JP7479336B2 - Semiconductor manufacturing process transport tape - Google Patents

Description

The present invention relates to a carrier tape for use in semiconductor manufacturing processes.

Adhesive tapes are used at various stages in the semiconductor manufacturing process. As an example of adhesive tape used in the semiconductor manufacturing process, Patent Document 1 describes an adhesive tape for semiconductor wafers having an adhesive layer using a silicone-based adhesive. Patent Document 2 describes an adhesive tape for semiconductor wafers having an adhesive layer using an acrylic adhesive.

In recent years, semiconductor packages have become increasingly multi-chip, and stacked multi-chip packages (stacked MCPs) in which semiconductor chips are stacked in multiple layers have become widespread. In the manufacturing process of multi-chip packages, semiconductor chips stacked in multiple layers are temporarily fixed to a highly heat-resistant adhesive tape (transport tape for semiconductor manufacturing processes), and a reflow process at over 200°C (for example, a reflow process at 260°C) is carried out to solder the chips together. Silicone-based adhesive resin crosslinkers have been proposed as adhesives for such highly heat-resistant adhesive tapes. Adhesives whose main components are acrylic resins and butadiene rubbers are also known as highly heat-resistant adhesives.

JP 2011-119427 A Patent No. 6053909

The silicone-based adhesive resin crosslinked body described above has excellent heat resistance, but is prone to generate low molecular weight siloxanes at high temperatures, and also contains a significant amount of low molecular weight siloxane compounds generated during the synthesis reaction. When the silicone-based adhesive resin crosslinked body is used as an adhesive tape in the manufacture of a multi-chip package, such low molecular weight siloxanes contaminate the surface of a silicone wafer, causing problems such as poor insulation. To avoid this problem, it becomes necessary to incorporate a cleaning process after the reflow process, which leads to a decrease in manufacturing throughput and product yield.
In addition, although high heat-resistant adhesives mainly composed of acrylic resins or butadiene rubbers can achieve a certain degree of heat resistance, there are limitations to improving the heat resistance level, and when exposed to high temperatures exceeding 200°C, the decomposition reaction of the main skeleton is likely to proceed. Therefore, when used as an adhesive for adhesive tapes in the manufacture of multi-chip packages, there is a problem that peeling failure is likely to occur after the reflow process. Furthermore, since non-silicone adhesives are highly hygroscopic, there is a problem that when exposed to high temperatures exceeding 200°C, bubbles are generated on the adhesion surface, which makes the adhesive easily peel off from the sheet substrate.

On the other hand, the cured product (crosslinked body) obtained by reacting an epoxy compound with its curing agent is known to have excellent heat resistance. However, this cured product is hard in nature and usually does not function as an adhesive at room temperature. It has also been proposed to mix phenoxy resin in the curing reaction of the epoxy compound to increase the molecular weight and create a cured product that is both flexible and adhesive. However, even if it exhibits flexibility and adhesiveness at room temperature, when exposed to high temperatures such as the reflow process in semiconductor manufacturing, this cured product undergoes a further curing reaction and acts like an adhesive, making it prone to peeling problems.

The present invention was made in consideration of the above circumstances, and aims to provide a new carrier tape for the semiconductor manufacturing process that has adhesive properties, can maintain its adhesive properties even at high temperatures exceeding 200°C, and is not contaminated by siloxane compounds.

The above object of the present invention can be achieved by the following means.
[1]
The sheet substrate includes a heat-resistant adhesive layer provided on the sheet substrate,
the heat-resistant adhesive layer is composed of a crosslinked reaction product of an epoxy compound and a curing agent for the epoxy compound,
A carrier tape for semiconductor manufacturing processes, wherein the surface of the heat-resistant adhesive layer has an OH group concentration of 0.15 atm % or more and an Si atom concentration of 5.00 atm % or less.
[2]
The carrier tape for semiconductor manufacturing processes according to [1], wherein the heat-resistant adhesive layer has a thickness of 1 to 50 μm.
[3]
The carrier tape for semiconductor manufacturing processes according to [1] or [2], wherein the heat-resistant adhesive layer has a glass transition temperature of 20° C. or lower.
[4]
The carrier tape for semiconductor manufacturing processes according to any one of [1] to [3], wherein the sheet base material contains a polyimide compound.
[5]
The carrier tape for semiconductor manufacturing processes according to any one of [1] to [4], wherein the thickness of the sheet base material is 30 μm or less.
[6]
The heat-resistant adhesive layer has a peak area at 910 cm ⁻¹ obtained by Fourier transform infrared spectroscopy before and after a heat treatment at 260° C. for 5 minutes, which satisfies the following formula (A):
(A) 0.70≦peak area after heat treatment/peak area before heat treatment≦1.30
[7]
The heat-resistant adhesive layer has a peel strength of 0.3 to 10.0 N/10 mm at 25° C., and a change in peel strength obtained by the following formula (B) before and after heat treatment at 260° C. for 5 minutes is 70 to 130%.
(B) Change in peel strength (%) = {(P2 - P1) / P1} x 100
P1: Peel strength before heat treatment P2: Peel strength after heat treatment [8]
The carrier tape for semiconductor manufacturing process according to any one of [1] to [7], which is used in a reflow process in semiconductor manufacturing.

