CN110272690B - Adhesive tape for semiconductor protection - Google Patents

Adhesive tape for semiconductor protection Download PDF

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Publication number
CN110272690B
CN110272690B CN201910185544.2A CN201910185544A CN110272690B CN 110272690 B CN110272690 B CN 110272690B CN 201910185544 A CN201910185544 A CN 201910185544A CN 110272690 B CN110272690 B CN 110272690B
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meth
acrylate
intermediate layer
adhesive tape
pressure
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CN110272690A (en
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佐佐木贵俊
秋山淳
东别府优树
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Nitto Denko Corp
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Nitto Denko Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/25Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255Polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/50Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00Presence of graft polymer
    • C09J2451/003Presence of graft polymer in the primer coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00Presence of polyester
    • C09J2467/006Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The invention provides an adhesive tape for semiconductor protection, which can well fill the concave-convex surface and has low solvent content. The adhesive tape for protecting a semiconductor of the present invention comprises: the pressure-sensitive adhesive layer is composed of an active energy ray-curable pressure-sensitive adhesive containing a (meth) acrylic polymer, the pressure-sensitive adhesive layer has a thickness of 1 [ mu ] m to 50 [ mu ] m, the intermediate layer is composed of a UV-polymerizable (meth) acrylic polymer, and the intermediate layer has a thickness of 50 [ mu ] m to 1000 [ mu ] m.

Description

Adhesive tape for semiconductor protection
Technical Field
The present invention relates to an adhesive tape for semiconductor protection.
Background
Conventionally, in a back grinding step for grinding the back surface of a semiconductor wafer to a desired thickness when processing the semiconductor wafer, an adhesive tape (back grinding tape) has been used in order to fix the semiconductor wafer or protect the surface opposite to the ground surface (for example, patent document 1). Generally, the back grinding tape is composed of a base material and an adhesive layer. Such a back grinding tape is used by attaching the pressure-sensitive adhesive layer side to the front surface of the semiconductor wafer (the surface opposite to the ground surface of the wafer), and is peeled off after grinding the back surface of the semiconductor wafer.
As the semiconductor wafer, a semiconductor wafer having bumps as electrodes on its surface is known. The back grinding tape used for such a semiconductor wafer is required to have appropriate rigidity and to be able to prevent wafer cracking in the back grinding process and to realize back grinding with good thickness accuracy, and is also required to be able to cover the bump surface well and to prevent moisture from entering during back grinding. As a method of filling the unevenness due to the bump and covering the bump surface satisfactorily, a method of increasing the thickness of the adhesive layer is exemplified. However, if the pressure-sensitive adhesive layer of the back grinding tape having the conventional structure is made thick, the influence of the residual solvent in the pressure-sensitive adhesive layer becomes large, and a problem arises in the health of the worker handling the back grinding tape.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-151163
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide an adhesive tape for protecting a semiconductor, which can well fill in concave and convex surfaces and has low solvent content.
Means for solving the problems
The adhesive tape for protecting a semiconductor of the present invention comprises: the pressure-sensitive adhesive layer is composed of an active energy ray-curable pressure-sensitive adhesive containing a (meth) acrylic polymer, the pressure-sensitive adhesive layer has a thickness of 1 [ mu ] m to 50 [ mu ] m, the intermediate layer is composed of a UV-polymerizable (meth) acrylic polymer, and the intermediate layer has a thickness of 50 [ mu ] m to 1000 [ mu ] m.
In one embodiment, when the adhesive tape for semiconductor protection is left in the air at 150 ℃ for 1 hour, the total amount of outgas of the 1 st organic solvent, the 2 nd organic solvent, or the 3 rd organic solvent according to the organic solvent poisoning prevention rule by the labor safety and health act is 25ppm or less.
In one embodiment, when the load value is measured by thermomechanical analysis (TMA) by pressing a probe having a diameter of 0.5mm into the pressure-sensitive adhesive layer with a pressing depth of 20% of the pressure-sensitive adhesive layer, the amount of change in load (μ N/(mm) is 1 to 300 seconds after the start of measurement2Second)) 1900 (. mu.N/(mm)2Seconds)) or less.
In one embodiment, the base material is made of a thermoplastic resin.
In one embodiment, the base material is made of a polyester resin.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an adhesive tape for semiconductor protection having a low solvent content, which can fill in irregularities well.
Drawings
Fig. 1 is a schematic cross-sectional view of a semiconductor protection adhesive tape according to an embodiment of the present invention.
Description of the reference numerals
10 base material
20 middle layer
30 adhesive layer
100 adhesive tape for semiconductor protection
Detailed Description
A. Outline of adhesive tape for semiconductor protection
Fig. 1 is a schematic cross-sectional view of a semiconductor protection adhesive tape according to an embodiment of the present invention. The adhesive tape 100 for protecting a semiconductor according to this embodiment includes: a substrate 10, an adhesive layer 30 disposed on at least one side of the substrate 10, and an intermediate layer 20 disposed between the substrate 10 and the adhesive layer 30. Although not shown, the adhesive tape for protecting a semiconductor of the present invention may be provided with a release liner on the outside of the adhesive layer until the adhesive tape is used for the purpose of protecting the adhesive surface.
