CN108977099B - Adhesive tape - Google Patents
Adhesive tape Download PDFInfo
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- CN108977099B CN108977099B CN201810806474.3A CN201810806474A CN108977099B CN 108977099 B CN108977099 B CN 108977099B CN 201810806474 A CN201810806474 A CN 201810806474A CN 108977099 B CN108977099 B CN 108977099B
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- adhesive layer
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- adhesive tape
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- acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dicing (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an adhesive tape, which can inhibit the increase of adhesive force even heated by laser cutting, is easy to take out a semiconductor element which is formed into a small piece, and is easy to process transfer to other adhesive tapes, and can inhibit the residual adhesive on an adherend. The adhesive tape of the present invention is an adhesive tape comprising a substrate and an adhesive layer provided on at least one surface of the substrate, wherein the indentation hardness of the surface of the adhesive layer at 100 ℃ by a nanoindenter is 20.0MPa or more.
Description
The present application is a divisional application of an application having an application date of 4/2014, an application number of 201410137377.1, and an invention name of "adhesive tape".
Technical Field
The present invention relates to an adhesive tape.
Background
The semiconductor chip (chip) is produced by cutting (dicing) a semiconductor wafer on which a circuit is formed. For example, a semiconductor wafer is diced (diced) into chips by dicing the semiconductor wafer on a dicing adhesive tape, and the chips are picked up from the dicing adhesive tape and used in a subsequent step (see, for example, patent document 1). In the cutting process, an adhesive tape is used for the purpose of fixing the semiconductor wafer.
In conventional cutting, a cutting edge such as a rotary blade is used. However, cutting using a cutting edge has a problem that chips are generated. Therefore, in recent years, laser dicing has been performed in which cutting is performed by laser.
However, when the conventional dicing adhesive tape is used for laser dicing, the following problems occur: the adhesive force of the pressure-sensitive adhesive tape for dicing after laser dicing is greatly increased, and subsequent processing (for example, an operation of taking out a semiconductor element formed into a small piece or transferring the semiconductor element to another pressure-sensitive adhesive tape) becomes difficult to perform, and a problem of adhesive residue occurring on an adherend taken out is caused.
This phenomenon is considered to be a result of the molecular chains of the pressure-sensitive adhesive in the dicing pressure-sensitive adhesive tape being cut by the laser beam, and the pressure-sensitive adhesive having a low molecular weight being increased in the adhesive strength. Thus, it is considered whether or not it is possible to cope with this by adding a light absorbing agent to the adhesive layer. However, such a countermeasure still has no effect on the elimination of the above phenomenon.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2005-019607
Disclosure of Invention
Problems to be solved by the invention
The inventors of the present invention have verified that the adhesive strength of the pressure-sensitive adhesive tape for dicing after laser dicing is significantly increased in the same manner as in the conventional case when the laser beam having a long wavelength is used, which cannot cut the molecular chain even in view of quantum chemistry. Therefore, the present inventors selected a silicon mirror wafer as a semiconductor wafer, adhered an adhesive tape to the silicon mirror wafer, and irradiated the semiconductor wafer with laser light used for laser dicing to observe the situation, in order to examine the situation that occurs when the semiconductor wafer is irradiated with laser light.
As a result, it was found that when a silicon mirror wafer was irradiated with laser light, the temperature rapidly increased in a minute region where the light was irradiated, and the wafer was heated to about 100 ℃ when it was cut, although the time was short. From the results, it is considered that the reason why the adhesive force of the pressure-sensitive adhesive tape for dicing is greatly increased after laser dicing is not chemical change of the pressure-sensitive adhesive due to laser light, but physical change, that is, softening of the pressure-sensitive adhesive due to heating increases the area of adhesion to an adherend (semiconductor wafer).
That is, an object of the present invention is to provide an adhesive tape which can suppress an increase in adhesive strength even when heated by laser dicing or the like, which can facilitate handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape, and which can suppress adhesive residue on an adherend.
Means for solving the problems
The present inventors have confirmed the degree of increase in adhesive strength of a pressure-sensitive adhesive tape for dicing after laser dicing using pressure-sensitive adhesives having various hardness at 100 ℃ and have found that if the indentation hardness of the surface of the pressure-sensitive adhesive at 100 ℃ obtained by a nanoindenter is not less than a predetermined level, the increase in adhesive strength which causes adverse effects is not caused in the treatment after laser dicing.
The adhesive tape of the present invention is an adhesive tape having an adhesive layer on at least one surface of a substrate,
the surface of the adhesive layer has an indentation hardness of 20.0MPa or more at 100 ℃ by a nanoindenter.
In a preferred embodiment, the surface of the pressure-sensitive adhesive layer has an indentation hardness of 0.5 to 10.0MPa at 23 ℃ as measured by a nanoindenter.
In a preferred embodiment, the adhesive layer has an adhesive strength at 23 ℃ for 30 minutes after the adhesive layer is attached and stored of 0.15N/20mm or more.
In a preferred embodiment, the adhesive layer contains an epoxy crosslinking agent.
In a preferred embodiment, the pressure-sensitive adhesive layer contains a (meth) acrylic polymer.
In a preferred embodiment, the substrate has a maximum elongation of 100% or more as measured according to JIS-K-7127 (1999).
In a preferred embodiment, the substrate is a plastic film.
In a preferred embodiment, the plastic film contains at least 1 selected from the group consisting of polyvinyl chloride, polyolefin, and ethylene-vinyl acetate copolymer.
In a preferred embodiment, the pressure-sensitive adhesive layer is provided on one surface of the substrate, and the non-pressure-sensitive adhesive layer is provided on the surface of the substrate opposite to the pressure-sensitive adhesive layer.
In a preferred embodiment, the non-adhesive layer is a mixed layer of polysiloxane and a (meth) acrylic polymer.
In a preferred embodiment, the mixing ratio of the polysiloxane and the (meth) acrylic polymer in the above non-adhesive layer is, in terms of weight ratio, polysiloxane: (meth) acrylic polymer ═ 1: 50-50: 1.
in a preferred embodiment, the non-adhesive layer has a phase separation structure.
In a preferred embodiment, the thickness of the non-adhesive layer is 0.01 to 10 μm.
In a preferred embodiment, a release liner is provided on the surface of the pressure-sensitive adhesive layer.
In a preferred embodiment, the adhesive tape of the present invention is used in semiconductor processing.
In a preferred embodiment, the adhesive tape of the invention is used for LED dicing applications.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an adhesive tape which can suppress an increase in adhesive strength even when heated by laser dicing or the like, which can facilitate handling such as removal of a semiconductor element which is formed into a small piece, transfer to another adhesive tape, and the like, and which can suppress adhesive residue on an adherend.
Drawings
Fig. 1 is a schematic cross-sectional view of a preferred embodiment of the adhesive tape of the present invention.
Fig. 2 is an SEM photograph showing a surface side state of a non-adhesive layer in the adhesive tape of the present invention.
Fig. 3 is an SEM photograph showing a state of a cross section of a non-adhesive layer in the adhesive tape of the present invention.
Fig. 4 is an SEM photograph explanatory-ally showing a state of a cross section of the non-adhesive layer in the adhesive tape of the present invention.
Description of the reference numerals
10 base material
20 adhesive layer
30 non-adhesive layer
100 adhesive tape
Detailed Description
The adhesive tape of the present invention includes an adhesive layer on at least one surface of a substrate. The pressure-sensitive adhesive tape of the present invention may have a pressure-sensitive adhesive layer on both surfaces of a substrate, or may have a pressure-sensitive adhesive layer on one surface of a substrate.
Fig. 1 is a schematic cross-sectional view of a preferred embodiment of the adhesive tape of the present invention. In fig. 1, the adhesive tape 100 of the present invention includes an adhesive layer 20 on one surface of a substrate 10. In fig. 1, a non-adhesive layer 30 is provided on the side of the substrate 10 opposite to the adhesive layer 20. A release liner (not shown) may be provided on the surface of the pressure-sensitive adhesive layer 20. In fig. 1, the adhesive tape 100 of the present invention is a laminate of a non-adhesive layer 30, a substrate 10, and an adhesive layer 20.
The thickness of the adhesive tape of the present invention is preferably 20 to 120 μm, more preferably 30 to 120 μm, and still more preferably 40 to 120 μm. By adjusting the thickness of the adhesive tape of the present invention within the above range, the effects of the present invention can become more easily exhibited. If the thickness of the pressure-sensitive adhesive tape of the present invention is too small, the handleability may be deteriorated, and particularly, the bonding operation may be difficult. If the thickness of the pressure-sensitive adhesive tape of the present invention is too large, the following property to deformation such as stretching may be deteriorated.
< substrate >
The thickness of the substrate is preferably 20 to 120. mu.m, more preferably 30 to 120. mu.m, and still more preferably 40 to 120. mu.m. By adjusting the thickness of the base material of the present invention within the above range, the effects of the present invention can become more readily exhibited. If the thickness of the base material is too small, handling properties may be deteriorated, and particularly, a bonding operation may be difficult when the pressure-sensitive adhesive tape is formed. If the thickness of the base material is too large, the following property to deformation such as stretching may be deteriorated.
