WO2016088677A1

WO2016088677A1 - Adhesive sheet, and method for manufacturing processed article

Info

Publication number: WO2016088677A1
Application number: PCT/JP2015/083414
Authority: WO
Inventors: 茂之山下; 優智中村
Original assignee: リンテック株式会社
Priority date: 2014-12-02
Filing date: 2015-11-27
Publication date: 2016-06-09
Also published as: JPWO2016088677A1; KR20170091578A; CN106795396A; KR102447759B1; TW202144516A; TWI811763B; CN106795396B; TW201629171A; TWI738633B; JP6731852B2; SG11201704347YA; TW202014490A

Abstract

An adhesive sheet for use in the manufacture of chips by irradiating a plate-like member with laser light to form modified portions in the plate-like member and then dividing the plate-like member, said adhesive sheet comprising a base member and an adhesive agent layer arranged on one surface of the base member, wherein each of one surface of the base member and a surface opposed to said one surface of the base member has an arithmetic average roughness Ra as defined in JIS B0601:2013 (ISO 4287:1997) of 0.01 to 0.2 μm inclusive, and the adhesive agent layer has a thickness of 2 to 12 μm inclusive. The adhesive sheet rarely has defects and can exhibit excellent pickup performance when used in a dicing process with laser light.

Description

Adhesive sheet and method for producing processed product

The present invention relates to a pressure-sensitive adhesive sheet that irradiates a plate-like member with laser light to form a modified portion, and divides the plate-like member into pieces to obtain a chip-like workpiece. Moreover, this invention relates to the method of manufacturing workpieces, such as a chip | tip, using said adhesive sheet.

After a circuit is formed on the surface of a semiconductor wafer, grinding is performed on the back side of the wafer, and a back grinding process for adjusting the thickness of the wafer and a dicing process for dividing the wafer into a predetermined chip size are performed.

In recent years, with the downsizing of electronic equipment casings and the increasing demand for semiconductor devices using multi-layered chips, the thinning of semiconductor chips, which are constituent members, is being promoted. For this reason, it has been required to reduce the thickness of a conventional wafer having a thickness of about 350 μm to 50 to 100 μm or less.

¡As wafers that are brittle members become thinner, there is a higher risk of breakage during processing and transportation. When such an ultra-thin wafer is cut by a dicing blade that rotates at high speed, chipping or the like occurs particularly on the back side of the semiconductor wafer, and the die strength of the chip is significantly reduced.

For this reason, a so-called stealth dicing method is proposed in which a dicing line is formed while a modified portion is selectively formed by irradiating the inside of a semiconductor wafer with a laser beam, and the semiconductor wafer is cut starting from the modified portion. (Patent Document 1). According to the stealth dicing method, after forming the modified portion by irradiating the inside of the semiconductor wafer with a laser beam, the ultrathin semiconductor wafer is attached to an adhesive sheet (dicing sheet) composed of a base material and an adhesive layer, By expanding the dicing sheet, the semiconductor wafer can be divided (diced) along the dicing line, and semiconductor chips can be produced with high yield. It has also been proposed to form a modified portion by irradiating a laser beam after a semiconductor wafer is attached to a dicing sheet. By adopting such a process, since there is no step of applying a dicing tape to a wafer that has become fragile due to the formation of a modified portion, the risk of breakage of the fragile wafer can be reduced. In this case, since the laser is usually irradiated from the circuit non-formation surface of the wafer, it is necessary to pass the laser through the dicing sheet.

In some cases, a laser is used as a processing means in the dicing process as described above, and a laser is also used as a tool for accurately aligning a plate-like member such as a semiconductor wafer in the dicing process. In these cases, the pressure-sensitive adhesive sheet used when laser light is used in the dicing process (in this specification, this pressure-sensitive adhesive sheet is also referred to as “laser dicing sheet”) is used when the laser dicing sheet is used. If the laser is transmitted, it must have excellent transparency to the laser light.

In order to meet this requirement, for example, Patent Document 2 discloses a laser dicing sheet comprising a base material and an adhesive layer formed on one side thereof, and has a total light transmittance in a wavelength region of 300 to 400 nm. There is disclosed a laser dicing sheet that is 60% or more, has a haze of 20% or less, and has a transmission definition of 30 or more when the width of the optical comb is 0.25 mm.

JP 2005-229040 A Japanese Patent No. 5124778

Patent Document 2 discloses the above-described laser dicing sheet, in which the center line average roughness Ra on one side of the substrate is larger than the center line average roughness Ra on the other side, and the center line average roughness Ra is large. A surface having a center line average roughness Ra of 0.3 to 0.7 μm is defined as a pressure-sensitive adhesive layer forming surface, and the center line of the surface on the opposite side of the surface of the substrate A laser dicing sheet having an average roughness Ra of 0.14 μm is disclosed (Example of Patent Document 2).

Such a laser dicing sheet has a smooth surface on the side opposite to the pressure-sensitive adhesive layer forming surface of the substrate, which is the surface on which the laser is incident. This prevents the laser light from being used effectively.

Incidentally, a workpiece such as a semiconductor chip manufactured from a plate-like member such as a semiconductor wafer using a laser dicing sheet tends to be thinner. In recent years, as mounting density has increased, a silicon wafer may be used instead of a substrate, and a chip may be stacked thereon using a Si through electrode (TSV, Through-Silicon Via). Thus, when the workpiece is thin or the workpiece has a structure based on TSV, the pressure-sensitive adhesive layer of the laser dicing sheet is easily peeled off from the workpiece attached to the pressure-sensitive adhesive layer. It is preferable that it can be (excellent pickup property).