The intermediate layer included in the adhesive tape for semiconductor protection of the present invention is composed of a UV-polymerized (meth) acrylic polymer. In the present specification, "UV-polymerized (meth) acrylic polymer" means: a polymer obtained by polymerizing a monomer composition containing a (meth) acrylic monomer and a photopolymerization initiator without using a solvent by ultraviolet irradiation. The adhesive tape for semiconductor protection of the present invention has advantages that the adhesive layer and the intermediate layer, which are layers having high flexibility, can favorably fill the uneven surface, and the intermediate layer made of a UV-polymerized (meth) acrylic polymer serves as a part of the layers having high flexibility, so that the adhesive tape has a small solvent content and is less likely to outgas. Further, by constituting the intermediate layer with a UV-polymerized (meth) acrylic polymer, the intermediate layer having a thickness can be formed as a single layer (that is, repeated coating performed when a thick layer is formed by solution coating is not required). As a result, an adhesive tape for semiconductor protection with very little warpage can be obtained.
When the adhesive tape for semiconductor protection of the present invention is left in the air at 150 ℃ for 1 hour, the total amount of outgas of the 1 st organic solvent, the 2 nd organic solvent, or the 3 rd organic solvent, which is an organic solvent poisoning prevention rule derived from the labor safety and health law, is preferably 25ppm or less. As described above, by including the intermediate layer composed of a UV-polymerized (meth) acrylic polymer, the pressure-sensitive adhesive tape having such a small amount of outgas can be obtained. The total amount of outgas is preferably 20ppm or less, more preferably 15ppm or less. The lower limit of the total amount of outgas is preferably smaller, for example, 0.5ppm (preferably 0.1ppm, more preferably 0 ppm).
Specific examples of the organic solvent of the above-mentioned type 1 include chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1, 2-dichloroethylene, 1,2, 2-tetrachloroethane, trichloroethane, and carbon disulfide. Specific examples of the 2 nd organic solvent include acetone, isobutanol, isopropanol, isoamyl alcohol, ethanol, ethylene glycol monoethyl ether acetate, ethylene glycol mono N-butyl ether, ethylene glycol monomethyl ether, o-dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, N-butyl acetate, N-propyl acetate, N-pentyl acetate, methyl acetate, cyclohexanol, cyclohexanone, 1, 4-dioxane, dichloromethane, N-dimethylformamide, styrene, tetrachloroethylene, tetrahydrofuran, 1,1, 1-trichloroethane, toluene, N-hexane, 1-butanol, 2-butanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, and methyl N-butanone. Specific examples of the 3 rd organic solvent include gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, turpentine, mineral spirits, and the like. In one embodiment, when the adhesive tape for semiconductor protection is left in the air at 150 ℃ for 1 hour, the total amount of the amount of outgas derived from ethyl acetate and the amount of outgas derived from toluene is in the above range (i.e., 25ppm or less, preferably 20ppm or less, and more preferably 15ppm or less).
The adhesive tape for semiconductor protection of the present invention preferably has an initial adhesive force at 23 ℃ of 0.4N/20mm or more, more preferably 0.5N/20mm or more, when it is bonded to a stainless steel plate. The upper limit of the initial adhesive force at 23 ℃ when the adhesive tape for semiconductor protection is bonded to a stainless steel plate is, for example, 35N/20 mm. The adhesive force was measured according to JIS Z0237: 2000. Specifically, the adhesive tape for semiconductor protection was bonded to a stainless steel plate (arithmetic average surface roughness Ra: 50. + -.25 nm) by reciprocating a 2kg roller 1 time, left at 23 ℃ for 30 minutes, and then peeled off at a peeling angle of 180 ℃ and a peeling speed (tensile speed) of 300 mm/minute. As described later, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for protecting a semiconductor of the present invention is composed of an active energy ray-curable pressure-sensitive adhesive, and the adhesive strength thereof can be changed by irradiation with an active energy ray.
In one embodiment, the adhesive force of the adhesive tape for semiconductor protection of the present invention can be changed by irradiation with active energy rays. An adhesive tape for semiconductor protection was adhered to a stainless steel plate and irradiated with a cumulative light amount of 500mJ/cm2~1500mJ/cm2(preferably 1000 mJ/cm)2) The adhesive strength at 23 ℃ after ultraviolet ray (using a high-pressure mercury lamp centered on 365nm in wavelength) of (A) is preferably 0.07N/20mm to 0.5N/20mm, more preferably 0.08N/20mm to 0.3N/20 mm. If the amount is within this range, a semiconductor protection pressure-sensitive adhesive tape having excellent releasability after a specific step (for example, a back grinding step) can be obtained.
The thickness of the adhesive tape for semiconductor protection is preferably 10 to 700. mu.m, more preferably 50 to 600. mu.m, and still more preferably 100 to 500. mu.m.
B. Intermediate layer
As described above, the intermediate layer is composed of a UV-polymerized (meth) acrylic polymer. Typically, UV polymerized (meth) acrylic polymers comprise structural units derived from alkyl (meth) acrylates.
In one embodiment, the intermediate layer is formed by UV irradiation of an intermediate layer-forming composition containing 1 or 2 or more kinds of alkyl (meth) acrylates. The composition for forming an intermediate layer contains no solvent.
Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, C1-20 alkyl (meth) acrylates such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate.
The UV-polymerized (meth) acrylic polymer may contain a structural unit corresponding to another monomer copolymerizable with the alkyl (meth) acrylate, if necessary, for the purpose of modifying the cohesive strength, heat resistance, crosslinking property, and the like. Examples of such monomers include carboxyl group-containing monomers such as acrylic acid and methacrylic acid; anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; sulfonic acid group-containing monomers such as styrenesulfonic acid and allylsulfonic acid; nitrogen-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, and acryloylmorpholine; aminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylate monomers such as methoxyethyl (meth) acrylate; maleimide monomers such as N-cyclohexylmaleimide and N-isopropylmaleimide; itaconimide monomers such as N-methylitaconimide and N-ethylitaconimide; a succinimide-based monomer; vinyl monomers such as vinyl acetate, vinyl propionate, N-vinylpyrrolidone and methyl-vinylpyrrolidone; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; glycol-based acrylate monomers such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; acrylate monomers having a heterocycle, a halogen atom, a silicon atom, and the like, such as tetrahydrofurfuryl (meth) acrylate, fluoro (meth) acrylate, and silicone (meth) acrylate; olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ether monomers such as vinyl ether. These monomer components may be used alone or in combination of 2 or more. The content ratio of the structural unit derived from the other monomer is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the acrylic polymer.