The maximum elongation of the substrate measured according to JIS-K-7127 (1999) is preferably 100% or more, more preferably 200 to 1000%. By using a substrate exhibiting such a maximum elongation, the effects of the present invention can become more easily exhibited. By using a substrate exhibiting such a maximum elongation, the pressure-sensitive adhesive tape of the present invention can be provided with appropriate extensibility, and for example, the following ability to an adherend can be improved.
As long as the above characteristics are satisfied, any suitable material can be selected as the base material within a range that does not impair the effects of the present invention. As such a substrate, a plastic film is preferable.
The plastic film may comprise any suitable resin material. Examples of such a resin material include polyvinyl chloride, polyolefin, ethylene-vinyl acetate copolymer, polyester, polyimide, polyamide, and the like, more preferably polyvinyl chloride, polyolefin, and ethylene-vinyl acetate copolymer, and still more preferably polyvinyl chloride. Polyvinyl chloride is excellent in stress relaxation, and therefore can be suitably used for an adhesive tape used in semiconductor processing such as LED dicing.
The content ratio of the resin material in the plastic film may be set to any suitable content ratio according to the purpose and use. The content ratio is, for example, preferably 50 to 100% by weight, more preferably 60 to 100% by weight, and still more preferably 70 to 100% by weight.
The plastic film may also contain a plasticizer. The content ratio of the plasticizer in the plastic film is preferably 0.5 to 50% by weight, and more preferably 1.0 to 40% by weight, based on the resin material in the plastic film. By including the plasticizer in the plastic film at the above content ratio, the pressure-sensitive adhesive tape of the present invention has better followability to deformation such as stretching.
Examples of the plasticizer include: phthalate esters, trimellitate esters (e.g., those produced by DIC CORPORATION, W-700, and trioctyl trimellitate), adipate esters (e.g., those produced by J-PLUS Co., Ltd, D620, dioctyl adipate, and diisononyl adipate), phosphate esters (e.g., tricresyl phosphate), adipate esters, citrate esters (e.g., tributyl acetylcitrate), sebacate esters, azelate esters, maleate esters, benzoate esters, polyether polyesters, epoxy polyesters (e.g., epoxidized soybean oil, and epoxidized linseed oil), polyesters (e.g., low-molecular polyesters composed of carboxylic acids and diols), and the like. In the present invention, ester-based plasticizers are preferably used. The number of the plasticizer may be only 1, or may be 2 or more.
The plastic film may contain any other suitable component as long as the effect of the present invention is not impaired.
The base material can be produced by any suitable production method within a range in which the effects of the present invention can be exhibited. Examples of such a production method include: injection molding, extrusion molding, inflation molding, calender molding, blow molding, and the like.
< adhesive layer >
The thickness of the pressure-sensitive adhesive layer is preferably 1.0 to 30 μm, more preferably 1.0 to 20 μm, and still more preferably 3.0 to 15 μm. When the thickness of the pressure-sensitive adhesive layer is less than 1.0 μm, there is a fear that sufficient adhesive force cannot be developed. When the thickness of the pressure-sensitive adhesive layer is more than 30 μm, the pressure-sensitive adhesive layer may have too high adhesive force and the adherend may be broken when peeled off.
As the material of the adhesive layer, any suitable adhesive may be used within a range not impairing the effects of the present invention.
Examples of the material of the pressure-sensitive adhesive layer include: a (meth) acrylic polymer; natural rubber; special natural rubber grafted with a monomer such as methyl methacrylate; synthetic rubbers such as SBS, SBR, SEPS, SIS, SEBS, polybutene, polyisobutylene (polyisobutene), polyisobutylene (polyisobutylene), and butyl rubber; and the like. Among these, the (meth) acrylic polymer is preferable in that it has little residual adhesive to an adherend after peeling, high cohesive property, and excellent transparency. The material of the adhesive layer may be only 1 kind, or 2 or more kinds. For example, when a (meth) acrylic polymer is selected, the number of the polymers may be only 1, or may be 2 or more.
In the present specification, "(meth) acrylic acid" means acrylic acid and/or (meth) acrylic acid, and "(meth) acrylate" means acrylate and/or (meth) acrylate.
When the pressure-sensitive adhesive layer contains a (meth) acrylic polymer, the content ratio of the (meth) acrylic polymer in the pressure-sensitive adhesive layer can be appropriately set according to the purpose.
The (meth) acrylic polymer is a resin composed of a monomer component containing a (meth) acrylic monomer as a main monomer. The content ratio of the (meth) acrylic monomer in the monomer component constituting the (meth) acrylic polymer is preferably 50% by weight or more, more preferably 70% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, and particularly preferably 95% by weight to 100% by weight. The monomer component may contain only 1 kind of monomer, or may contain 2 or more kinds of monomers.
Preferable examples of the (meth) acrylic monomer include (meth) acrylate and (meth) acrylic acid.
Examples of the (meth) acrylate include: alkyl (meth) acrylates having an alkyl group (including cycloalkyl groups) having 1 to 30 carbon atoms, hydroxyl group-containing (meth) acrylates, and the like. The number of (meth) acrylic acid esters may be only 1, or may be 2 or more.
Examples of the alkyl (meth) acrylate ester having an alkyl group (including cycloalkyl group) having 1 to 30 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate ((meth) acrylic acid amyl), (meth) acrylic acid hexyl, (meth) acrylate cyclohexyl, (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, isopropyl (meth) acrylate, dodecyl (, Alkyl (meth) acrylates having an alkyl group (including cycloalkyl group) having 1 to 30 carbon atoms such as tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and lauryl (meth) acrylate. Among these (meth) acrylates, alkyl (meth) acrylates having an alkyl group (including cycloalkyl groups) having 2 to 20 carbon atoms are preferable, and alkyl (meth) acrylates having an alkyl group (including cycloalkyl groups) having 4 to 18 carbon atoms are more preferable.
Examples of the hydroxyl group-containing (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
In order to sufficiently exhibit the effect as a binder, the monomer component constituting the above (meth) acrylic polymer preferably contains at least 1 selected from a hydroxyl group-containing monomer and a carboxyl group-containing monomer. More preferably a carboxyl group-containing monomer.
In order to sufficiently exhibit the effect as a binder, the monomer component constituting the (meth) acrylic polymer may contain acrylonitrile.
Examples of the hydroxyl group-containing monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl alcohol, and the like. The hydroxyl group-containing monomer may be only 1 kind or 2 or more kinds.
Examples of the carboxyl group-containing monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. The carboxyl group-containing monomer may be only 1 kind or 2 or more kinds.
When the monomer component constituting the (meth) acrylic polymer contains a hydroxyl group-containing monomer, the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer is preferably 0.1 to 20% by weight, and more preferably 0.1 to 10% by weight. When the monomer component constituting the (meth) acrylic polymer contains a carboxyl group-containing monomer, the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer is preferably 0.1 to 20% by weight, and more preferably 0.1 to 10% by weight. By thus containing at least 1 monomer selected from the group consisting of the hydroxyl group-containing monomer and the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer, when a crosslinking agent is used, the crosslinking reaction with the crosslinking agent can be more effectively caused, and the effect as a binder can be sufficiently exhibited. Further, by adjusting the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer and the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer to fall within the above ranges, the adherend can be effectively prevented from being broken at the time of the peeling operation. When the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer and the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer are more than the above ranges, the adhesive force becomes too large, and blocking is likely to occur, and the adherend is likely to be broken during a peeling operation.
The adhesive layer preferably comprises a crosslinking agent. When the pressure-sensitive adhesive layer contains a crosslinking agent, the content of the crosslinking agent in the pressure-sensitive adhesive layer may be appropriately set according to the purpose, and is preferably 0.1 to 30 parts by weight, more preferably 1.0 to 27 parts by weight, even more preferably 3.0 to 25 parts by weight, and particularly preferably 5.0 to 23 parts by weight, based on 100 parts by weight of the main resin component (preferably, the (meth) acrylic polymer). By making the content ratio of the crosslinking agent in the adhesive layer within the above range, the following adhesive tape can be provided: the adhesive strength can be inhibited from increasing even when heated by laser dicing or the like, handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape is facilitated, and adhesive residue on an adherend can be inhibited. In addition, when the content ratio of the crosslinking agent in the pressure-sensitive adhesive layer is within the above range, an appropriate crosslinking reaction can be generated, and the adherend can be effectively prevented from being broken during the peeling operation.
Examples of the crosslinking agent include: epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, and the like. The number of the crosslinking agents may be only 1, or may be 2 or more.
The crosslinking agent preferably contains an epoxy-based crosslinking agent. By necessarily including an epoxy-based crosslinking agent as a crosslinking agent, the following adhesive tape can be provided: the adhesive strength can be inhibited from increasing even when heated by laser dicing or the like, handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape is facilitated, and adhesive residue on an adherend can be inhibited.