On the other hand, in the laser dicing sheet described in Patent Document 2, there may be a portion where the pressure-sensitive adhesive layer is not properly formed on the substrate. Such a portion is observed as a defect in a plan view of the laser dicing sheet, and may cause nonuniformity in the arrival light of the laser plate member incident to process the plate member.

The present invention provides a pressure-sensitive adhesive sheet that is used when laser light is used in a dicing process, and that provides a pressure-sensitive adhesive sheet that is less prone to defects and has excellent pick-up properties. It is an object to provide a method for producing a workpiece from a member.

When the present inventors examined in order to achieve the said objective, the thickness of an adhesive layer shall be 2 micrometers or more and 12 micrometers or less, and arithmetic mean roughness Ra of both surfaces of a base material shall be 0.2 micrometers or less. The present inventors have obtained new knowledge that a pressure-sensitive adhesive sheet having excellent pickup properties can be obtained while stably reducing the possibility of occurrence of defects.
The present invention completed based on the above findings is as follows.

(1) A pressure-sensitive adhesive sheet used for irradiating a plate-like member with laser light to form a modified portion, and dividing the plate-like member into chips to form a base material and one of the base materials An adhesive layer provided on the surface, and the base material is arithmetically defined in JIS B0601: 2013 (ISO 4287: 1997) for both the one surface and the surface opposite to the one surface. The pressure-sensitive adhesive sheet is characterized in that an average roughness Ra is 0.01 μm or more and 0.2 μm or less, and a thickness of the pressure-sensitive adhesive layer is 2 μm or more and 12 μm or less.

(2) The pressure-sensitive adhesive sheet has a haze specified in JIS K7136: 2000 (ISO 14782: 1999) of 0.01% or more and 10% or less when the base material side is the incident side (1) ) Adhesive sheet.

(3) The pressure-sensitive adhesive layer according to (1) or (2), wherein the pressure-sensitive adhesive layer contains an acrylic polymer, and the acrylic polymer has a glass transition temperature Tg of −40 ° C. or higher and −10 ° C. or lower. Sheet.

(4) The acrylic polymer includes a structural unit derived from methyl methacrylate, and the mass ratio of methyl methacrylate to the whole monomer giving the acrylic polymer is 5% by mass or more and 20% by mass or less. The pressure-sensitive adhesive sheet according to (3).

(5) The pressure-sensitive adhesive sheet according to (3) or (4), wherein the acrylic polymer has an energy ray polymerizable group.

(6) The pressure-sensitive adhesive sheet according to any one of (1) to (5), wherein the base material contains a polyolefin-based material.

(7) The pressure-sensitive adhesive sheet according to any one of (1) to (6), wherein the arithmetic average roughness Ra of the base material is set by roll-pressing the base material.

(8) The pressure-sensitive adhesive sheet according to (7), wherein the roll used for pressurizing the roll is a roll having a surface made of a metal material.

(9) A surface closer to the pressure-sensitive adhesive layer than the base material of the pressure-sensitive adhesive sheet described in any one of (1) to (8) is set to one surface of an adherend including a plate-like member. Affixing step to obtain a first laminate including the pressure-sensitive adhesive sheet and the plate-like member; elongating the base material provided in the first laminate, whereby the plate-like member on the pressure-sensitive adhesive sheet Dividing step of obtaining a second laminated body in which a plurality of chips each including a divided body of the plate-like member are disposed on the adhesive sheet; and the plurality of chips provided in the second laminated body A pickup step of separating each of the adhesive sheet from the pressure-sensitive adhesive sheet and obtaining the chip as a workpiece so that the chip is focused on a focal point set inside the plate-like member before the division step is started. Irradiate a laser beam to Method for producing a workpiece, wherein the modified part forming step of forming a modified section on the section is performed.

(10) The first laminate provided for the dividing step includes an additional layer between the pressure-sensitive adhesive layer and the plate-like member, and the additional layer is also divided by the dividing step, and the pickup step The chip separated from the pressure-sensitive adhesive sheet comprises a divided body of the plate-like member and a divided body of the additional layer formed on a surface proximal to the pressure-sensitive adhesive sheet of the divided body of the plate-like member. The manufacturing method of the workpiece as described in 9).

(11) The method for manufacturing a workpiece according to (10), wherein the additional layer includes a protective layer.

(12) Manufacture of a workpiece according to (11), further including a protective film forming step of forming the protective layer included in the first laminate from a protective film forming film before the division step is started. Method.

(13) The method for manufacturing a workpiece according to (10), wherein the additional layer includes a die bonding layer.

According to the present invention, there is provided an adhesive sheet that is less prone to defects and has excellent pick-up properties. Moreover, it becomes possible to manufacture a processed material stably from a plate-shaped member by using this adhesive sheet.

Hereinafter, embodiments of the present invention will be described.

1. Adhesive sheet The adhesive sheet which concerns on one Embodiment of this invention is equipped with a base material and an adhesive layer.

