produced in Example 1 (a laminate of a base material and a pressure-sensitive adhesive) was 532 nm using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation). And transmittance at respective wavelengths of 1064 nm.
As a result of the measurement, the transmittance at 532 nm was 81%, and the transmittance at 1064 nm was 84%.

(Test Example 2) Evaluation of gas release properties A 6-inch unpolished silicon wafer was prepared by using a grinding machine (DFG-840, manufactured by Disco Corporation) to make a semiconductor wafer having a thickness of 150 μm by # 2000.

For each of the pressure-sensitive adhesive sheets produced in Examples 1 and 3 to 7 and Comparative Examples 1 and 2, the surface on the pressure-sensitive adhesive layer side was attached to the polished surface of the semiconductor wafer.
Moreover, it stuck on the grinding | polishing surface of said semiconductor wafer to the surface at the side of the film for protective film formation of the composite sheet for protective film formation manufactured in Example 2. FIG. Subsequently, the wafer having the protective sheet-forming composite sheet is heated at 130 ° C. for 2 hours to cure the protective film-forming film included in the protective film-forming composite sheet, and the laminate of the adhesive sheet and the protective film-attached wafer is formed. Obtained.

  The outer peripheral portion of the pressure-sensitive adhesive sheet in the thus obtained laminate including the pressure-sensitive adhesive sheet and the semiconductor wafer (the laminate according to Example 2 further includes a protective layer) was fixed with a ring frame. Next, using a YAG laser marker (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., LM5000, laser wavelength: 532 nm), laser light was irradiated from the pressure-sensitive adhesive sheet side of the above laminate, and characters of 400 μm length and 200 μm width were marked. .

The gas release property was evaluated by visually confirming whether or not contamination based on the contaminating substance generated by laser irradiation occurred at the interface between the wafer or the wafer with the protective film and the adhesive sheet. The evaluation criteria were as follows.
A: No gas stagnation B: Gas stagnation is low C: Gas stagnation is high Table 2 shows the evaluation results of gas release properties.

(Test Example 3) Visibility evaluation and confirmation of presence / absence of residual matter A dicing apparatus (manufactured by DISCO, DFD-651) was applied to a laminate including a pressure-sensitive adhesive sheet and a semiconductor wafer subjected to laser marking in Test Example 2. Dicing processing was performed, and the semiconductor wafer or the wafer with the protective film was separated into chips of 8 mm × 8 mm. For the structure in which the obtained chip or chip with protective film is disposed on the adhesive sheet, a pick-up process is performed using a die bonder (BESTEM-D02, manufactured by Canon Machinery Co., Ltd.), and the chip with marking chip or marking protective film Got. Visibility was evaluated by checking whether or not the marked characters on these chips could be read with a CCD camera. In addition, the marked surface of the chip and the chip with the protective film was observed with an optical microscope at a magnification of 100 times to confirm the presence or absence of a residue based on the pollutant.

The evaluation criteria for visibility were as follows.
A: The characters of all the chips to be observed could be read. B: There was a chip that could not read the characters. C: The characters of any chip to be observed could not be read. The criteria for the presence / absence confirmation were as follows.
A: No residue is observed for all the chips to be observed. B: Some chips have residuals observed. C: Many of the chips to be observed have residuals. Table 2 shows the results of the visibility evaluation and the confirmation of the presence or absence of residues.

  As can be seen from Table 2, the chip manufactured according to the example satisfying the conditions of the present invention and the chip with the protective film are not easily contaminated by the markings, and defects caused by the contamination are less likely to occur.

  INDUSTRIAL APPLICABILITY The present invention is suitably used as a means for providing a pressure-sensitive adhesive sheet, a protective film-forming film, and a protective film-forming composite sheet used when manufacturing a chip with a marking chip protective film from a device-related member such as a semiconductor wafer. .

DESCRIPTION OF SYMBOLS 1 ... Adhesive sheet 1A ... Main surface by the side of the adhesive layer 3 of the adhesive sheet 1 (adhesive sheet 1st main surface)
DESCRIPTION OF SYMBOLS 1a ... 1st uneven | corrugated surface area | region 1b ... Area | region 1c where the protective film formation film 4 in the adhesive sheet 1st main surface 1A is laminated | stacked ... Area | region 2 which is a surface which consists of the interface adhesion adjustment layer 5 ... Base material 2A ... Base material Main surface facing the adhesive layer 3 of 2 (substrate facing surface)
3 ... Adhesive layer 4 ... Protective film forming film 4A ... The other main surface of the protective film forming film 4 (main surface to be attached to the workpiece W during use, first film main surface)
4B: One main surface of the protective film-forming film 4 (main surface on the side proximal to the adhesive sheet 1, second film main surface)
4a ... second uneven surface area 40 ... protective film forming film laminate 41 ... release sheet 42 ... release sheet 5 ... interfacial adhesion adjusting layer 6 ... jig adhesive layer 10 ... protective film forming composite sheet 10A ... protective film formation Main surface 10b on the protective film forming film 4 side of the composite sheet 10 for the protective film ... A part of the main surface 10A on the protective film forming film 4 side of the composite sheet 10 for forming the protective film, and the outer periphery of the main surface 10A Region proximal to the region (region where the jig bonding layer 6 is provided)
20 ... release sheet 20A ... release surface 100 of release sheet 20 ... protective sheet-forming composite sheet-release sheet laminate (PR laminate)
W: Workpiece member WA: One surface R of the workpiece member W: Ring frame