The intermediate layer-forming composition may contain an active energy ray-reactive compound (monomer or oligomer). Examples of the active energy ray-reactive compound include photoreactive monomers or oligomers having a functional group having a polymerizable carbon-carbon multiple bond, such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an ethynyl group. When a polyfunctional monomer such as a polyfunctional acrylate having 2 or more functional groups is used, a high molecular weight UV-polymerizable (meth) acrylic polymer can be obtained by bonding with the alkyl (meth) acrylate. Specific examples of the photoreactive monomer include (meth) acrylic acid and polyol esters such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and polyethylene glycol di (meth) acrylate; a polyfunctional urethane (meth) acrylate; epoxy (meth) acrylates; oligoester (meth) acrylates, and the like. Further, monomers such as methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), and m-isopropenyl- α, α -dimethylbenzyl isocyanate may be used. Specific examples of the photoreactive oligomer include dimers to pentamers of the above monomers.
As the active energy ray-reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinyl siloxane; or an oligomer composed of the monomer.
Further, as the active energy ray-reactive compound, a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocyclic rings in the molecule may be used. The mixture is irradiated with active energy rays (e.g., ultraviolet rays and electron rays) to cleave an organic salt to generate ions, which serve as starting species to initiate a ring-opening reaction of the heterocycle, thereby forming a three-dimensional network structure. Examples of the organic salts include iodonium salts, phosphonium salts, antimony salts, sulfonium salts, and borate salts. Examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include ethylene oxide, oxetane, oxolane, thiirane, aziridine, and the like.
When the intermediate layer-forming composition contains the active energy ray-reactive compound, the content of the active energy ray-reactive compound is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and still more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the base polymer.
The composition for forming an intermediate layer may contain a photopolymerization initiator. As the photopolymerization initiator, any suitable photopolymerization initiator can be used. Examples thereof include trade names "Irgacure 184", "Irgacure 651", "Irgacure 369", "Irgacure 379 ex", "Irgacure 819", "Irgacure OXE 2", "Irgacure 127", manufactured by BASF corporation; trade names "ESACURE one", "ESACURE 1001 m" manufactured by Lamberti; trade names "ADEKA OPTOMER N-1414", "ADEKA OPTOMER N-1606", and "ADEKA OPTOMER N-1717", manufactured by Asahi Denka Kogyo K.K. ". The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, and more preferably 2 to 10 parts by weight, based on 100 parts by weight of the polymer component in the intermediate layer-forming composition.
In one embodiment, the intermediate layer-forming composition includes a crosslinking agent. Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, and amine-based crosslinking agents.
When the intermediate layer-forming composition contains a crosslinking agent, the content of the crosslinking agent is preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight, based on 100 parts by weight of the polymer component in the intermediate layer-forming composition. If the elastic modulus is within such a range, a pressure-sensitive adhesive layer having an appropriately adjusted elastic modulus can be formed.
The intermediate layer-forming composition may further contain any appropriate additive as needed. Examples of the additives include an active energy ray polymerization accelerator, a radical scavenger, a thickener, a plasticizer (e.g., a trimellitate ester-based plasticizer, a pyromellitic ester-based plasticizer, etc.), a pigment, a dye, a filler, an antioxidant, a conductive material, an antistatic agent, an ultraviolet absorber, a light stabilizer, a release modifier, a softener, a surfactant, a flame retardant, an antioxidant, and the like. The composition for forming the intermediate layer contains no solvent.
The weight average molecular weight of the UV-polymerized (meth) acrylic polymer is preferably 30 to 1500 ten thousand, and more preferably 50 to 150 ten thousand. The weight average molecular weight can be measured by GPC (solvent: THF).
The glass transition temperature of the UV-polymerized (meth) acrylic polymer is preferably-50 to 30 ℃ and more preferably-40 to 20 ℃. When the amount is within this range, a pressure-sensitive adhesive sheet having excellent heat resistance and being applicable to a heating step can be obtained.
The thickness of the intermediate layer is 50 μm to 1000 μm. By forming the intermediate layer having such a thickness, a semiconductor protection adhesive tape in which the uneven surface can be favorably embedded can be obtained. The thickness of the intermediate layer is preferably 100 to 900 μm, more preferably 150 to 800 μm, still more preferably 200 to 700 μm, and particularly preferably 250 to 600 μm.
The elastic modulus of the intermediate layer is preferably 0.07 to 0.70MPa, more preferably 0.075 to 0.60MPa, and still more preferably 0.08 to 0.50 MPa. If the thickness falls within this range, a semiconductor protection pressure-sensitive adhesive tape in which the uneven surface can be satisfactorily filled can be obtained.
In the present specification, the elastic modulus means: modulus of elasticity measured by nanoindentation method at room temperature (23 ℃). The elastic modulus measured by the nanoindentation method can be measured under the following conditions.