(1) Base Material The base material of the pressure-sensitive adhesive sheet according to this embodiment is a surface opposite to the pressure-sensitive adhesive layer (also referred to as “pressure-sensitive adhesive processing surface” in this specification) and the pressure-sensitive adhesive processing surface. For both surfaces (also referred to as “laser incident surface” in this specification), arithmetic average roughness Ra (hereinafter referred to as “arithmetic average roughness Ra”) defined in JIS B0601: 2013 (ISO 4287: 1997). “Is used in this sense.)” Is 0.2 μm or less. When the arithmetic average roughness Ra of these surfaces is 0.2 μm or less, defects are hardly observed in a plan view of the pressure-sensitive adhesive sheet. For this reason, the laser light incident from the base material side of the pressure-sensitive adhesive sheet easily reaches the plate-like member to which the pressure-sensitive adhesive sheet is stuck uniformly. When such laser light reaches the plate-like member non-uniformly, for example, there is a portion where the modified portion is not properly formed in the plate-like member, and the plate-like member is appropriately separated at this portion. There is a high possibility that problems such as failure to occur will occur. From the viewpoint of improving the uniformity of the incident laser light, the arithmetic average roughness Ra is preferably 0.18 μm or less, and preferably 0.16 μm or less for both the pressure-sensitive adhesive processed surface and the laser incident surface. More preferably, it is 0.14 μm or less, and particularly preferably 0.12 μm or less. From the viewpoint of obtaining a pressure-sensitive adhesive sheet that is less prone to defects in plan view, the lower limit of the arithmetic average roughness Ra is not limited for the pressure-sensitive adhesive processed surface. From the viewpoint of maintaining manufacturing stability, the arithmetic average roughness Ra is preferably 0.01 μm or more for both the pressure-sensitive adhesive processed surface and the laser incident surface.

The constituent material of the base material according to an embodiment of the present invention can satisfy the condition regarding the arithmetic average roughness Ra, and can be used as a base material of a laser dicing sheet, that is, a laser beam having a desired wavelength. In particular, as long as it satisfies the requirement that it is difficult to break even when it is stretched in the in-plane direction or locally protruded in the thickness direction, it can transmit with a transmittance in a practical range. There is no limitation. The base material according to an embodiment of the present invention is usually composed of a film mainly composed of a resin-based material. This film may be a single layer or a laminate.

Specific examples of resin materials contained in such films include polypropylene such as random copolymer polypropylene and block copolymer polypropylene, polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE). Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-based copolymer such as ethylene-norbornene copolymer, norbornene resin, etc. Polyolefin materials such as cycloolefin polymer (COP) polybutene, polybutadiene, and polymethylpentene; polyvinyl chloride materials such as polyvinyl chloride and vinyl chloride copolymers; polyethylene terephthalate, polybutylene terephthalate Polyester materials such as: Polyurethane materials; Polyimide materials; Ionomer resin materials; Polyacrylic materials such as alkyl (meth) acrylate homopolymers and alkyl (meth) acrylate copolymers; Polystyrene materials; Polycarbonate materials Examples thereof include resin materials, fluororesin materials, and resin materials mainly composed of water additives and modified products of these resin materials. The resin material may be a cross-linked product of the above material and a cross-linking agent. In addition, “(meth) acrylic acid” in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms. The resin-based material that provides the base material may be a single type or a mixture of two or more types. From the viewpoint of high laser transmittance, ease of local deformation in the in-plane direction and thickness direction, and low environmental load, the substrate according to an embodiment of the present invention contains a polyolefin-based material. Among the polyolefin-based materials, it is more preferable to contain a polypropylene such as a random copolymer polypropylene.

When the resin-based material contained in the base material is a polyolefin-based material, in general, the control of the arithmetic surface roughness Ra of both surfaces of the base material is a roll that sandwiches the base material using two rolls. Performed by pressurization. By adjusting the material constituting the surfaces of these rolls and the surface roughness, the arithmetic surface roughness Ra of both surfaces of the substrate is set. Conventionally, the surfaces of these rolls are generally made of one material made of metal and the other made of an elastic material such as rubber. For this reason, the arithmetic surface roughness Ra of the surface of the base material in contact with the roll made of a metal surface could be made relatively low, but the base material in contact with the roll made of an elastic material It was difficult to make the arithmetic surface roughness Ra of the surface low. Then, like the base material according to the present embodiment, when it is desired to reduce the arithmetic surface roughness Ra of both surfaces of the base material, both the rolls required for roll pressurization are made of metal. It is preferable. However, in this case, it is necessary to more strictly control the relative arrangement of both the rolls and the substrate as compared with the case where the surface of one roll is made of an elastic material. When the resin-based material contained in the base material is a polyvinyl chloride-based material, the base material can be manufactured by inflation molding, so the arithmetic surface roughness Ra on both sides of the base material is low. Setting to a value is easy. However, since the polyvinyl chloride-based material contains a halogen element, it is preferable not to use it as a base material when it is required to reduce the environmental load.

The base material may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in a film mainly composed of the resin-based material. Examples of the colorant include pigments such as titanium dioxide and carbon black, and various dyes. 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 should be within a range in which the substrate exhibits a desired function, particularly a function of transmitting laser, and does not lose desired smoothness and flexibility.

When ultraviolet rays are used as energy rays to be irradiated to cure the pressure-sensitive adhesive layer, it is preferable that the substrate has transparency to the ultraviolet rays. In addition, when using an electron beam as an energy beam, it is preferable that a base material has the transparency of an electron beam.

The thickness of the substrate is not limited as long as the pressure-sensitive adhesive sheet can function properly in each of the aforementioned steps. The thickness is preferably 20 to 450 μm, more preferably 25 to 200 μm, and particularly preferably 50 to 150 μm.