When the epoxy crosslinking agent is required to be contained as the crosslinking agent, the content of the epoxy crosslinking agent in the pressure-sensitive adhesive layer may be appropriately set according to the purpose, and is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 25 parts by weight, further preferably 0.5 to 20 parts by weight, and particularly preferably 0.7 to 15 parts by weight, based on 100 parts by weight of the main resin component (preferably, the (meth) acrylic polymer). When the content ratio of the epoxy crosslinking agent in the adhesive layer is within the above range, the following adhesive tape can be provided: the adhesive strength can be inhibited from increasing even when heated by laser dicing or the like, handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape is facilitated, and adhesive residue on an adherend can be inhibited.
As the epoxy-based crosslinking agent, any suitable epoxy-based crosslinking agent can be used. Examples of commercially available products include: "TETRAD C" manufactured by Mitsubishi gas chemical, and "ADEKA RESIN EPU SERIES" and "ADEKA RESIN EPR SERIES" manufactured by ADEKA CORPORATION, and "CELLOXIDE" manufactured by DAICEL CORPORATION. In particular, liquid epoxy resins such as these are preferred in terms of ease of mixing the adhesive in the production of the adhesive layer.
When an epoxy-based crosslinking agent is required as the crosslinking agent, other crosslinking agents may be used in combination. Examples of such a crosslinking agent include the isocyanate crosslinking agent, the melamine crosslinking agent, the peroxide crosslinking agent, the metal alkoxide crosslinking agent, the metal chelate crosslinking agent, the metal salt crosslinking agent, the carbodiimide crosslinking agent, the oxazoline crosslinking agent, the aziridine crosslinking agent, and the amine crosslinking agent. Among these crosslinking agents, from the viewpoint of sufficiently exhibiting the effects of the present invention, a melamine-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and a melamine-based crosslinking agent is more preferable.
The adhesive layer may also contain a plasticizer. When the pressure-sensitive adhesive layer contains a plasticizer, the content of the plasticizer in the pressure-sensitive adhesive layer may be appropriately set according to the purpose, and is 0.1 to 70 parts by weight relative to 100 parts by weight of the main resin component (preferably, the (meth) acrylic polymer). When the content ratio of the plasticizer in the pressure-sensitive adhesive layer is within the above range, the effects of the present invention can be more effectively exhibited. If the content of the plasticizer in the pressure-sensitive adhesive layer is greater than 70 parts by weight based on 100 parts by weight of the main resin component (preferably, the (meth) acrylic polymer), the pressure-sensitive adhesive layer becomes too soft, and adhesive residue and adherend contamination may easily occur.
Examples of the plasticizer include: phthalate esters, trimellitate esters (e.g., those produced by DIC CORPORATION, W-700, and trioctyl trimellitate), adipate esters (e.g., those produced by J-PLUS Co., Ltd, D620, dioctyl adipate, and diisononyl adipate), phosphate esters (e.g., tricresyl phosphate), adipate esters, citrate esters (e.g., tributyl acetylcitrate), sebacate esters, azelate esters, maleate esters, benzoate esters, polyether polyesters, epoxy polyesters (e.g., epoxidized soybean oil, and epoxidized linseed oil), polyesters (e.g., low-molecular polyesters composed of carboxylic acids and diols), and the like. In the present invention, ester-based plasticizers are preferably used. The number of the plasticizer may be only 1, or may be 2 or more.
The adhesive layer may contain any suitable catalyst in order to promote a crosslinking reaction or the like. When the pressure-sensitive adhesive layer contains a catalyst, the content of the catalyst in the pressure-sensitive adhesive layer may be appropriately set according to the purpose, and is 0.01 to 20 parts by weight relative to 100 parts by weight of the main resin component (preferably, the (meth) acrylic polymer). When the content ratio of the catalyst in the pressure-sensitive adhesive layer is within the above range, the effects of the present invention can be more effectively exhibited.
Examples of such a catalyst include: organic metal compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin maleate; basic compounds such as butylamine, dibutylamine, hexylamine, tert-butylamine, ethylenediamine, isophoronediamine, imidazole, lithium hydroxide, potassium hydroxide, and sodium methoxide; acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid esters of β -hydroxyethyl acrylate, monoalkyl phosphorous acid, and dialkyl phosphorous acid; and the like. The number of the catalyst may be only 1, or may be 2 or more.
The surface of the pressure-sensitive adhesive layer has an indentation hardness at 100 ℃ of 20.0MPa or more, preferably 20.0MPa to 1000MPa, and more preferably 20.0MPa to 100MPa, as measured by a nanoindenter. By making the indentation hardness at 100 ℃ of the surface of the adhesive layer by the nanoindenter within the above range, the following adhesive tape can be provided: the adhesive strength can be inhibited from increasing even when heated by laser dicing or the like, handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape is facilitated, and adhesive residue on an adherend can be inhibited. If the indentation hardness of the surface of the pressure-sensitive adhesive layer at 100 ℃ obtained by the nanoindenter is too small as outside the above range, for example, the treatment after laser dicing may be deteriorated. If the indentation hardness of the surface of the pressure-sensitive adhesive layer at 100 ℃ obtained by the nanoindenter is too large outside the above range, there is a concern that: for example, floating between the pressure-sensitive adhesive tape and the adherend, positional displacement, detachment of the pressure-sensitive adhesive tape from the adherend, and the like are caused by external forces such as vibration generated during conveyance and the like of a workpiece (a sample actually subjected to laser dicing, to which a ring frame and the like are bonded in addition to the adherend on the dicing tape) in the laser dicing step. The details of the measurement of indentation hardness by the nanoindenter will be described later.
The indentation hardness of the surface of the pressure-sensitive adhesive layer at 23 ℃ by a nanoindenter is preferably 0.5MPa to 10.0MPa, more preferably 0.5MPa to 8.0MPa, still more preferably 0.5MPa to 7.0MPa, and particularly preferably 1.0MPa to 6.0 MPa. By setting the indentation hardness at 100 ℃ obtained by nanoindenter on the surface of the pressure-sensitive adhesive layer within the above range and the indentation hardness at 23 ℃ obtained by nanoindenter on the surface of the pressure-sensitive adhesive layer within the above range, the pressure-sensitive adhesive tape of the present invention can be reliably attached to an adherend in a room temperature region because the pressure-sensitive adhesive force in the room temperature region around 23 ℃ can be appropriately ensured, and the following pressure-sensitive adhesive tape can be provided: the adhesive strength can be inhibited from increasing even when heated by laser dicing or the like, handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape is facilitated, and adhesive residue on an adherend can be inhibited. The details of the measurement of indentation hardness by the nanoindenter will be described later.
The adhesive strength of the pressure-sensitive adhesive layer after the application and storage at 23 ℃ for 30 minutes is preferably 0.15N/20mm or more, more preferably 0.15N/20mm to 2.00N/20mm, still more preferably 0.15N/20mm to 1.00N/20mm, and particularly preferably 0.20N/20mm to 1.00N/20 mm. The pressure-sensitive adhesive tape of the present invention can be reliably attached to an adherend in a room temperature region by setting the adhesive strength of the pressure-sensitive adhesive layer in the above range after 23 ℃ x 30 minutes of storage. The details of the measurement of the adhesion strength for storage at the time of attachment will be described later.
The adhesive strength of the pressure-sensitive adhesive layer after the application and storage is preferably 2.00N/20mm or less, more preferably 0.15N/20mm to 1.50N/20mm, further preferably 0.15N/20mm to 1.00N/20mm, particularly preferably 0.15N/20mm to 0.50N/20mm, after heating at 100 ℃ for 30 minutes and further 23 ℃ X30 minutes. By making the adhesive strength of the adhesive layer in the above range after heating at 100 ℃ for 30 minutes and further after heating at 23 ℃ for 30 minutes, the following adhesive tape can be provided: the adhesive strength can be inhibited from increasing even when heated by laser dicing or the like, handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape is facilitated, and adhesive residue on an adherend can be inhibited. The details of the measurement of the adhesion strength for storage at the time of attachment will be described later.
The adhesive layer may contain any suitable additive within a range not to impair the effects of the present invention. Examples of such additives include: ultraviolet ray absorbent, filler, anti-aging agent, tackifier, pigment, dye, silane coupling agent, etc.
The pressure-sensitive adhesive tape of the present invention may be provided with a release liner on the surface of the pressure-sensitive adhesive layer.
Any suitable separator may be used as the release liner. Examples of such a release liner include: a substrate having a release layer such as a plastic film or paper surface-treated with a release agent such as a polysiloxane, a long-chain alkyl, a fluorine, or a molybdenum sulfide; low-adhesion base materials made of fluorine-based polymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, chlorofluoroethylene-vinylidene fluoride copolymers, and the like; a low-adhesion substrate made of a nonpolar polymer such as an olefin resin (for example, polyethylene, polypropylene, etc.); and the like.
As a method for providing an adhesive layer on a substrate, any appropriate means may be employed within a range not impairing the effects of the present invention. As such means, a method of providing an adhesive layer by applying a coating liquid for forming an adhesive layer onto a substrate is preferable.