Claims (14)

A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface of the base material,
The main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side has, as at least a partial region of the main surface, a first uneven surface area composed of an uneven surface,
When using the pressure-sensitive adhesive sheet, one surface of the adherend to be laser-marked is laminated on the pressure-sensitive adhesive sheet so as to cover a part or all of the first uneven surface area,
In a state where one surface of the adherend and the first uneven surface region are arranged to face each other,
Of the recesses in the first uneven surface area, at least a part of the recesses located in an area covered by one surface of the adherend does not contact the one surface of the adherend and the main surface A pressure-sensitive adhesive sheet, wherein a gap portion is defined, and the gap portion serves as a diffusion path for a pollutant generated during laser marking. A protective film-forming film that can be cured to form a protective film,
One main surface of the protective film-forming film has, as at least a partial region of the main surface, a second uneven surface region composed of an uneven surface,
The second uneven surface area can be marked with a laser beam,
At the time of use of the protective film-forming film, a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on one main surface of the base material is the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet. It is laminated on the protective film-forming film so as to cover a part or all of the second uneven surface area,
In a state where the second uneven surface region of the protective film-forming film and the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet are arranged to face each other,
Of the recesses in the second uneven surface area, at least part of the recesses located in the area covered by the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet is the main part on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet. A film for forming a protective film, wherein the main surface and a void are defined without contacting the surface, and the void serves as a diffusion path for a pollutant generated during laser marking.   The said 2nd uneven | corrugated surface area | region is a film for protective film formation of Claim 2 which has a part which touches the outer periphery of the said film for protective film formation by planar view. A base material, and a pressure-sensitive adhesive layer laminated on one main surface of the base material, wherein the main surface on the pressure-sensitive adhesive layer side is an uneven surface as at least a partial region of the main surface. A protective film-forming composite sheet comprising a pressure-sensitive adhesive sheet having an uneven surface area of 1 and a protective film-forming film that can be cured to form a protective film,
The protective film-forming film is laminated on the pressure-sensitive adhesive sheet so that one main surface of the protective film-forming film covers part or all of the first uneven surface area,
Of the recesses in the first uneven surface region, at least part of the recesses located in the region covered with one main surface of the protective film forming film is on one main surface of the protective film forming film. A composite sheet for forming a protective film, wherein the main surface and a void are defined without contact, and the void serves as a diffusion path for a pollutant generated during laser marking. 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 a protective film-forming composite sheet comprising the protective film-forming film according to claim 2 or 3. There,
The protective film-forming film is laminated on the pressure-sensitive adhesive sheet so that the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet covers part or all of the second uneven surface area,
Of the recesses in the second uneven surface area, at least part of the recesses located in the area covered by the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet is the main part on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet. A composite sheet for forming a protective film, wherein the main surface and a void are defined without contacting the surface, and the void serves as a diffusion path for a pollutant generated during laser marking.   The pressure-sensitive adhesive sheet is the pressure-sensitive adhesive sheet according to claim 1, wherein the first uneven surface area is positioned so that at least a part thereof faces the second uneven surface area. The composite sheet for protective film formation of description.   Among the gaps, in a plan view, the inner gap located in a processing area that is an area that is affixed to a workpiece when used on the main surface on the distal side of the base material of the composite sheet for forming a protective film Is communicated with an outside void portion located in a non-working region that is a region other than the working region on the main surface distal to the base material of the composite sheet for forming a protective film in a plan view. The composite sheet for forming a protective film according to any one of claims 4 to 6.   The outer space portion has an opening portion with the space portion as an open system, and the peripheral edge portion of the opening portion is a main surface of the pressure-sensitive adhesive sheet on the pressure-sensitive adhesive layer side, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. The composite sheet for forming a protective film according to claim 7, which is located on at least one of a side surface and a side surface of the protective film-forming film.   The jig further comprises a jig adhesion layer laminated in a region other than a region to be pasted on a workpiece when the main surface of the protective film-forming composite sheet is distal to the base material. The composite sheet for protective film formation according to any one of 8.   10. The composite sheet for forming a protective film according to claim 9, wherein a main surface of the jig adhesive layer that is proximal to the pressure-sensitive adhesive sheet is attached to the main surface of the pressure-sensitive adhesive sheet in at least one region.   11. The composite sheet for forming a protective film according to claim 9, wherein a main surface of the jig adhesive layer that is proximal to the pressure-sensitive adhesive sheet is attached to the main surface of the protective film-forming film in at least one region. . In the laminated state in which the main surface on the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet according to claim 1 stretched on the ring frame is affixed to one surface of the workpiece,
A marking method comprising irradiating a laser beam from the pressure-sensitive adhesive sheet side to mark one surface of the workpiece. One main surface of the film for forming a protective film provided in the composite sheet for forming a protective film according to any one of claims 4 to 11 stretched on a ring frame is formed on one surface of a workpiece. In the affixed laminated state,
A marking method comprising irradiating a laser beam from the protective film-forming composite sheet side and marking the other main surface of the protective film-forming film. The protective film containing obtained by hardening | curing the said film for protective film formation with which the composite sheet for protective film formation as described in any one of Claims 4-11 stretched by the ring frame is equipped. In the composite sheet, in the laminated state where one main surface of the protective film is fixed to one surface of the workpiece,
A marking method comprising irradiating a laser beam from the protective film-forming composite sheet side and marking the other main surface of the protective film.

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