The base material preferably has a Young's modulus of 50 to 500 MPa. By setting the Young's modulus within this range, the mechanical strength of the base material can be improved while maintaining good extensibility, and the process suitability when forming the pressure-sensitive adhesive layer can be improved. For example, when a film containing a polyolefin resin as a base material is set on a coater, unintended elongation of the base material when tension is applied can be prevented.
The Young's modulus is more preferably 60 to 450 MPa, and further preferably 100 to 420 MPa, from the viewpoint of making blocking difficult to occur and improving the expandability while improving the mechanical strength. More preferably, the pressure is 150 to 300 MPa.

(2) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer provided in the pressure-sensitive adhesive sheet according to this embodiment has a thickness of 2 μm or more and 12 μm or less. Since the thickness of the pressure-sensitive adhesive layer is within the above range and the arithmetic average roughness Ra of both surfaces of the base material is within the above range, defects are unlikely to occur in a plan view and excellent pick-up properties are obtained. An adhesive sheet can be obtained. From the viewpoint of more stably reducing the possibility of occurrence of the above disadvantages, the thickness of the pressure-sensitive adhesive layer is preferably 3 μm or more, and more preferably 4 μm or more. From the viewpoint of more stably realizing an adhesive sheet having excellent pick-up properties, the thickness of the adhesive layer is preferably 10 μm or less, more preferably 8 μm or less, and 6 μm or less. It is particularly preferred.

The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet according to this embodiment is not limited. Examples of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive composition include rubber-based, acrylic-based, silicone-based, and polyvinyl ether-based pressure-sensitive adhesives. Hereinafter, the case where the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive will be described as an example. Acrylic pressure-sensitive adhesives are excellent in transparency, and are easy to transmit laser beams.

The acrylic pressure-sensitive adhesive contains an acrylic polymer. An acrylic polymer is a polymer containing a structural unit based on an acrylic compound as a unit constituting its skeleton. The acrylic polymer may be a homopolymer obtained by polymerizing one kind of monomer, or may be a copolymer obtained by polymerizing plural kinds of monomers. From the viewpoint of easily controlling physical properties and chemical properties of the polymer, the acrylic polymer is preferably a copolymer.

The acrylic polymer preferably has a glass transition temperature Tg of −40 ° C. or higher and −10 ° C. or lower. When the pressure-sensitive adhesive composition contains an acrylic polymer having a glass transition temperature Tg of −40 ° C. or higher, the pressure-sensitive adhesive layer is reduced in stickiness, and pickup properties can be further improved. From the viewpoint of more stably obtaining the effect of improving the pickup property, the glass transition temperature Tg of the acrylic polymer is more preferably −35 ° C. or higher. The glass transition temperature Tg of the acrylic polymer is preferably −20 ° C. or lower from the viewpoint that it is easy to maintain the performance of holding the chip after dividing the wafer into chips.

The weight average molecular weight (Mw) of the acrylic polymer is not limited. Usually, it is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000. Further, the molecular weight distribution (Mw / Mn, Mn is the number average molecular weight) is not limited. Usually, it is preferably 1.0 to 10, and more preferably 1.0 to 3.0.

The specific type of monomer that gives the acrylic polymer is not limited. Examples of such monomers include (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile and the like. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (Meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, etc. alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms; cycloalkyl (meth) acrylate, benzyl (meth) acrylate, iso (Meth) acrylates having a cyclic skeleton such as bornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, imide acrylate; Le (meth) acrylate, 2-hydroxypropyl having (meth) hydroxyl group, such as acrylates (meth) acrylate; glycidyl methacrylate, (meth) acrylate having an epoxy group such as glycidyl acrylate.

The acrylic polymer preferably contains methyl methacrylate from the viewpoint of increasing its glass transition temperature Tg. From the viewpoint of more stably enjoying the effect brought about by the acrylic polymer containing methyl methacrylate, the mass ratio of methyl methacrylate to the whole monomer giving the acrylic polymer is 5% by mass or more and 20% by mass. Or less, more preferably 7% by mass or more and 15% by mass or less.

The acrylic polymer may be a copolymer containing vinyl acetate, styrene, vinyl acetate or the like as a monomer.

The acrylic polymer may have at least one of an energy ray polymerizable group and a reactive functional group capable of reacting with the crosslinking agent (hereinafter abbreviated as “reactive functional group”).

When the acrylic polymer contains an energy ray-polymerizable group, the pressure-sensitive adhesive sheet having excellent pick-up properties can be reduced by irradiating the pressure-sensitive adhesive layer with energy rays. Can be easily obtained. Examples of the energy beam polymerizable group include a group containing a polymerizable double bond. The preparation method of the acrylic polymer having an energy ray polymerizable group is not limited. As an example of such a preparation method, an acrylic polymer having a functional group having an active hydrogen such as a hydroxyl group, a carboxylic acid group, or an amino group, and functional group capable of reacting with the above functional group such as an isocyanate group and energy beam polymerization Reacting a substance having a functional group (specific examples include (meth) acryloyloxyethyl isocyanate). When the acrylic pressure-sensitive adhesive contains an acrylic polymer containing an energy beam polymerizable group by such an adjustment method, the glass transition temperature Tg of the acrylic polymer described above is Tg before reacting a substance having a functional group capable of reacting with a group and an energy ray polymerizable group.