As the coating method, any suitable coating method may be employed within a range not impairing the effects of the present invention. Examples of such coating methods include: a reverse system, a direct system, various systems combined with a metering roll, and the like.
< non-adhesive layer >
The pressure-sensitive adhesive tape of the present invention preferably has a pressure-sensitive adhesive layer on one surface of a substrate, and a non-pressure-sensitive adhesive layer on the surface of the substrate opposite to the pressure-sensitive adhesive layer.
The composition of the non-adhesive layer is not particularly limited, and examples thereof include: a polysiloxane layer, a (meth) acrylic polymer layer, a mixed layer of a polysiloxane layer and a (meth) acrylic polymer layer, a polysiloxane layer to which a (meth) acrylic polymer is graft-polymerized, and the like. Among these, a mixed layer of polysiloxane and (meth) acrylic polymer is preferable. By using a mixed layer of polysiloxane and a (meth) acrylic polymer as the non-adhesive layer, the non-adhesive layer can be suitably used for a substrate (particularly a plastic film), and the pressure-sensitive adhesive tape of the present invention can have good conformability to deformation such as stretching.
The surface of the non-adhesive layer preferably has a textured structure. By providing the uneven structure on the surface of the non-adhesive layer, excessive adhesion to the base can be effectively suppressed. Specifically, the uneven structure has an arithmetic average surface roughness Ra of the non-adhesive layer of preferably 0.1 μm or more, more preferably 0.1 to 3.0. mu.m, still more preferably 0.2 to 2.0. mu.m, particularly preferably 0.3 to 2.0. mu.m, and most preferably 0.5 to 2.0. mu.m. By setting the arithmetic average surface roughness Ra of the non-adhesive layer within the above range, it is possible to suppress the occurrence of excessive adhesion when performing suction fixation by negative pressure. Among them, the method for measuring the arithmetic average surface roughness Ra of the non-adhesive layer will be described later.
The glass transition temperature Tg of the non-adhesive layer by differential scanning calorimetry (DSC measurement) is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, further preferably 50 ℃ or higher, and particularly preferably 55 ℃ or higher. The upper limit of the glass transition temperature Tg of the non-adhesive layer measured by differential scanning heat is not particularly limited, but from the viewpoint of handling properties and the like, it is preferably 200 ℃ or less, more preferably 170 ℃ or less, still more preferably 150 ℃ or less, particularly preferably 130 ℃ or less, and most preferably 100 ℃ or less. When the glass transition temperature Tg of the non-adhesive layer measured by differential scanning calorimetry is within the above range, the hardness of the surface of the non-adhesive layer is moderately increased even at high temperatures, and therefore, the heat resistance is increased, and when the pressure-sensitive adhesive tape of the present invention is suction-fixed to a fixing base by negative pressure and cut or the like, the occurrence of excessive adhesion due to heat generation or the like of the base can be effectively suppressed. The method for measuring the glass transition temperature Tg of the non-adhesive layer by differential scanning calorimetry (DSC measurement) will be described later.
When the non-adhesive layer contains a (meth) acrylic polymer, the SP value of the (meth) acrylic polymer in the non-adhesive layer is preferably 9.0 (cal/cm)3)0.5~12.0(cal/cm3)0.5More preferably 9.5 (cal/cm)3)0.5~11.5(cal/cm3)0.5More preferably 9.5 (cal/cm)3)0.5~11.0(cal/cm3)0.5. The SP value is a solubility parameter calculated according to the Small formula. The SP value can be calculated by a method described in a known literature (for example, Journal of Applied Chemistry, 3, 71, 1953, etc.).
The non-adhesive layer preferably has a phase separation structure. By providing the non-adhesive layer with a phase separation structure, a minute uneven structure can be effectively formed on the surface of the non-adhesive layer. This can be presumably: for example, in the case where the non-adhesive layer is a mixed layer of a polysiloxane and a (meth) acrylic polymer, unevenness is generated due to a difference in substance mobility of the polysiloxane and the (meth) acrylic polymer when a phase-separated structure is generated. Due to the formation of the uneven structure, the pressure-sensitive adhesive tape of the present invention can effectively suppress blocking in a rolled form while suppressing excessive adhesion at the time of suction fixation by negative pressure, and can suppress breakage or breakage at the time of unwinding from the rolled form.
The non-adhesive layer preferably contains: a polysiloxane-rich phase comprising more polysiloxane than (meth) acrylic polymer, and a (meth) acrylic polymer-rich phase comprising more (meth) acrylic polymer than polysiloxane. More specifically, the non-adhesive layer preferably contains the silicone-rich phase and the (meth) acrylic polymer-rich phase in a phase-separated structure independent of each other, and more preferably the silicone-rich phase is present on the air interface side (the side opposite to the substrate (particularly, plastic film)), and the (meth) acrylic polymer-rich phase is present on the substrate (particularly, plastic film). By having such a phase separation structure, blocking is effectively suppressed due to the polysiloxane-rich phase present on the air interface side, and the non-adhesive layer is well adapted to the substrate (particularly, plastic film) due to the (meth) acrylic polymer-rich phase present on the substrate (particularly, plastic film) side, and deformation following properties are good. Such a phase separation structure can be formed by adjusting the mixing ratio of the polysiloxane and the (meth) acrylic polymer in the non-adhesive layer as described below.
The case where the non-adhesive layer has a phase-separated structure, the case where the silicone-rich phase containing more silicone than (meth) acrylic polymer and the (meth) acrylic polymer-rich phase containing more (meth) acrylic polymer than silicone as described above are contained can be observed by any suitable method. Examples of such observation methods include: and a method of observing the morphology of the cross section of the non-adhesive layer using an electron microscope such as a Transmission Electron Microscope (TEM), a Scanning Electron Microscope (SEM), or a field emission scanning electron microscope (FE-SEM). The 2-layer separation structure can be recognized by the depth of the morphological observation image. Further, the following methods may be mentioned: the composition was observed by observing the change in the content of silicon, carbon, and the like contained in the composition by infrared absorption spectroscopy by total reflection, while changing the probe light depth from the non-adhesive layer air interface side to the inside. Further, there can be mentioned a method of observation by an X-ray microanalyzer or X-ray photoelectron spectroscopy. In addition, these methods can be combined as appropriate to perform observation.
In the case where the non-adhesive layer has a phase separation structure of a polysiloxane-rich phase present on the air interface side (the side opposite to the substrate (particularly, the plastic film)) and a (meth) acrylic polymer-rich phase present on the substrate (particularly, the plastic film), when the non-adhesive layer is adsorbed and fixed to the fixing base by negative pressure and cut, if the fixing base generates heat, the surface structure of the phase separation structure is broken by the heat load due to the heat generation, and particularly, the surface structure of the phase separation structure is broken in a convex portion which is in contact with the fixing base that generates heat, and the (meth) acrylic polymer-rich phase may be exposed on the air interface side in the convex portion. However, since the glass transition temperature Tg measured by differential scanning calorimetry of the non-adhesive layer of the pressure-sensitive adhesive tape of the present invention is preferably in the above range, the hardness of the convex portion subjected to a thermal load is moderately increased, and the heat resistance is increased. Therefore, when the pressure-sensitive adhesive tape of the present invention is sucked and fixed to a fixing base by negative pressure and cut, excessive adhesion due to heat generation of the base can be effectively suppressed.
When the non-adhesive layer is a mixed layer of polysiloxane and a (meth) acrylic polymer, the mixing ratio of polysiloxane and (meth) acrylic polymer in the non-adhesive layer is preferably polysiloxane: (meth) acrylic polymer ═ 1: 50-50: 1, more preferably a polysiloxane: (meth) acrylic polymer ═ 1: 30-30: 1, more preferably polysiloxane: (meth) acrylic polymer ═ 1: 10-10: 1, particularly preferably a polysiloxane: (meth) acrylic polymer ═ 1: 5-5: 1, most preferably a polysiloxane: (meth) acrylic polymer ═ 1: 3-5: 1. if the content of the polysiloxane in the non-adhesive layer is too large, the chemical affinity with the back surface of the substrate (particularly, plastic film) is lowered, and there is a fear that it is difficult to adapt to the back surface of the substrate (particularly, plastic film). If the content ratio of the polysiloxane in the non-adhesive layer is too large, the non-adhesive layer may be broken to cause contamination because the non-adhesive layer may be deteriorated in followability to deformation such as stretching when the adhesive tape is manufactured. If the content ratio of the (meth) acrylic polymer in the non-adhesive layer is too large, the non-adhesive layer may function as an acrylic pressure-sensitive adhesive, and blocking may easily occur.