(measurement apparatus and measurement conditions)
The device comprises the following steps: hysitron Inc. manufactured Tribo Inder
Using a pressure head: berkovich (triangular pyramid type)
The determination method comprises the following steps: single indentation assay
Setting the pressing depth: 2500nm
Pressing-in speed: 2000 nm/sec
And (3) measuring atmosphere: in the air
Sample size: 1cm x 1cm
When the intermediate layer is left in the air at 50 ℃ for 1 hour, the total amount of outgas of the 1 st organic solvent, the 2 nd organic solvent, or the 3 rd organic solvent, which is a rule for preventing organic solvent poisoning by the labor safety and health law, is preferably 25ppm or less, more preferably 20ppm or less, still more preferably 15ppm or less, still more preferably 10ppm or less, particularly preferably 5ppm or less, and most preferably 1ppm or less. The lower limit of the total amount of outgas is preferably smaller, for example, 0.5ppm (preferably 0.1ppm, more preferably 0 ppm). In one embodiment, when the intermediate layer is left in the air at 150 ℃ for 1 hour, the total amount of the amount of outgas derived from ethyl acetate and the amount of outgas derived from toluene is preferably within the above range.
C. Adhesive layer
The adhesive layer is composed of an active energy ray-curable adhesive containing a (meth) acrylic polymer. Typically, the active energy ray-curable adhesive further contains a crosslinking agent and a photopolymerization initiator. The adhesive force, rigidity, and the like of the adhesive layer formed of the active energy ray-curable adhesive can be changed by irradiation with active energy rays. Examples of the active energy rays include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio waves, alpha rays, beta rays, electron beams, plasma current, ionizing radiation rays, particle beams, and the like. In one embodiment, the irradiation of the active energy ray is performed with a cumulative light amount of 500mJ/cm2~1500mJ/cm2(preferably 1000 mJ/cm)2) The ultraviolet light (using a high-pressure mercury lamp having a wavelength of 365nm as a center) was irradiated.
The (meth) acrylic polymer contained in the active energy ray-curable pressure-sensitive adhesive is typically an acrylic polymer (homopolymer or copolymer) comprising 1 or 2 or more kinds of alkyl (meth) acrylates as monomer components. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and mixtures thereof, C1-20 alkyl (meth) acrylates such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate.
The (meth) acrylic polymer contained in the active energy ray-curable adhesive may contain a structural unit corresponding to another monomer copolymerizable with the alkyl (meth) acrylate, if necessary, for the purpose of modifying the cohesive force, heat resistance, crosslinking property, and the like. Examples of such monomers include carboxyl group-containing monomers such as acrylic acid and methacrylic acid; anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; sulfonic acid group-containing monomers such as styrenesulfonic acid and allylsulfonic acid; nitrogen-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, and acryloylmorpholine; aminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylate monomers such as methoxyethyl (meth) acrylate; maleimide monomers such as N-cyclohexylmaleimide and N-isopropylmaleimide; itaconimide monomers such as N-methylitaconimide and N-ethylitaconimide; a succinimide-based monomer; vinyl monomers such as vinyl acetate, vinyl propionate, N-vinylpyrrolidone and methyl-vinylpyrrolidone; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; glycol-based acrylate monomers such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; acrylate monomers having a heterocycle, a halogen atom, a silicon atom, and the like, such as tetrahydrofurfuryl (meth) acrylate, fluoro (meth) acrylate, and silicone (meth) acrylate; olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ether monomers such as vinyl ether. These monomer components may be used alone or in combination of 2 or more. In one embodiment, the (meth) acrylic polymer contained in the active energy ray-curable adhesive contains, as a structural unit corresponding to another monomer component copolymerizable with the alkyl (meth) acrylate, a structural unit derived from a carboxyl group-containing monomer (particularly preferably acrylic acid or methacrylic acid) or a hydroxyl group-containing monomer (particularly preferably hydroxyethyl (meth) acrylate). The content ratio of the structural unit derived from the carboxyl group-containing monomer is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the acrylic polymer. The content ratio of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the acrylic polymer.
The active energy ray-curable adhesive may contain an active energy ray-reactive compound (monomer or oligomer) described in the above item B.
The weight average molecular weight of the (meth) acrylic polymer contained in the active energy ray-curable pressure-sensitive adhesive is preferably 30 to 200 ten thousand, and more preferably 50 to 150 ten thousand. The weight average molecular weight can be measured by GPC (solvent: THF).
The glass transition temperature of the (meth) acrylic polymer contained in the active energy ray-curable pressure-sensitive adhesive is preferably-50 to 30 ℃, more preferably-40 to 20 ℃. When the amount is within this range, a pressure-sensitive adhesive sheet having excellent heat resistance and being applicable to a heating step can be obtained.
The active energy ray-curable adhesive may contain a photopolymerization initiator. As the photopolymerization initiator, any suitable photopolymerization initiator can be used. For example, the photopolymerization initiators listed in the above item B can be used. The content of the photopolymerization initiator is preferably 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight, based on 100 parts by weight of the base polymer in the adhesive.
The adhesive layer preferably contains a crosslinking agent. Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, and amine-based crosslinking agents.
The content of the crosslinking agent is preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight, based on 100 parts by weight of the base polymer of the binder. If the elastic modulus is within such a range, a pressure-sensitive adhesive layer having an appropriately adjusted elastic modulus can be formed.
In one embodiment, an isocyanate-based crosslinking agent is preferably used. The isocyanate-based crosslinking agent is preferable in that it can react with various functional groups. Specific examples of the isocyanate-based crosslinking agent include the compounds described in the item B.
The active energy ray-curable adhesive may further contain any appropriate additive as needed. Examples of the additives include an active energy ray polymerization accelerator, a radical scavenger, a thickener, a plasticizer (e.g., a trimellitate ester-based plasticizer, a pyromellitic ester-based plasticizer, etc.), a pigment, a dye, a filler, an antioxidant, a conductive material, an antistatic agent, an ultraviolet absorber, a light stabilizer, a release modifier, a softener, a surfactant, a flame retardant, an antioxidant, and the like.