When the acrylic polymer has a reactive functional group, the cohesiveness of the pressure-sensitive adhesive layer is adjusted by reacting this reactive functional group with a cross-linking agent. It becomes easy to suppress the generation of a residue or to further improve the pickup property by reducing the adhesiveness of the adhesive layer. The combination of the reactive functional group and the crosslinking agent is not limited. Examples of reactive functional groups include groups having active hydrogen such as hydroxyl groups, carboxylic acid groups, and amino groups. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
The isocyanate-based crosslinking agent contains at least a polyisocyanate compound having a plurality of isocyanate groups. Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; dicyclohexylmethane-4,4′-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methyl Alicyclic isocyanate compounds such as cyclohexylene diisocyanate and hydrogenated xylylene diisocyanate; acyclic aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, and their biuret and isocyanurate forms, compounds having an isocyanate group And ethylene glycol, trimethylolpropane, castor Examples include modified products such as adducts which are reaction products with non-aromatic low-molecular active hydrogen-containing compounds such as oil.

Examples of the epoxy-based crosslinking agent include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl. Examples include ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like.

Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinyl propionate, tetramethylolmethane tri-β-aziridinyl. Propionate, toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, And trimethylolpropane tri-β- (2-methylaziridine) propionate.

Metal chelate crosslinking agents include chelate compounds whose metal atoms are aluminum, zirconium, titanium, zinc, iron, tin and the like. Among these, an aluminum chelate compound is preferable because of its excellent performance. Examples of the aluminum chelate compound include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy Examples thereof include aluminum monostearyl acetoacetate and diisopropoxy aluminum monoisostearyl acetoacetate.

When the pressure-sensitive adhesive composition contains an acrylic polymer, the pressure-sensitive adhesive composition may contain components other than the acrylic polymer. An example of such a material is an energy beam polymerizable compound. The energy beam polymerizable compound is a compound that polymerizes when irradiated with energy rays such as ultraviolet rays and electron beams. Examples of the energy beam polymerizable compound include low molecular weight compounds (monofunctional and polyfunctional monomers and oligomers) having an energy beam polymerizable group, and specifically include trimethylolpropane triacrylate and tetramethylolmethane. Tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, dicyclopentadiene dimethoxydiacrylate, isobornyl Cyclic aliphatic skeleton-containing acrylate such as acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy Modified acrylate, acrylate compounds, such as polyether acrylate is employed. Such a compound has at least one polymerizable double bond in the molecule, and usually has a molecular weight of about 100 to 30,000, preferably about 300 to 10,000. When the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive and contains an acrylic polymer containing an energy ray polymerizable group, the pressure sensitive adhesive composition contains a low molecular weight compound having an energy ray polymerizable group. Even if it does not contain or contains only a small amount, the adhesiveness with respect to a to-be-adhered body can be reduced by irradiating an energy ray to an adhesive layer. When there is much content of the low molecular weight compound which has an energy-beam polymeric group in an adhesive composition, there exists a tendency for pick-up property to fall. Therefore, the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive, and by using an acrylic polymer containing an energy ray polymerizable group, the amount of low molecular weight compound having an energy ray polymerizable group is reduced, The pickup property can be further improved. When the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive, the pressure-sensitive adhesive composition preferably contains 0 to 30 parts by mass of the energy ray polymerizable compound with respect to 100 parts by mass of the acrylic polymer. The content is more preferably 0 to 15 parts by mass, and further preferably 0 to 10 parts by mass.

When the pressure-sensitive adhesive composition contains an acrylic polymer having an energy ray polymerizable group or contains an energy ray polymerizable compound, it preferably contains a photopolymerization initiator. 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. By including a photopolymerization initiator, when ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced.

Examples of the energy beam for reacting the energy beam polymerizable group and the energy beam polymerizable compound include ionizing radiation, that is, X-rays, ultraviolet rays, and electron beams. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.

When ultraviolet rays are used as ionizing radiation, 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 light may be appropriately selected according to the type of energy ray polymerizable group or energy ray polymerizable compound contained in the pressure sensitive adhesive layer and the thickness of the pressure sensitive adhesive layer, and is usually about 50 to 500 mJ / cm ^2. 100 to 450 mJ / cm ² is preferable, and 150 to 400 mJ / cm ² is more preferable. The ultraviolet illumination is usually 50 ~ 500mW / cm ² or so, preferably 100 ~ 450mW / cm ^2, more preferably 150 ~ 400mW / cm ^2. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a metal halide lamp, etc. are used.

When an electron beam is used as the ionizing radiation, the acceleration voltage is appropriately selected according to the type of energy beam polymerizable group and energy beam polymerizable compound contained in the pressure sensitive adhesive layer and the thickness of the pressure sensitive adhesive layer. Usually, the acceleration voltage is preferably about 10 to 1000 kV. The irradiation dose may be set in a range in which the reaction of the energy beam polymerizable group or energy beam polymerizable compound contained in the pressure-sensitive adhesive layer appropriately proceeds, and is usually selected in the range of 10 to 1000 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.

(3) Optical properties The pressure-sensitive adhesive sheet according to one embodiment of the present invention is such that the haze specified by JIS K7136: 2000 (ISO 14782: 1999) is a surface closer to the base material than the pressure-sensitive adhesive layer. Is preferably 0.01% or more and 10% or less. When the haze is 10% or less, the laser light incident on the pressure-sensitive adhesive sheet can be effectively used. From the viewpoint of enabling more stable and effective use of laser light incident on the pressure-sensitive adhesive sheet, the haze is preferably 5% or less, more preferably 2.5% or less. . From the viewpoint of effective utilization of the laser light incident on the adhesive sheet, the lower limit of the above haze is not set. From the viewpoint of improving production stability, the haze is preferably about 0.01% or more.