As the polysiloxane, any suitable polysiloxane may be used. Examples of such polysiloxanes include: an addition polysiloxane obtained by curing an alkenyl group-containing polydialkylsiloxane and a polydialkylhydrogenpolysiloxane by an addition reaction using a platinum compound as a catalyst to form a release film; and a condensation-type polysiloxane obtained by reacting a methylol-containing polydialkylsiloxane and a polydialkylhydrogenpolysiloxane using a tin-based catalyst. Examples of addition polysiloxanes include, for example: Shin-Etsu Silicone Co., Ltd, "KS-776A", "KS-839L" and the like. Examples of the condensation-type polysiloxane include: "KS 723A/B" manufactured by Shin-Etsu Silicone Co., Ltd. In addition, in the production of polysiloxane, other crosslinking agents, crosslinking accelerators, and the like may be suitably used in addition to the platinum-based catalyst and the tin-based catalyst. Further, properties of the polysiloxane can be classified into: a type of dissolving in an organic solvent such as toluene, an emulsion type of emulsifying these, a solvent-free type containing only silicone, and the like. In addition, in addition to addition type polysiloxane, condensation type polysiloxane, can also use polysiloxane/acrylic acid graft polymer, polysiloxane/acrylic acid block polymer. Examples of the polysiloxane/acrylic acid graft polymer include: SYMAC GS-30, GS101, US-270, US-350, US-380 (manufactured by Toyo Kabushiki Kaisha, Ltd.), and the like. Examples of the polysiloxane/acrylic block polymer include: MODIPER FS700, FS710, FS720, FS730, and FS770 (manufactured by japan oil co., ltd.).
As the (meth) acrylic polymer, any suitable (meth) acrylic polymer can be used. In the present invention, "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid".
The (meth) acrylic polymer is a polymer composed of a monomer component containing a (meth) acrylic monomer as a main monomer. The content ratio of the (meth) acrylic monomer in the monomer component constituting the (meth) acrylic polymer is preferably 50% by weight or more, more preferably 70% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, and particularly preferably 95% by weight to 100% by weight. The monomer component may contain only 1 kind of monomer, or may contain 2 or more kinds of monomers.
Preferable examples of the (meth) acrylic monomer include (meth) acrylate and (meth) acrylic acid.
Examples of the (meth) acrylate include: alkyl (meth) acrylates having an alkyl group (including cycloalkyl groups) having 1 to 30 carbon atoms, hydroxyl group-containing (meth) acrylates, and the like. The number of (meth) acrylic acid esters may be only 1, or may be 2 or more.
Examples of the alkyl (meth) acrylate ester having an alkyl group (including cycloalkyl group) having 1 to 30 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate ((meth) acrylic acid amyl), (meth) acrylic acid hexyl, (meth) acrylate cyclohexyl, (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, isopropyl (meth) acrylate, dodecyl (, Alkyl (meth) acrylates having an alkyl group (including cycloalkyl group) having 1 to 30 carbon atoms such as tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and lauryl (meth) acrylate. Among these (meth) acrylates, alkyl (meth) acrylates having an alkyl group (including cycloalkyl groups) having 2 to 20 carbon atoms are preferable, and alkyl (meth) acrylates having an alkyl group (including cycloalkyl groups) having 4 to 18 carbon atoms are more preferable.
Examples of the hydroxyl group-containing (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
In order to sufficiently exhibit the effect of the present invention, the monomer component constituting the (meth) acrylic polymer may contain at least 1 selected from a hydroxyl group-containing monomer and a carboxyl group-containing monomer.
Examples of the hydroxyl group-containing monomer include: allyl alcohol, and the like. The hydroxyl group-containing monomer may be only 1 kind or 2 or more kinds.
Examples of the carboxyl group-containing monomer include: carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. The carboxyl group-containing monomer may be only 1 kind or 2 or more kinds.
When the non-adhesive layer contains a (meth) acrylic polymer, the content of the hydroxyl group-containing (meth) acrylate in the monomer components constituting the (meth) acrylic polymer in the non-adhesive layer is preferably 2 to 30% by weight, more preferably 3 to 25% by weight, and particularly preferably 5 to 20% by weight, based on the total amount of the monomer components other than the hydroxyl group-containing (meth) acrylate. When the non-adhesive layer contains a (meth) acrylic polymer, if the content ratio of the hydroxyl group-containing (meth) acrylate in the monomer components constituting the (meth) acrylic polymer in the non-adhesive layer is within the above range relative to the total amount of the monomer components other than the hydroxyl group-containing (meth) acrylate, a fine uneven structure is more effectively formed on the surface of the non-adhesive layer, and by forming the uneven structure, the adhesive tape of the present invention can further suppress the occurrence of excessive adhesion when suction fixation is performed by negative pressure, can more effectively suppress blocking in the form of a roll, and can further suppress breakage or breakage when unwinding from the form of a roll.
When the non-adhesive layer contains a (meth) acrylic polymer, the (meth) acrylic polymer in the non-adhesive layer preferably contains (meth) acrylic acid and/or (meth) acrylate in a monomer component other than the hydroxyl group-containing (meth) acrylate among the monomer components constituting the (meth) acrylic polymer. At this time, the content ratio of (meth) acrylic acid to (meth) acrylic acid ester is in terms of weight ratio, (meth) acrylic acid: the (meth) acrylate is preferably 0: 100-20: 80, more preferably 0: 100-10: 90, more preferably 0: 100-5: 95.
when the content ratio of (meth) acrylic acid and (meth) acrylic ester is within the above range, a fine uneven structure is more effectively formed on the surface of the non-adhesive layer, and by forming this uneven structure, in the adhesive tape of the present invention, it is possible to further suppress the occurrence of excessive adhesion when suction-fixing is performed by negative pressure, and it is possible to further effectively suppress blocking in the form of a roll, and it is possible to further suppress breakage or breakage when unwinding from the form of a roll.
The (meth) acrylic polymer can be produced by any suitable polymerization method.
The non-adhesive layer may contain any appropriate additive within a range not to impair the effects of the present invention. Examples of such additives include: catalyst, ultraviolet absorbent, filler, anti-aging agent, tackifier, pigment, dye, silane coupling agent, etc.
The thickness of the non-adhesive layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm, and still more preferably 0.1 to 2 μm. If the thickness of the non-adhesive layer is less than 0.01 μm, blocking is likely to occur. If the thickness of the non-adhesive layer is more than 10 μm, the following property to deformation such as stretching may be deteriorated. If the thickness of the non-adhesive layer is less than 0.01 μm, the effects of the present invention may not be exhibited, and the production may be difficult.
Examples of a method for forming a non-adhesive layer on one surface of a substrate (particularly, a plastic film) include: a method for forming a non-adhesive layer by coating a material of the non-adhesive layer on one surface of a substrate (particularly a plastic film) and drying the coating. Examples of the coating method include: a method using a bar coater, a gravure coater, a spin coater, a roll coater, a blade coater, an applicator, or the like.
< use >
The adhesive tape of the present invention can be used for any suitable purpose. As described above, the pressure-sensitive adhesive tape of the present invention can suppress an increase in the adhesive strength even when heated by laser dicing or the like, can facilitate handling such as removal of a semiconductor element formed into a small piece and transfer to another pressure-sensitive adhesive tape, and can suppress adhesive residue on an adherend. Further, it is preferable that the non-adhesive layer is capable of effectively suppressing occurrence of excessive adhesion due to heat generation or the like of the base when the non-adhesive layer is fixed to the fixing base by negative pressure suction and cut, and also capable of effectively suppressing blocking in the rolled form, and is free from breakage or breakage when the non-adhesive layer is unwound from the rolled form, and that the non-adhesive layer has good adaptability to the plastic film and good conformability to deformation such as stretching. Therefore, the method can be suitably used for semiconductor processing in which a semiconductor wafer made of a brittle material and capable of having a fine and precise circuit pattern is used as an adherend. When the pressure-sensitive adhesive tape of the present invention is used for semiconductor processing, it is possible to suppress an increase in the adhesive strength even when heated by laser dicing or the like, to facilitate handling such as removal of a semiconductor element formed into a small piece and transfer to another pressure-sensitive adhesive tape, and to suppress adhesive residue on an adherend. Further, it is preferable that, when the dicing or the like is performed by fixing the base for fixing by suction under negative pressure, occurrence of excessive adhesion due to heat generation or the like of the base can be effectively suppressed, and therefore, the semiconductor manufacturing process including the dicing can be smoothly performed. Further, when the adhesive tape of the present invention is used for semiconductor processing, it is possible to suppress an increase in adhesive strength even when heated by laser dicing or the like, to facilitate handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape, to suppress adhesive residue on an adherend, and to satisfactorily prevent film deformation and accumulation of stress strain which have conventionally occurred due to blocking, and therefore, it is possible to accurately perform bonding following a fine and precise circuit pattern of a semiconductor wafer, and further, to prevent natural release of stress strain after bonding to a semiconductor wafer, and therefore, it is possible to effectively prevent breakage of a semiconductor wafer. In particular, since the wafer for LED is made of a very brittle material such as gallium nitride, gallium arsenide, or silicon carbide, the adhesive tape of the present invention is particularly suitable for dicing (LED dicing) of the wafer for LED, or the like.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts means parts by weight and% means% by weight. The amount of the reagent supplied as a solution is expressed by the amount of solid components remaining by volatilizing the solution (solid component equivalent).