The thickness of the pressure-sensitive adhesive layer is 1 to 50 μm, preferably 1 to 40 μm, more preferably 3 to 30 μm, particularly preferably 3 to 25 μm, and most preferably 5 to 20 μm. If the amount is within this range, a pressure-sensitive adhesive tape having a preferable adhesive strength as a pressure-sensitive adhesive tape used in the back grinding step can be obtained. In the present invention, the provision of the intermediate layer makes it possible to obtain an adhesive tape capable of satisfactorily filling the uneven surface even if the thickness of the adhesive layer is reduced. In the present invention, since the pressure-sensitive adhesive layer is thin, a pressure-sensitive adhesive tape having a small solvent content and a small outgassing amount can be obtained.
In one embodiment, when the load value is measured by thermomechanical analysis (TMA) with a penetration depth of 20% of the pressure-sensitive adhesive layer and a probe having a diameter of 0.5mm penetrating the pressure-sensitive adhesive layer, the amount of change in load (μ N/(mm) is 1 to 300 seconds after the start of measurement2Second)) 1900 (. mu.N/(mm)2Seconds)) or less. The amount of change in the load can be determined by { (value of load (. mu.N/mm) after 300 seconds from the start of measurement2) - (load value (. mu.N/mm) 1 second after the start of measurement2) Praxis of) }/299 (seconds). The load value was measured in an environment of 23 ℃. In addition, the rigidity of the adhesive layerThe load value is a load value before irradiation with the active energy ray.
The amount of change in the load was 1900(μ N/(mm)2Second) or less, the pressure-sensitive adhesive layer has excellent relaxability, and the pressure-sensitive adhesive tape provided with the pressure-sensitive adhesive layer has excellent unevenness follow-up properties, and can favorably fill in the unevenness of the adherend surface. In particular, an adhesive tape provided with such an adhesive layer is advantageous in that good unevenness follow-up properties can be maintained over time. The amount of change in the load is preferably 1500(μ N/(mm)2Second)) or less, more preferably 1000(μ N/(mm)2Second)) or less, and more preferably 500(μ N/(mm)2Second)) or less, and particularly preferably 100(μ N/(mm)2Seconds)) or less. The lower limit of the amount of change in the load is, for example, 10(μ N/(mm)2Second)).
The elastic modulus (before irradiation with active energy rays) of the pressure-sensitive adhesive layer is preferably 0.07 to 0.70MPa, more preferably 0.075 to 0.60MPa, still more preferably 0.08 to 0.50MPa, and particularly preferably 0.1 to less than 0.7 MPa. If the amount is within this range, a pressure-sensitive adhesive tape having a preferable adhesive strength as a pressure-sensitive adhesive tape used in the back grinding step can be obtained.
The elastic modulus of the pressure-sensitive adhesive layer after irradiation with active energy rays is preferably 1MPa or more, more preferably 5MPa or more, and still more preferably 10MPa or more. If the amount is within this range, a semiconductor protection pressure-sensitive adhesive tape having excellent releasability after a specific step (for example, a back grinding step) can be obtained. The upper limit of the elastic modulus of the pressure-sensitive adhesive layer after irradiation with active energy rays is preferably 1000MPa or less, more preferably 500MPa or less, and still more preferably 400MPa or less.
D. Base material
The substrate may be made of any suitable resin. In one embodiment, the substrate is composed of a thermoplastic resin. Examples of the resin include low-density polyethylene, linear polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homo polypropylene, polyolefin such as polybutene and polymethylpentene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane resin, polyester resin such as polyethylene naphthalate, polyimide resin, polyetherketone, polystyrene resin, polyvinyl chloride, polyvinylidene chloride, fluorine resin, silicon resin, and cellulose resin. Among them, polyester-based resins are preferable.
The glass transition temperature of the resin constituting the substrate is preferably 60 to 500 ℃, more preferably 100 to 500 ℃. When the amount is within this range, a pressure-sensitive adhesive sheet having excellent heat resistance and being applicable to a heating step can be obtained. The "glass transition temperature" means: in the DMA method (stretching method), the temperature at which the peak of loss tangent (tan. delta.) is observed under the conditions of a temperature rise rate of 5 ℃/min, a sample width of 5mm, a distance between chucks of 20mm, and a frequency of 10 Hz.
The thickness of the substrate is preferably 50 to 300. mu.m, more preferably 80 to 250. mu.m, and still more preferably 100 to 200. mu.m.
The elastic modulus of the base material is preferably 300MPa to 6000MPa, and more preferably 400MPa to 5000 MPa. If the thickness falls within such a range, a semiconductor protection adhesive tape that can appropriately follow the unevenness of the bonding surface can be obtained.
The surface of the substrate may be subjected to an arbitrary surface treatment in order to improve adhesion to an adjacent layer, retention, and the like. Examples of the surface treatment include chemical treatment, physical treatment, and coating treatment such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, and ionizing radiation treatment.
E. Method for producing adhesive tape for semiconductor protection
The adhesive tape for semiconductor protection can be produced by any suitable method. The adhesive tape for semiconductor protection can be formed, for example, as follows: the intermediate layer-forming composition is applied to the substrate, and then the applied layer is irradiated with ultraviolet rays to form an intermediate layer, and the active energy ray-curable adhesive is applied to the intermediate layer.
As a method of applying the composition for forming the intermediate layer, various methods such as bar coater coating, air knife coating, gravure coating, reverse roll coating, lip coating, die coating, dip coating, offset printing, flexographic printing, screen printing, and the like can be used.