The pressure-sensitive adhesive sheet according to one embodiment of the present invention has a total light transmittance of 85% or more when the surface closer to the substrate than the pressure-sensitive adhesive layer is the incident surface, as defined in JIS K7375: 2000. Preferably there is. When the total light transmittance is 85% or more, the laser light incident on the adhesive sheet can be effectively used. From the viewpoint of enabling more stable and effective use of the laser light incident on the pressure-sensitive adhesive sheet, the total light transmittance is preferably 90% or more. From the viewpoint of effective utilization of the laser light incident on the adhesive sheet, the upper limit of the total light transmittance is not set. From the viewpoint of improving the production stability, the total light transmittance is preferably about 99.99% or less.

(4) Additional layer The adhesive sheet which concerns on one Embodiment of this invention is provided with the additional layer in the surface at the side of an adhesive layer, and is an adherend of an adhesive sheet in the case of use of an adhesive sheet. The additional layer may be attached to the plate-like member. The configuration of the additional layer is not limited. Specific examples of the additional layer include a case where the additional layer includes a protective film-forming film and a case where the additional layer includes a die bonding layer.

The protective film-forming film is made of a material that can be cured by external energy such as heat to form a protective film. The protective film-forming film or the protective film is separated from the pressure-sensitive adhesive layer in a state where the divided body is attached to a chip-shaped member obtained by separating the plate-shaped member. Therefore, when the additional layer is a protective film-forming film, it is possible to obtain a processed product in which the protective film-forming film or the protective film divided body is laminated on one surface of the chip-like member.

Also when the additional layer is a die bonding layer, the die bonding layer is separated from the pressure-sensitive adhesive layer in a state where the divided body of the die bonding layer is attached to the chip-like member obtained by separating the plate-like member. Therefore, when the additional layer is a die bonding layer, it is possible to obtain a processed product in which the die bonding layer divided body is laminated on one surface of the chip-like member.

(5) Release sheet The pressure-sensitive adhesive sheet according to an embodiment of the present invention is for the purpose of protecting the pressure-sensitive adhesive layer or the additional layer until the pressure-sensitive adhesive layer or the additional layer is applied to the plate-like member as the adherend. The release surface of the release sheet may be bonded to the surface closer to the adhesive layer than the base material of the adhesive sheet, specifically to the surface of the adhesive layer or the surface of the additional layer. The configuration of the release sheet is arbitrary, and examples include a plastic film coated with a release agent. 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. Instead of the plastic film of the release sheet, a paper base such as glassine paper, coated paper, and high-quality paper, or a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on a paper base may be used. Although there is no restriction | limiting in particular about the thickness of this peeling sheet, Usually, they are about 20 micrometers or more and 250 micrometers or less.

2. Manufacturing method of processed material By using the pressure-sensitive adhesive sheet according to one embodiment of the present invention, it is possible to manufacture a processed material from a plate-like member as described below.

(1) Sticking step First, in the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the surface closer to the pressure-sensitive adhesive layer than the base material, specifically, the surface of the pressure-sensitive adhesive layer or the surface of the additional layer, Affixed to one surface of the adherend including the plate-like member to obtain a first laminate including the adhesive sheet and the plate-like member. The plate member is not limited. Examples thereof include a semiconductor wafer such as a silicon wafer, a laminate having a structure based on TSV, and the like. The thickness of the plate member is not limited. A range of several tens of μm to several hundreds of μm is exemplified.

The first laminate may be provided with an additional layer. Examples of the additional layer include a protective film forming film, a protective film formed from the protective film forming film, and a die bonding layer. The additional layer may be affixed to the plate-like member as a part of the pressure-sensitive adhesive sheet, or the additional layer may be previously laminated on one surface of the plate-like member. In the latter case, the surface of the additional layer opposite to the surface facing the plate member is the surface to which the adhesive sheet is attached as one surface of the adherend including the plate member.

(2) Dividing process By extending the base material provided in the first laminate, the plate-like member on the pressure-sensitive adhesive sheet is divided, and a plurality of chips including the plate-like member divided body are arranged on the pressure-sensitive adhesive sheet. A second laminated body is obtained. When the first laminate includes an additional layer, the additional layer is also divided by extending the base material. After the dividing step is performed, a portion with a large degree of elongation in the base material may be contracted by means such as heating to eliminate excessive slack in the pressure-sensitive adhesive sheet.

(3) Reformation part forming process Before the above dividing process is started, the laser beam is irradiated so as to be focused on the focal point set inside the plate-like member, and the inside of the plate-like member is reformed. Forming part. The wavelength of the laser beam and the irradiation method are appropriately set according to the structure of the plate member, the structure such as the thickness, and the like. When the modified part forming step is performed after the pasting step is performed, the plate member may be irradiated with laser light through an adhesive sheet. Even in such a case, the pressure-sensitive adhesive sheet according to an embodiment of the present invention is less likely to have a defect in a plan view. The problem that the generation of the modified portion in the shaped member becomes locally inappropriate is unlikely to occur. Thus, if the modified product is locally inappropriately formed in the plate-like member, the plate-like member may not be properly divided in the above-described dividing step. If the plate-shaped member is improperly divided, the possibility that the quality of the workpiece is lowered increases.

(4) Pickup process A chip can be obtained as a workpiece by separating each of the plurality of chips included in the second laminate from the adhesive sheet. The separation method is not limited. Usually, the adhesive sheet is deformed locally by pushing up pins and the like from the surface opposite to the chip facing side of the adhesive sheet, thereby reducing the adhesiveness of the adhesive layer to the chip to be separated. Next, the chip is separated from the pressure-sensitive adhesive sheet by peeling off the chip to be separated from the pressure-sensitive adhesive sheet using a vacuum collet or the like. In this case, when the pin is pushed up or when the chip is pulled up with a vacuum collet, a force for peeling off the adhesive layer from the chip is applied. When the chip is thin or has a structure based on TSV, there is a possibility that the chip may be cracked during the peeling. However, in the pressure-sensitive adhesive sheet according to an embodiment of the present invention, since the thickness of the pressure-sensitive adhesive layer is appropriately controlled, the possibility that the chip breaks during the peeling is appropriately reduced. That is, the pressure-sensitive adhesive sheet according to one embodiment of the present invention is excellent in pickup properties.