< indentation test >
The surface of the pressure-sensitive adhesive layer was subjected to an indentation test under the following conditions, and the indentation hardness and indentation elastic modulus were determined from the results.
(measurement apparatus and measurement conditions)
The device comprises the following steps: tribo Inder manufactured by Hysitron Inc
Using a pressure head: berkovich (triangular pyramid type)
The determination method comprises the following steps: single indentation determination
Measuring temperature: 25 ℃ and 100 DEG C
And (3) indentation depth setting: about 300nm
Pressing-in speed: about 10nm/sec
And (3) measuring atmosphere: in the air
Sample size: about 1cm by about 1cm
(measurement method)
After the above-described apparatus was kept at room temperature (23 ℃) for 1 hour, or after the temperature was raised from room temperature to 100 ℃ and kept for 1 hour, a Berkovich diamond indenter was vertically pushed from the surface of the adhesive layer to a depth of 300 nm. The indentation hardness of the surface was determined from the displacement and load obtained when the indenter was pressed in and the theoretically calculated indentation area using the analytical software "Triboscan ver.9.2.12.0". Further, using the software described above, the elastic modulus of the surface was determined from the displacement and load obtained after removing the indenter and the indentation area calculated theoretically.
< adhesive residue Property >
With reference to JIS-Z-0237 (2000), a PVC film (arithmetic average surface roughness Ra of 0.5 μm) and an adhesive tape as an adherend were held at 23 ℃ for 1 hour or more, and then the adhesive layer surface of the adhesive tape was pressure-bonded to the PVC film at a line pressure of 8kg/m and a pressure-bonding speed of 0.3 m/min, heated at 100 ℃ for 30 minutes, left at 23 ℃ for 30 minutes, and the adhesive tape was peeled off at a stretching speed of 0.01 m/min and 180 ° to visually confirm adhesive residue on the adherend surface. The case where no residual glue was observed was evaluated as "o", and the case where residual glue was observed was evaluated as "x".
< adhesion strength for storage of attachment >
Referring to JIS-Z-0237 (2000), an SUS430BA plate and an adhesive tape as an adherend were held at 23 ℃ for 1 hour or more, and then the adhesive layer surface of the adhesive tape was pressure-bonded to SUS430BA at a line pressure of 8kg/m and a pressure-bonding speed of 0.3 m/min, and peeled off at a tensile rate of 0.3 m/min and 180 degrees, and the peel force after 23 ℃ C. × 30 minutes and the peel force after heating at 100 ℃ for 30 minutes and further leaving to stand at 23 ℃ C. × 30 minutes were measured.
< transferability test >
A pressure-sensitive adhesive tape for back grinding (trade name; ELEP HOLDER, manufactured by NITTON ELECTRIC CORPORATION) was attached to the mirror surface of a 4-inch Si mirror wafer, and the wafer was back-ground to a thickness of 0.1 mm. After the adhesive tape for back grinding was peeled off, the adhesive tape of the example or the comparative example as a dicing tape was attached to the mirror surface side, and the load was applied by reciprocating the hand roller 1 time, whereby the adhesion between the tape and the wafer was sufficiently performed.
The above-mentioned sample was fixed to a cutting ring, allowed to stand at 23 ℃ and 50% humidity for 30 minutes, and then cut under the following conditions. The cut sample was stored at 100 ℃ for 30 minutes, and further allowed to stand at 23 ℃ and 50% humidity for 30 minutes.
After the above operation, an adhesive tape of the same type as the tape used as the dicing tape was attached to the ground surface of the wafer, and the tape and the wafer were sufficiently bonded by applying a load 1 time in a reciprocating manner with a hand roller.
The sample was left to stand at a temperature of 23 ℃ and a humidity of 50% for 30 minutes, and then the adhesive tape attached to the mirror surface side was peeled from the wafer at a stretching speed of 10m/min in an environment of 23 ℃ and a humidity of 50%.
The ratio of the number of chips of the pressure-sensitive adhesive tape transferred to the surface of the wafer subjected to grinding by the peeling operation was evaluated as ×, 95.0% or more and less than 99.0% as ≈ and 99.0% or more as ∈.
(conditions for cleavage)
Cutting equipment: DFD-6450 (manufactured by DISCO CORPORATION)
Chip size: 0.5mm × 0.5mm
The blade types are as follows: NBC-ZH205O-SE-27HECC (manufactured by DISCO CORPORATION)
The rotating speed of the blade is as follows: 30000rpm
Cutting speed: 80mm/sec
The height of the blade is as follows: 45 μm
< maximum elongation >
The maximum elongation was measured in accordance with JIS-K-7127 (1999) using an INSTRON tensile tester (AUTOGRAPH, manufactured by Shimadzu corporation). Specifically, a sample having a width of 20mm × a length of 100mm was set at a distance of 50mm between chucks, and then the sample was stretched at a stretching speed of 0.3 m/min, and the value at the time of fracture was measured.
< elastic modulus >
The measurement was carried out in accordance with JIS-K-7127 (1999), using an INSTRON type tensile tester (AUTOGRAPH, manufactured by Shimadzu corporation). Specifically, a sample having a width of 20mm × a length of 100mm was set at an inter-chuck distance of 50mm, and then stretched at a stretching speed of 0.3 m/min to determine an initial elastic modulus. The initial modulus of elasticity was set to the following value: a tangent line in a region of 0-2% elongation at break is drawn, and the tangent line is extended to a value of 100% elongation by a straight line, and the value is corrected by conversion of the cross-sectional area of the sample.
< observation of non-adhesive layer >
(Observation by SEM)
The non-adhesive layer was processed so that the cross section thereof could be observed, and then the morphology was observed by a transmission electron microscope (SEM).
(Observation by Infrared Spectroscopy (ATR-IR) based on Total reflection method)
The total reflection measurement method was selected using an infrared spectrometer (manufactured by Perkinermer, Spectrum One), and ATR-IR measurement of the non-adhesive layer was performed using 2 types of prisms for total reflection measurement (ZnSe45 °, Ge45 °) in order to change the analysis depth of the probe light.
< arithmetic average surface roughness Ra >
The measurement was performed in a 3D mode using a confocal laser microscope "LEXT 3000" manufactured by OLYMPUS, with a 20-fold objective lens. The determination of the observation range of the 3D mode is performed as follows: the positions where the CF image (confocal image) becomes completely black when the lens is moved up and down are set as Top and Bottom of the observation range, respectively.
The image acquisition method in the 3D mode performs image acquisition at a pitch of 0.2 μm by a Step method.
Measurement of arithmetic average surface roughness Ra was measured at an arbitrary position by roughness analysis in an analysis mode. The value is determined by averaging n to 5.
[ production example 1 ]: manufacture of substrates
A flexible polyvinyl chloride film containing 27 parts by weight of DOP plasticizer (bis (2-ethylhexyl) phthalate, J-PLUS co., Ltd) per 100 parts by weight of polyvinyl chloride having a polymerization degree P of 1050 was produced by a calendering method. The thickness of the obtained flexible polyvinyl chloride film was 70 μm, the elastic Modulus (MD) measured according to JIS-K-7127 (1999) was 250MPa, and the maximum elongation (MD) measured according to JIS-K-7127 (1999) was 400%. The arithmetic average surface roughness Ra immediately after production was 0.1. mu.m.
[ example 1]
(non-adhesive layer)
60 parts by weight of a silicone resin (KS-723A, manufactured by shin-Etsu chemical industries), 40 parts by weight of a silicone resin (KS-723B, manufactured by shin-Etsu chemical industries), 50 parts by weight of an acrylic copolymer (methyl methacrylate (MMA)/Butyl Acrylate (BA)/hydroxyethyl acrylate (HEA) ═ 70/30/10), and 10 parts by weight of a tin-based catalyst (Cat-PS3, manufactured by shin-Etsu chemical industries) were mixed in a solution state to obtain a mixed solution (1). The mixing ratio of the polysiloxane and the (meth) acrylic polymer in the mixed solution (1) is polysiloxane: (meth) acrylic polymer ═ 2: 1.
the above-mentioned mixed solution (1) was applied to one side of the flexible polyvinyl chloride film obtained in production example 1, and dried to form a non-adhesive layer (1) having a thickness of 1.0 μm and an arithmetic average surface roughness Ra of 0.5 μm.
When the non-adhesive layer (1) was observed by SEM, as shown in fig. 2, 3, and 4, depending on the depth of the morphological observation image, it was confirmed that the composition was different between the air interface side and the plastic film side, a phase separation structure was formed in which a polysiloxane-rich phase containing more polysiloxane than (meth) acrylic polymer and a (meth) acrylic polymer-rich phase containing more (meth) acrylic polymer than polysiloxane were contained, and the polysiloxane-rich phase and the (meth) acrylic polymer-rich phase were independent of each other, and it was observed that the polysiloxane-rich phase was present on the air interface side (the side opposite to the plastic film) and the (meth) acrylic polymer-rich phase was present on the plastic film side.