The cumulative amount of ultraviolet light irradiated to the composition for forming an intermediate layer is preferably 1000mW/cm2~5000mW/cm2More preferably 2000mW/cm2~4000mW/cm2
As the method for applying the active energy ray-curable adhesive, the above-described application method exemplified as the method for applying the intermediate layer-forming composition can be used. In addition, a method of separately forming an adhesive layer on a release liner and then bonding the adhesive layer to a substrate may be employed.
F. Use of adhesive tape for semiconductor protection
The adhesive tape for protecting a semiconductor of the present invention can be suitably used when an electromagnetic wave shield is provided to an electronic component having an uneven surface (for example, an electronic component having bumps) and the uneven surface (bump formation surface) on which the electromagnetic wave shield is not required to be formed is masked.
In one embodiment, the adhesive tape for semiconductor protection of the present invention can be used for masking a surface having a bump with a height of 50 μm or more (for example, 50 μm to 300 μm). Typically, a plurality of bumps are provided in the face. The arrangement interval of the bumps (the distance from the center of the bump to the center of the adjacent bump) is, for example, 100 to 500 μm. In one embodiment, the bump has a circular shape in plan view and a diameter of 100 to 300 μm. The adhesive tape for semiconductor protection of the present invention can satisfactorily mask the surface having the bumps as described above, and can be peeled from the surface without leaving adhesive residue.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The test and evaluation methods in the examples are as follows. In addition, "part" and "%" are based on weight unless otherwise specified.
(1) Gas release amount
Cutting the adhesive tape for semiconductor protection into 5cm pieces2The size of (3) was defined as an evaluation sample. The evaluation samples were sealed into 20mL headspace vials under shade conditions. The headspace vial containing the evaluation sample was heated at 150 ℃ for 1 hour by a headspace sampler (HSS). Thereafter, the ethyl acetate amount and the toluene amount were measured for 1mL of the gas portion by Gas Chromatography (GC).
< HSS Condition >
The device comprises the following steps: agilent Technologies, 7697A
Heating temperature: 150 ℃ C
Heating time: 1 hour
Sample quantitative loop temperature: 160 deg.C
Transfer line temperature: 200 deg.C
Pressurizing time: 0.1 minute
Injection time: 0.50 min
< GC Condition >
The device comprises the following steps: agilent Technologies, 7890B
Column: HP-1(0.250 mm. phi. times.30 m, df. 1.0. mu.m)
Column temperature: 40 ℃ (3 minutes) → 10 ℃/minute → 120 → 20 ℃/minute → 300 ℃ (10 minutes)
Column flow rate: 1 mL/min (He)
Column pressure: constant flow mode (81kPa)
Injection port temperature: 250 deg.C
Injection amount: 1mL of
The injection mode is as follows: flow dividing ratio (20:1)
A detector: FID
Detector temperature: 250 deg.C
(2) Thermomechanical analysis (TMA)
Thermomechanical analysis (TMA) of the adhesive layer was performed under the following conditions, and the amount of change in load (μ N/(mm)) from 1 second to 300 seconds after the start of the measurement was measured2Second)).
The device comprises the following steps: TMA/SS7100 manufactured by SII Nano Technology
Measurement mode: compression expansion process
Diameter of the probe: 0.5mm phi (compression expansion method)
Temperature program: constant at 23 deg.C
And (3) measuring atmosphere: n is a radical of2(flow rate 200 ml/min)
Pressing amount: thickness of the adhesive layer X20%
(3) Burying property of bump
An adhesive tape for semiconductor protection was attached to a bumped 8-inch wafer having a bump pitch of 400 μm using a taping machine DR-3000II (manufactured by Nindon Seiko Co., Ltd.) (attachment conditions: speed 10 mm/sec, attachment temperature: 23 ℃, attachment pressure: 0.45MPa, roll hardness: 80 degrees). After the bonding, the filling property of the bump was confirmed by a microscope. Bubbles are generally generated around the bumps so as to surround the bumps, and if the bubbles are not connected to bubbles of adjacent bumps, the connection is regarded as acceptable (indicated by "o" in the table), and the connection of the bubbles is regarded as unacceptable (indicated by "x" in the table).
(4) Warping after grinding
An adhesive tape for semiconductor protection was attached to an 8-inch silicon mirror wafer using DR-3000 III. The bonding conditions were the same as the evaluation of the burying property of the bump. The bonded wafer with an adhesive tape was ground to a silicon thickness of 200 μm by a wafer grinder DFG-8560(DISCO Co.). After grinding, the warpage amount of the chip (the difference between the maximum value and the minimum value of the distance from the horizontal plane for the lower surface of the wafer when the wafer is placed on the horizontal plane) is measured using a straight edge/steel rule.
[ example 1]
(preparation of composition a for intermediate layer formation)
90 parts by weight of 2-ethylhexyl acrylate (2EHA), 10 parts by weight of Acrylic Acid (AA), 0.05 part by weight of a photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF corporation), 0.05 part by weight of a photopolymerization initiator (trade name: Irgacure651, manufactured by BASF corporation), and 0.10 part by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kagaku corporation) were put in a flask and sufficiently stirred to obtain an intermediate layer-forming composition a (acrylic polymer syrup).
(preparation of active energy ray-curable adhesive a)
An active energy ray-curable adhesive a was prepared which contained 100 parts by weight of an acrylic polymer composed of 2-ethylhexyl acrylate (2-EHA)/acryloylmorpholine/hydroxyethyl acrylate (HEA) 75/25/10 (weight ratio), 2 parts by weight of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.), 7 parts by weight of a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF corporation), and toluene.