When the first laminate includes an additional layer, the chip separated from the pressure-sensitive adhesive sheet by this pick-up step is on the surface of the plate-shaped member divided body and the pressure-sensitive adhesive sheet of the plate-shaped member divided body. The division body of the formed additional layer is provided. That is, in the pick-up process, peeling occurs between the pressure-sensitive adhesive layer and the divided body of the additional layer, and the workpiece is separated from the pressure-sensitive adhesive sheet.

When the additional layer which gives the divided body of an additional layer is a protective film, the time when a protective film is formed from a protective film formation film is not limited. The additional layer provided in the first laminate is a protective film-forming film, and the work of forming the protective film from the protective film-forming film may be performed before the start of the separation step. The additional layer that gives the divided body of the additional layer is a protective film-forming film, and the protective film may be formed from the divided body of the protective film-forming film provided in the workpiece.

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.

Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.

[Example 1]
(1) Production of base material Extrusion molding is performed using a resin composition made of a random copolymer polypropylene resin with a small T-die extruder (“Lab Plast Mill” manufactured by Toyo Seiki Seisakusho Co., Ltd.), and one surface (adhesive processing) A film having an arithmetic surface roughness Ra of 0.03 μm and an other surface (corresponding to a laser incident surface) of 0.03 μm. did. The surface roughness of the substrate was measured using a surface roughness measuring machine (“SV-3000” manufactured by Mitutoyo Corporation).

(2) Preparation of pressure-sensitive adhesive composition A copolymer (glass transition temperature) obtained by copolymerizing 62 parts by mass of butyl acrylate, 10 parts by mass of methyl methacrylate and 28 parts by mass of 2-hydroxyethyl acrylate (HEA) Tg-34 ° C) is reacted with methacryloyloxyethyl isocyanate (MOI) at 80 mol% with respect to the copolymer HEA to obtain an acrylic polymer having an energy ray polymerizable group (weight average molecular weight 500,000). It was.
With respect to 100 parts by mass of the above acrylic polymer, 3.0 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by BASF, concentration: 100%), an isocyanate compound (“BHS-8515” manufactured by Toyo Ink) 1.0 mass parts was mix | blended and the adhesive composition diluted with the solvent was obtained.

(3) Preparation of pressure-sensitive adhesive sheet The pressure-sensitive adhesive composition was applied on the release surface of the release sheet. The obtained coating film and the release sheet were allowed to pass through an environment of 80 ° C. for 1 minute to obtain a laminate comprising the release sheet and an adhesive layer (the measured thickness was 10 μm).
The pressure-sensitive adhesive layer side of the above laminate is affixed to the pressure-sensitive adhesive processed surface of the base material, and the pressure-sensitive adhesive sheet composed of the base material and the pressure-sensitive adhesive layer is attached to the pressure-sensitive adhesive layer side surface. Further, it was obtained in a laminated state.

[Example 2]
A pressure-sensitive adhesive sheet was obtained in a state where a release sheet was laminated on the surface on the pressure-sensitive adhesive layer side in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was 5 μm.

Example 3
Except for the following changes, the pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, with the release sheet laminated on the surface on the pressure-sensitive adhesive layer side.
(Changes) The molding conditions of the base material were changed so that the arithmetic surface roughness Ra of the pressure-sensitive adhesive processed surface of the base material was 0.16 μm, and the arithmetic surface roughness Ra of the laser incident surface was 0.03 μm.

[Comparative Example 1]
Except that the thickness of the pressure-sensitive adhesive layer was 15 μm, the pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3 with the release sheet laminated on the surface on the pressure-sensitive adhesive layer side.

[Comparative Example 2]
Except for the following changes 1 and 2, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, with the release sheet laminated on the surface on the pressure-sensitive adhesive layer side.
(Change 1) The molding conditions of the base material were changed so that the arithmetic surface roughness Ra of the adhesive processing surface of the base material was 1.3 μm, and the arithmetic surface roughness Ra of the laser incident surface was 0.04 μm.
(Change 2) The thickness of the pressure-sensitive adhesive layer was 15 μm.

[Comparative Example 3]
Except that the thickness of the pressure-sensitive adhesive layer was 10 μm, a pressure-sensitive adhesive sheet was obtained in a state where the release sheet was laminated on the surface on the pressure-sensitive adhesive layer side in the same manner as in Comparative Example 2.

[Comparative Example 4]
Except for the following changes, the pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, with the release sheet laminated on the surface on the pressure-sensitive adhesive layer side.
(Changes) The molding conditions of the substrate were changed so that the arithmetic surface roughness Ra of the pressure-sensitive adhesive processed surface of the substrate was 0.04 μm, and the arithmetic surface roughness Ra of the laser incident surface was 1.3 μm.

[Test Example 1] <Measurement of haze>
In accordance with JIS K7136: 2000, the haze of the test piece obtained by peeling the release sheet from the pressure-sensitive adhesive sheet produced in Examples and Comparative Examples and cutting it to an appropriate size is used. “NDH-5000”) Measurement light was incident from the substrate side surface of the adhesive sheet. The results are shown in Table 1.