Further, when infrared spectroscopic measurement (ATR-IR) by total reflection method is performed on the non-adhesive layer (1), measurement is made from Si-CH3Of (2) is 800cm-1The nearby peak was 1725cm with respect to the carbonyl group derived from the (meth) acrylic polymer phase-1As a result of the absorbance ratio of the near peak, 800cm was found when a prism of Ge45 ℃ was used, as compared with ZnSe45 DEG-1The peak in the vicinity becomes large. Therefore, it is found that the silicon content is higher on the air interface side than on the substrate side.
In addition, the presence of a polysiloxane-rich phase on the air interface side (the side opposite to the plastic film) in the non-adhesive layer (1) was also confirmed in FT-IR. Measurement by FT-IR the air interface side was measured by ATR method using "Spectrum One" manufactured by Perkinermer by analyzing 2 kinds of prisms (ZnSe45 DEG, Ge45 DEG) having different depth directions. When the obtained graph was confirmed, it was confirmed that: when a prism of Ge45 ° shallow in the analysis depth direction was used, relative to 1720cm of C ═ O assigned to the (meth) acrylic polymer derived from the non-adhesive layer-1~1730cm-1Of a peak of (A) is derived from Si-CH3Of (2) is 800cm-1The absorbance ratio of the near peak becomes larger. Thus, it was confirmed that the concentration of polysiloxane became higher on the air interface side.
Taking these observations and the principle of minimizing the surface free energy into consideration, it was found that a 2-layer structure having a polysiloxane-rich phase on the air interface side was formed in the non-adhesive layer.
(adhesive layer)
A toluene solution containing 100 parts by weight of AN acrylic copolymer composed of Butyl Acrylate (BA)/Acrylonitrile (AN)/Acrylic Acid (AA) ═ 85/15/2.5 (weight ratio), 10 parts by weight of a melamine-based crosslinking agent (butanol-modified melamine formaldehyde resin, "SUPER BECKAMINE J-820-60N", manufactured by japan polyurethane), 1.0 part by weight of AN epoxy-based crosslinking agent (1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, "TETRAD C", manufactured by mitsubishi gas chemical corporation), 60 parts by weight of a DOP plasticizer (bis (2-ethylhexyl) phthalate, J-PLUS co., manufactured by Ltd) was prepared.
The pressure-sensitive adhesive solution was applied to the surface of the flexible polyvinyl chloride film opposite to the non-pressure-sensitive adhesive layer (1), and then dried at 130 ℃ for 90 seconds to form a pressure-sensitive adhesive layer (1) having a thickness of 10 μm on the surface of the flexible polyvinyl chloride film opposite to the non-pressure-sensitive adhesive layer (1).
(adhesive tape)
The adhesive tape (1) was produced by constructing a laminate structure of the non-adhesive layer (1)/the flexible polyvinyl chloride film/the adhesive layer (1) in the manner described above.
The results are summarized in table 1.
[ example 2 ]
(non-adhesive layer)
60 parts by weight of a silicone resin (KS-723A, manufactured by shin-Etsu chemical industries), 40 parts by weight of a silicone resin (KS-723B, manufactured by shin-Etsu chemical industries), 50 parts by weight of an acrylic copolymer (methyl methacrylate (MMA)/Butyl Acrylate (BA)/hydroxyethyl acrylate (HEA) ═ 70/30/10), and 10 parts by weight of a tin-based catalyst (Cat-PS3, manufactured by shin-Etsu chemical industries) were mixed in a solution state to obtain a mixed solution (2). The mixing ratio of the polysiloxane and the (meth) acrylic polymer in the mixed solution (2) is polysiloxane: (meth) acrylic polymer ═ 2: 1.
the above-mentioned mixed solution (2) was applied to one side of the flexible polyvinyl chloride film obtained in production example 1, and dried to form a non-adhesive layer (2) having a thickness of 1.0 μm and an arithmetic average surface roughness Ra of 0.5 μm.
(adhesive layer)
A toluene solution containing 100 parts by weight of AN acrylic copolymer composed of Butyl Acrylate (BA)/Acrylonitrile (AN)/Acrylic Acid (AA) ═ 85/15/2.5 (weight ratio), 10 parts by weight of a melamine-based crosslinking agent (butanol-modified melamine formaldehyde resin, "SUPER BECKAMINE J-820-60N", manufactured by japan polyurethane), 10 parts by weight of AN epoxy-based crosslinking agent (1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, "tetra d C", manufactured by mitsubishi gas chemical corporation), and 60 parts by weight of a DOP plasticizer (bis (2-ethylhexyl) phthalate, J-PLUS co., manufactured by Ltd) was prepared.
The pressure-sensitive adhesive solution was applied to the surface of the flexible polyvinyl chloride film opposite to the non-pressure-sensitive adhesive layer (2), and then dried at 130 ℃ for 90 seconds to form a pressure-sensitive adhesive layer (2) having a thickness of 10 μm on the surface of the flexible polyvinyl chloride film opposite to the non-pressure-sensitive adhesive layer (2).
(adhesive tape)
The adhesive tape (2) was produced by constructing a laminate structure of the non-adhesive layer (2)/the flexible polyvinyl chloride film/the adhesive layer (2) in the manner described above.
The results are summarized in table 1.
[ example 3 ]
(non-adhesive layer)
60 parts by weight of a silicone resin (KS-723A, manufactured by shin-Etsu chemical industries), 40 parts by weight of a silicone resin (KS-723B, manufactured by shin-Etsu chemical industries), 50 parts by weight of an acrylic copolymer (methyl methacrylate (MMA)/Butyl Acrylate (BA)/hydroxyethyl acrylate (HEA) ═ 70/30/10), and 10 parts by weight of a tin-based catalyst (Cat-PS3, manufactured by shin-Etsu chemical industries) were mixed in a solution state to obtain a mixed solution (3). The mixing ratio of the polysiloxane and the (meth) acrylic polymer in the mixed solution (3) is polysiloxane: (meth) acrylic polymer ═ 2: 1.
the above-mentioned mixed solution (3) was applied to one side of the flexible polyvinyl chloride film obtained in production example 1, and dried to form a non-adhesive layer (3) having a thickness of 1.0 μm and an arithmetic average surface roughness Ra of 0.5 μm.
(adhesive layer)
A toluene solution containing 100 parts by weight of AN acrylic copolymer composed of Butyl Acrylate (BA)/Acrylonitrile (AN)/Acrylic Acid (AA) ═ 85/15/2.5 (weight ratio), 1.0 part by weight of a melamine-based crosslinking agent (butanol-modified melamine formaldehyde resin, "SUPER BECKAMINE J-820-60N", manufactured by japan polyurethane), 10 parts by weight of AN epoxy-based crosslinking agent (1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, "TETRAD C", manufactured by mitsubishi chemical corporation), 60 parts by weight of a DOP plasticizer (bis (2-ethylhexyl) phthalate, J-PLUS co., manufactured by Ltd) was prepared.
The pressure-sensitive adhesive solution was applied to the surface of the flexible polyvinyl chloride film opposite to the non-pressure-sensitive adhesive layer (3), and then dried at 130 ℃ for 90 seconds to form a pressure-sensitive adhesive layer (3) having a thickness of 10 μm on the surface of the flexible polyvinyl chloride film opposite to the non-pressure-sensitive adhesive layer (3).
(adhesive tape)
The adhesive tape (3) was produced by constructing a laminate structure of the non-adhesive layer (3)/the flexible polyvinyl chloride film/the adhesive layer (3) in the above manner.
The results are summarized in table 1.
[ comparative example 1]
(non-adhesive layer)
60 parts by weight of a silicone resin (KS-723A, manufactured by shin-Etsu chemical industries), 40 parts by weight of a silicone resin (KS-723B, manufactured by shin-Etsu chemical industries), 50 parts by weight of an acrylic copolymer (methyl methacrylate (MMA)/Butyl Acrylate (BA)/hydroxyethyl acrylate (HEA) ═ 70/30/10), and 10 parts by weight of a tin-based catalyst (Cat-PS3, manufactured by shin-Etsu chemical industries) were mixed in a solution state to obtain a mixed solution (C1). The mixing ratio of the polysiloxane and the (meth) acrylic polymer in the mixed solution (C1) was polysiloxane: (meth) acrylic polymer ═ 2: 1.
the above-mentioned mixed solution (C1) was applied to one side of the flexible polyvinyl chloride film obtained in production example 1, and dried to form a non-adhesive layer (C1) having a thickness of 1.0 μm and an arithmetic average surface roughness Ra of 0.5 μm.
(adhesive layer)
A toluene solution containing 100 parts by weight of AN acrylic copolymer composed of Butyl Acrylate (BA)/Acrylonitrile (AN)/Acrylic Acid (AA) in a weight ratio of 85/15/2.5, 10 parts by weight of a melamine-based crosslinking agent (butanol-modified melamine formaldehyde resin, "SUPER BECKAMINE J-820-60N", manufactured by japan polyurethane), and 60 parts by weight of a DOP plasticizer (bis (2-ethylhexyl) phthalate, J-PLUS co., Ltd) was prepared.