(preparation of adhesive tape for semiconductor protection)
The intermediate layer-forming composition a was applied to a 75 μm-thick polyester film (trade name: Lumiror ES10#75, manufactured by Toray corporation) whose one surface was peeled off with silicone to form a coating layer. The coating layer is irradiated with ultraviolet rays in an oxygen-isolated atmosphere. At this time, a high-pressure mercury lamp (Toshiba Lighting) was used&Technology Corporation), an illumination intensity of 100mW/cm2(measured with TOPCON UVR-T1 having maximum sensitivity at about 350 nm) until the quantity of light reaches 3000mW/cm2Until now. In the above manner, a laminate A comprising the substrate and the intermediate layer a having a thickness of 300 μm was obtained.
On the other hand, the active energy ray-curable adhesive a was applied to a silicone-treated surface of a 38 μm thick polyester separator (trade name "Diafil MRF", manufactured by Mitsubishi resin corporation), and heated at 140 ℃ for 120 seconds to form an adhesive layer a having a thickness of 10 μm.
The pressure-sensitive adhesive layer a was transferred to the intermediate layer a side of the laminate A to obtain a semiconductor protection pressure-sensitive adhesive tape having a thickness of 385. mu.m, which comprises a substrate (75 μm)/an intermediate layer (300 μm) composed of a UV-polymerizable (meth) acrylic polymer)/a pressure-sensitive adhesive layer (10 μm) composed of an active energy ray-curable pressure-sensitive adhesive.
The results of subjecting the obtained adhesive tape for semiconductor protection to the above evaluation are shown in table 1.
[ example 2]
(preparation of composition b for intermediate layer formation)
An intermediate layer-forming composition b was obtained in the same manner as in example 1, except that dipentaerythritol hexaacrylate was not blended.
(preparation of adhesive tape for semiconductor protection)
A semiconductor protective adhesive tape was obtained in the same manner as in example 1, except that the intermediate layer-forming composition b was used instead of the intermediate layer-forming composition a.
The results of subjecting the obtained adhesive tape for semiconductor protection to the above evaluation are shown in table 1.
Comparative example 1
(preparation of composition c for intermediate layer formation)
An intermediate layer-forming composition C was prepared which contained 100 parts by weight of an acrylic polymer composed of Ethyl Acrylate (EA)/Butyl Acrylate (BA)/Acrylic Acid (AA) in a mass ratio of 50/50/5, 15 parts by weight of a UV oligomer (trade name "ARONIX M321", manufactured by tokyo chemical corporation), 1 part by weight of a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF corporation), 0.05 part by weight of a crosslinking agent (trade name "TETRAD C", manufactured by mitsubishi gas chemical corporation), and toluene.
(preparation of active energy ray-curable adhesive c)
An active energy ray-curable adhesive c was prepared which contained 100 parts by weight of an acrylic polymer composed of Ethyl Acrylate (EA)/Butyl Acrylate (BA)/2-hydroxyethyl acrylate (HEA) ═ 50/50/20 (weight ratio), 15 parts by weight of a UV oligomer (trade name "aroneix M321", manufactured by tokyo chemical corporation), 1 part by weight of a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF corporation), 0.07 part by weight of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co.
(preparation of adhesive tape)
The intermediate layer-forming composition c was applied to a 50 μm-thick PET film (trade name "Lumiror S105", manufactured by Toray corporation), and then heated at 120 ℃ for 120 seconds to form an intermediate layer c1 having a thickness of 60 μm.
Subsequently, the interlayer C1 was transferred onto the embossed surface of an EVA film (trade name: FANCLAIR NRW135, manufactured by GUNZE) having a thickness of 135 μm to obtain a 195 μm-thick laminate C1(EVA base material (135 μm)/interlayer C1(60 μm)).
Further, another intermediate layer C1 '(having a thickness of 60 μm) was formed on another PET film by the same method as described above, and this intermediate layer C1' was transferred onto the intermediate layer C1 of the laminate C1, thereby obtaining a laminate C2 having a thickness of 255 μm and composed of a base material (135 μm)/the intermediate layer C (120 μm).
On the other hand, the above active energy ray-curable adhesive c was applied to a 50 μm thick PET film (trade name "Lumiror S105", manufactured by Toray corporation) and heated at 120 ℃ for 120 seconds to form an adhesive layer c having a thickness of 30 μm.
The pressure-sensitive adhesive layer C was transferred to the intermediate layer C side of the laminate C1, to obtain a pressure-sensitive adhesive tape having a thickness of 285 μm and composed of a base material (135 μm)/intermediate layer C (120 μm)/pressure-sensitive adhesive layer (30 μm).
The results of subjecting the obtained adhesive tape to the above evaluation are shown in table 1.
Comparative example 2
(preparation of composition d for intermediate layer formation)
An intermediate layer-forming composition d was obtained in the same manner as in comparative example 1, except that the blending amount of the crosslinking agent (trade name "TETRAD C", manufactured by mitsubishi gas chemical corporation) was changed to 0.2 parts by weight.
(preparation of adhesive tape)
An adhesive tape was obtained in the same manner as in comparative example 1, except that the intermediate layer-forming composition d was used instead of the intermediate layer-forming composition c.
The results of subjecting the obtained adhesive tape to the above evaluation are shown in table 1.
Comparative example 3
(formation of intermediate layer)
An EVA resin pellet (trade name "EV 150", manufactured by DuPont-Mitsui polychemics co., ltd.) was dissolved in toluene at a concentration of 20 wt% to prepare a composition e for forming an intermediate layer.
Subsequently, the intermediate layer-forming composition E was applied to a 100 μm thick PET film (trade name "Lumiror ES 10", manufactured by Toray corporation) and dried at 120 ℃ for 2 minutes to obtain a laminate E1(PET substrate (100 μm)/intermediate layer E1(200 μm)).