[Test Example 2] <Observation of defects>
The release sheet was peeled off from the pressure-sensitive adhesive sheets produced in Examples and Comparative Examples, and an arbitrary range of 100 mm × 100 mm on the pressure-sensitive adhesive layer side surface of each pressure-sensitive adhesive sheet was taken as the observation range. Each of these observation ranges was observed using an optical microscope and evaluated according to the following criteria based on the degree of existence of defects. The results are shown in Table 1.
A: No defects were observed in the observation range.
B: 5 or less defects were observed within the observation range.
C: Six or fewer defects were observed within the observation range.

[Test Example 3] <Pickup evaluation>
The pressure-sensitive adhesive sheets produced in Examples and Comparative Examples were cut into a circle in plan view, the release sheet was peeled off, and the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet was attached to a silicon wafer (thickness: 100 μm) and a ring frame.

Using a laser irradiation device, a laser focused on the inside of the wafer through the adhesive sheet from the side facing the adhesive layer of the silicon wafer is cut so that an 8 mm × 8 mm chip is formed. Irradiation was performed while scanning along the planned line. After irradiating all the planned cutting lines with laser, using an expander, pull out the 10 mm adhesive sheet at a speed of 10 mm / second, and remove the area where the silicon wafer is attached on the adhesive layer side of the adhesive sheet inside and outside the main surface. Stretched in the direction.

In this state, the adhesive sheet was irradiated with ultraviolet rays under the following irradiation conditions.
Illuminance: 220 mW / cm ²
Light intensity: 190 mJ / cm ²

Subsequently, the load at the time of pickup was measured with a push-pull gauge (push-up jig: 1 pin) manufactured by Aiko Engineering. The load required for pushing up was measured, and the pickup property was evaluated according to the following criteria based on the measured value. The results are shown in Table 1.
A: 1.7N or less B: Greater than 1.7N

As can be seen from Table 1, the pressure-sensitive adhesive sheet of the example satisfying the conditions of the present invention had a low haze, hardly suffered from defects, was excellent in pickup properties, and was suitable as a laser dicing sheet.

The pressure-sensitive adhesive sheet according to the present invention is suitably used as a laser dicing sheet.

Claims

A pressure-sensitive adhesive sheet used for forming a modified portion by irradiating a plate-like member with laser light, and dividing the plate-like member into chips,
A substrate and a pressure-sensitive adhesive layer provided on one surface of the substrate;
As for the said base material, arithmetic mean roughness Ra prescribed | regulated to JIS B0601: 2013 (ISO 4287: 1997) is 0.01 micrometer or more and 0.2 micrometer about both said one surface and the surface on the opposite side to said one surface. And
The pressure-sensitive adhesive sheet is characterized in that the pressure-sensitive adhesive layer has a thickness of 2 μm or more and 12 μm or less.
The said adhesive sheet is 0.01% or more and 10% or less when the haze prescribed | regulated to JISK7136: 2000 (ISO 14782: 1999) makes the base material side the incident side. Adhesive sheet.
The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the pressure-sensitive adhesive layer contains an acrylic polymer, and the acrylic polymer has a glass transition temperature Tg of -40 ° C or higher and -10 ° C or lower.
The said acrylic polymer contains the structural unit derived from methyl methacrylate, The mass ratio of the methyl methacrylate with respect to the whole monomer which gives the said acrylic polymer is 5 mass% or more and 20 mass% or less. The adhesive sheet as described.
The pressure-sensitive adhesive sheet according to claim 3 or 4, wherein the acrylic polymer has an energy ray polymerizable group.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the base material contains a polyolefin-based material.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the arithmetic average roughness Ra of the base material is set by roll-pressing the base material.
The pressure-sensitive adhesive sheet according to claim 7, wherein the roll used for pressurizing the roll is a roll having a surface made of a metal material.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 8, wherein a surface closer to the pressure-sensitive adhesive layer than the base material is attached to one surface of an adherend including a plate-shaped member, and the pressure-sensitive adhesive sheet A sticking step of obtaining a first laminate comprising a sheet and the plate-like member;
The plate-like member on the pressure-sensitive adhesive sheet is divided by extending the base material provided in the first laminate, and a plurality of chips including the plate-like member divided body are arranged on the pressure-sensitive adhesive sheet. A dividing step of obtaining a second laminated body; and a pickup step of separating each of the plurality of chips provided in the second laminated body from the pressure-sensitive adhesive sheet and obtaining the chips as a workpiece,
A reforming unit that irradiates a laser beam so as to be focused on a focal point set inside the plate-like member before the dividing step is started to form a reforming unit inside the plate-like member A method for producing a workpiece, wherein a forming step is performed.
The first laminate provided for the dividing step includes an additional layer between the pressure-sensitive adhesive layer and the plate-like member, the additional layer is also divided by the dividing step, and the adhesive layer is divided by the pickup step. The chip separated from the sheet is provided with a divided body of the plate-like member and a divided body of the additional layer formed on a surface proximal to the adhesive sheet of the divided body of the plate-like member. Method of manufacturing the workpiece.
The method for manufacturing a workpiece according to claim 10, wherein the additional layer includes a protective layer.
The manufacturing method of the workpiece of Claim 11 provided with the protective film formation process which forms the said protective layer with which a said 1st laminated body is provided from a protective film formation film before the said division | segmentation process is started.
The method of manufacturing a workpiece according to claim 10, wherein the additional layer includes a die bonding layer.