The adhesive solution was applied to the surface of the flexible polyvinyl chloride film opposite to the non-adhesive layer (C1), and then dried at 130 ℃ for 90 seconds to form an adhesive layer (C1) having a thickness of 10 μm on the surface of the flexible polyvinyl chloride film opposite to the non-adhesive layer (C1).
(adhesive tape)
The adhesive tape (C1) was produced by constructing a laminate structure of the non-adhesive layer (C1)/the flexible polyvinyl chloride film/the adhesive layer (C1) in the above-described manner.
The results are summarized in table 1.
[ comparative example 2 ]
(non-adhesive layer)
60 parts by weight of a silicone resin (KS-723A, manufactured by shin-Etsu chemical industries), 40 parts by weight of a silicone resin (KS-723B, manufactured by shin-Etsu chemical industries), 50 parts by weight of an acrylic copolymer (methyl methacrylate (MMA)/Butyl Acrylate (BA)/hydroxyethyl acrylate (HEA) ═ 70/30/10), and 10 parts by weight of a tin-based catalyst (Cat-PS3, manufactured by shin-Etsu chemical industries) were mixed in a solution state to obtain a mixed solution (C2). The mixing ratio of the polysiloxane and the (meth) acrylic polymer in the mixed solution (C2) was polysiloxane: (meth) acrylic polymer ═ 2: 1.
the above-mentioned mixed solution (C2) was applied to one side of the flexible polyvinyl chloride film obtained in production example 1, and dried to form a non-adhesive layer (C2) having a thickness of 1.0 μm and an arithmetic average surface roughness Ra of 0.5 μm.
(adhesive layer)
A toluene solution containing 100 parts by weight of AN acrylic copolymer composed of Butyl Acrylate (BA)/Acrylonitrile (AN)/Acrylic Acid (AA) ═ 85/15/2.5 (weight ratio), 10 parts by weight of a melamine-based crosslinking agent (butanol-modified melamine formaldehyde resin, "SUPER BECKAMINE J-820-60N", manufactured by japan polyurethane), 0.7 parts by weight of p-toluenesulfonic acid (grade 1, p-toluenesulfonic acid, KISHIDA CHEMICAL co., manufactured by Ltd.), and 60 parts by weight of a DOP plasticizer (bis (2-ethylhexyl) phthalate, J-PLUS co., manufactured by Ltd.) was prepared.
The adhesive solution was applied to the surface of the flexible polyvinyl chloride film opposite to the non-adhesive layer (C2), and then dried at 130 ℃ for 90 seconds to form an adhesive layer (C2) having a thickness of 10 μm on the surface of the flexible polyvinyl chloride film opposite to the non-adhesive layer (C2).
(adhesive tape)
The adhesive tape (C2) was produced by constructing a laminate structure of the non-adhesive layer (C2)/the flexible polyvinyl chloride film/the adhesive layer (C2) in the above-described manner.
The results are summarized in table 1.
[ Table 1]
Industrial applicability
When the pressure-sensitive adhesive tape of the present invention is used for semiconductor processing, it is possible to suppress an increase in the adhesive strength even when heated by laser dicing or the like, to facilitate handling such as removal of a semiconductor element formed into a small piece and transfer to another pressure-sensitive adhesive tape, and to suppress adhesive residue on an adherend. Further, it is preferable that, when the dicing or the like is performed by fixing the base for fixing by suction under negative pressure, occurrence of excessive adhesion due to heat generation or the like of the base can be effectively suppressed, and therefore, the semiconductor manufacturing process including the dicing can be smoothly performed. Further, when the adhesive tape of the present invention is used for semiconductor processing, it is possible to suppress an increase in adhesive strength even when heated by laser dicing or the like, to facilitate handling such as removal of a semiconductor element formed into a small piece and transfer to another adhesive tape, to suppress adhesive residue on an adherend, and to satisfactorily prevent film deformation and accumulation of stress strain which have conventionally occurred due to blocking, and therefore, it is possible to accurately perform bonding following a fine and precise circuit pattern of a semiconductor wafer, and further, to prevent natural release of stress strain after bonding to a semiconductor wafer, and therefore, it is possible to effectively prevent breakage of a semiconductor wafer. In particular, since the wafer for LED is made of a very brittle material such as gallium nitride, gallium arsenide, or silicon carbide, the adhesive tape of the present invention is particularly suitable for dicing (LED dicing) of the wafer for LED, or the like.
Claims (13)
1. A pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive layer on one surface of a substrate, a non-pressure-sensitive adhesive layer on the surface of the substrate opposite to the pressure-sensitive adhesive layer,
the surface of the adhesive layer has indentation hardness of 20.0MPa or more at 100 ℃ obtained by a nanoindenter,
the adhesive layer contains a (meth) acrylic polymer and a crosslinking agent, the content ratio of the crosslinking agent in the adhesive layer is 11 parts by weight or more and less than 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer,
the non-adhesive layer is a mixed layer of polysiloxane and a (meth) acrylic polymer.
2. The adhesive tape according to claim 1, wherein the surface of the adhesive layer has an indentation hardness of 0.5 to 10.0MPa at 23 ℃ by a nanoindenter.
3. The adhesive tape according to claim 1, wherein the adhesive layer has an adhesion at 23 ℃ for 30 minutes and 0.15N/20mm or more in storage.
4. The adhesive tape according to claim 1, wherein the adhesive layer contains an epoxy-based crosslinking agent.
5. The adhesive tape according to claim 1, wherein the substrate has a maximum elongation of 100% or more as measured according to JIS-K-7127 (1999).
6. The adhesive tape of claim 1, wherein the substrate is a plastic film.
7. The adhesive tape of claim 6, wherein the plastic film comprises at least 1 selected from polyvinyl chloride, polyolefin, ethylene-vinyl acetate copolymer.
8. The adhesive tape according to claim 1, wherein a mixing ratio of the polysiloxane to the (meth) acrylic polymer in the non-adhesive layer is, in terms of a weight ratio, polysiloxane: (meth) acrylic polymer ═ 1: 50-50: 1.
9. the adhesive tape according to claim 1, wherein the non-adhesive layer has a phase separation structure.
10. The adhesive tape according to claim 1, wherein the thickness of the non-adhesive layer is 0.01 to 10 μm.
11. The adhesive tape according to claim 1, wherein a release liner is provided on a surface of the adhesive layer.
12. The adhesive tape of claim 1, which is used in semiconductor processing.
13. The adhesive tape according to claim 1, which is used for LED dicing use.
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JP2013079332A JP6071712B2 (en) | 2013-04-05 | 2013-04-05 | Adhesive tape |
JP2013-079332 | 2013-04-05 | ||
CN201410137377.1A CN104099032B (en) | 2013-04-05 | 2014-04-04 | Adhesive tape |
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CN201410137377.1A Division CN104099032B (en) | 2013-04-05 | 2014-04-04 | Adhesive tape |
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JP6494264B2 (en) * | 2014-12-02 | 2019-04-03 | 日東電工株式会社 | Surface protection adhesive sheet |
KR102447759B1 (en) * | 2014-12-02 | 2022-09-27 | 린텍 가부시키가이샤 | Adhesive sheet, and method for manufacturing processed article |
MY196409A (en) * | 2015-10-21 | 2023-03-29 | Furukawa Electric Co Ltd | Surface Protection Adhesive Tape for Semiconductor Wafer Backgrinding, And Semiconductor Wafer Grinding Method |
JP2017132940A (en) * | 2016-01-29 | 2017-08-03 | 日東電工株式会社 | Adhesive tape |
JP6837879B2 (en) * | 2016-08-26 | 2021-03-03 | 日東電工株式会社 | Adhesive tape |
JP6790032B2 (en) * | 2018-09-06 | 2020-11-25 | 日東電工株式会社 | Adhesive sheet |
JP7217118B2 (en) * | 2018-09-26 | 2023-02-02 | 日東電工株式会社 | Optical film with protective film |
JP7075326B2 (en) * | 2018-10-05 | 2022-05-25 | 日東電工株式会社 | Dicing die bond film |
JP7311312B2 (en) * | 2019-05-17 | 2023-07-19 | 東レフィルム加工株式会社 | Base film for dicing sheet |
KR20220022113A (en) * | 2019-06-19 | 2022-02-24 | 쇼와덴코머티리얼즈가부시끼가이샤 | Temporary protective film for semiconductor encapsulation molding, lead frame with temporary protective film, encapsulation molded article with temporary protective film, and method for manufacturing semiconductor device |
JP7007446B2 (en) * | 2020-11-04 | 2022-02-10 | 日東電工株式会社 | Adhesive sheet |
JP7007445B2 (en) * | 2020-11-04 | 2022-02-10 | 日東電工株式会社 | Adhesive sheet |
JP2022116798A (en) * | 2021-01-29 | 2022-08-10 | 日東電工株式会社 | Adhesive sheet for electronic component transfer and method for processing electronic component using adhesive sheet for electronic component transfer |
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KR20140121350A (en) | 2014-10-15 |
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JP6071712B2 (en) | 2017-02-01 |
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