Further, the intermediate layer-forming composition E was applied to the intermediate layer E1 of the laminate E1 and dried to obtain a laminate E2(PET substrate (100 μm)/intermediate layer E2(300 μm)).
Further, the intermediate layer-forming composition E was applied to the intermediate layer E2 of the laminate E2 and dried to obtain a laminate E3(PET substrate (100 μm)/intermediate layer E (400 μm)).
(formation of adhesive layer)
AN active energy ray-curable adhesive e was prepared which contained 90/2/5/3 parts by weight of AN acrylic polymer composed of Butylacrylate (BA)/2-hydroxyethyl acrylate (HEA)/Acrylonitrile (AN)/Acrylic Acid (AA), 1.75 parts by weight of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co corporation), 0.8 part by weight of a crosslinking agent (trade name "TETRAD C", manufactured by mitsubishi gas chemical corporation) and toluene.
The active energy ray-curable adhesive e was applied to a 50 μm-thick PET film (trade name "Lumiror S105", manufactured by Toray corporation), and then heated at 120 ℃ for 120 seconds to form an adhesive layer e having a thickness of 10 μm.
(preparation of adhesive tape)
The pressure-sensitive adhesive layer E was transferred onto the intermediate layer E of the laminate E3 to obtain a pressure-sensitive adhesive tape having a thickness of 510 μm and composed of a substrate (100 μm)/intermediate layer E (400 μm)/pressure-sensitive adhesive layer E (10 μm)).
The results of subjecting the obtained adhesive tape to the above evaluation are shown in table 1.
Comparative example 4
(preparation of composition f for intermediate layer formation)
An intermediate layer-forming composition f was prepared which contained 100 parts by weight of an acrylic polymer composed of Ethyl Acrylate (EA)/Butyl Acrylate (BA)/Acrylic Acid (AA) 50/50/5 (mass ratio), 3 parts by weight of a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF corporation), 1 part by weight of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) and toluene.
(preparation of active energy ray-curable adhesive f)
An active energy ray-curable adhesive f was prepared which contained 100 parts by weight of an acrylic polymer composed of 2-ethylhexyl acrylate (2-EHA)/acryloylmorpholine/hydroxyethyl acrylate (HEA) 75/25/10 (weight ratio), 5 parts by weight of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.), 3 parts by weight of a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF corporation), and toluene.
(preparation of adhesive tape)
The intermediate layer-forming composition F was applied to a 50 μm-thick PET film (trade name "Lumiror S105", manufactured by Toray corporation), and then heated at 120 ℃ for 120 seconds to obtain a laminate F1(PET substrate (50 μm)/intermediate layer F1(75 μm)).
Further, the intermediate layer-forming composition F was applied to the intermediate layer F1 of the laminate F1 and dried to obtain a laminate F2(PET substrate (50 μm)/intermediate layer F (150 μm)).
On the other hand, the above active energy ray-curable adhesive f was applied to a 50 μm thick PET film (trade name "Lumiror S105", manufactured by Toray corporation) and heated at 120 ℃ for 120 seconds to form an adhesive layer f having a thickness of 5 μm.
The pressure-sensitive adhesive layer F was transferred to the intermediate layer F side of the laminate F2, to obtain a pressure-sensitive adhesive tape having a thickness of 205 μm and comprising a substrate (50 μm)/intermediate layer F (150 μm)/pressure-sensitive adhesive layer F (5 μm).
The results of subjecting the obtained adhesive tape to the above evaluation are shown in table 1.
[ Table 1]
Figure BDA0001992724730000231
Industrial applicability
The adhesive tape for semiconductor protection of the present invention can be suitably used for semiconductor protection (e.g., protection of bump surfaces) in, for example, a vacuum process (e.g., a vacuum process in semiconductor manufacturing).

Claims (4)

1. An adhesive tape for protecting a semiconductor, comprising: a substrate, an adhesive layer disposed on at least one side of the substrate, and an intermediate layer disposed between the substrate and the adhesive layer,
the adhesive layer is composed of an active energy ray-curable adhesive containing a (meth) acrylic polymer,
the thickness of the adhesive layer is 1-50 μm,
the intermediate layer is composed of a UV-polymerized (meth) acrylic polymer,
the thickness of the intermediate layer is 50-1000 μm,
when the load value was measured by thermomechanical analysis (TMA) with a penetration depth of 20% of the pressure-sensitive adhesive layer and a probe having a diameter of 0.5mm pressed into the pressure-sensitive adhesive layer, the amount of change in load from 1 second to 300 seconds after the start of measurement was 1900 μ N/(mm)2Second) or less, the unit of the change amount of the load is [ mu ] N/(mm)2Seconds).
2. The adhesive tape for semiconductor protection according to claim 1, wherein the total amount of outgas of the 1 st organic solvent, the 2 nd organic solvent or the 3 rd organic solvent according to the organic solvent poisoning prevention regulation by the labor safety and health act is 25ppm or less when left in air at 150 ℃ for 1 hour.
3. The adhesive tape for semiconductor protection according to claim 1 or 2, wherein the base material is composed of a thermoplastic resin.
4. The adhesive tape for semiconductor protection according to claim 1 or 2, wherein the base material is composed of a polyester resin.
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JP7152233B2 (en) * 2018-09-25 2022-10-12 日東電工株式会社 Adhesive tape for semiconductor protection
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JP7386088B2 (en) * 2020-01-21 2023-11-24 日東電工株式会社 Adhesive composition and adhesive sheet using the adhesive composition
TWI808517B (en) * 2021-10-28 2023-07-11 山太士股份有限公司 Protection tape that suppresses deformation and grinding method
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