In the present invention, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower and upper limits. For example, when it is written as "A~B", the numerical range is "A or more and B or less".

The semiconductor manufacturing process carrier tape of the present invention has adhesive properties and can maintain its adhesive properties even at high temperatures exceeding 200°C, and is also less susceptible to contamination by siloxane compounds.

1 is a schematic diagram showing a preferred embodiment of a carrier tape for semiconductor manufacturing processes of the present invention.

The following describes preferred embodiments of the carrier tape for semiconductor manufacturing processes of the present invention (hereinafter also referred to as the "carrier tape of the present invention"); however, the present invention is not limited to the following embodiments except as specified in the present invention.

[Characteristics of carrier tape for semiconductor manufacturing process]
FIG. 1 is a schematic diagram showing an example of the configuration of a semiconductor manufacturing process carrier tape 1 (hereinafter referred to as carrier tape 1), which is one embodiment of the carrier tape of the present invention. As shown in FIG. 1, the carrier tape 1 has a heat-resistant adhesive layer 10 (hereinafter referred to as adhesive layer 10) and a sheet substrate 20. The carrier tape according to the present invention is, for example, an adhesive tape that temporarily fixes multi-layered semiconductor chips in the manufacturing process of a multi-chip package and goes through a reflow process exceeding 200 ° C. (for example, a reflow process at 260 ° C.). The above-mentioned "temporary fixation" means a state in which semiconductor components, etc. are detachably adhered to the carrier tape 1 (adhesive layer 10), and the same applies in the following explanation. In addition, the explanation of each layer described in the carrier tape 1 is not limited to the form of the carrier tape 1, but is also preferable as the form of each layer in the carrier tape of the present invention in general.

The adhesive layer 10 is a film-like adhesive laminated on the sheet substrate 20. As shown in FIG. 1, the adhesive layer 10 has a first surface S1 and a second surface S2 opposite the first surface S1. The first surface S1 is an adhesive surface that temporarily fixes the semiconductor chip. The second surface S2 covers the sheet substrate 20 and is attached to the sheet substrate 20.

The thickness of the adhesive layer 10 is preferably 1 to 200 μm, more preferably 1 to 100 μm, even more preferably 1 to 50 μm, even more preferably 2 to 50 μm, preferably 3 to 45 μm, and even more preferably 4 to 40 μm. By controlling the thickness of the adhesive layer 10 to the above thickness range, the organic solvent can be sufficiently removed during production, and a form exhibiting appropriate film tackiness can be obtained. The thickness of the adhesive layer 10 can be measured, for example, by a contact linear gauge method (desktop contact thickness measuring device).

The material of the sheet substrate 20 used in the above-mentioned conveying tape 1 is not particularly limited as long as it has the desired heat resistance. Examples include polyimide resin, PEN (polyethylene naphthalate) resin, PEEK (polyether ether ketone) resin, PES (polyethersulfone) resin, PCT (polycyclohexane dimethylene terephthalate) resin, PEI (polyetherimide) resin, aromatic polyamide resin, and LCP (liquid crystal polymer) resin.

The thickness of the sheet substrate 20 is preferably 1 to 50 μm, more preferably 1 to 30 μm, even more preferably 2 to 30 μm, and also preferably 4 to 30 μm.

In the carrier tape of the present invention, the OH group concentration on the surface of the adhesive layer is 0.15 atm% or more, and the Si atom concentration on this surface is 5.00 atm% or less.

<Surface OH group concentration>
The carrier tape of the present invention has a OH group concentration on the surface of the adhesive layer of 0.15 atm or more, and has sufficient adhesive properties. The OH group concentration on the surface of the adhesive layer can be determined by measuring the surface of the adhesive layer in which the hydrogen atoms of the OH groups are replaced by trifluoroacetyl groups using XPS (X-ray photoelectron spectroscopy). Specifically, it can be determined by the method described in the section [Examples] below.
The OH group concentration on the surface of the pressure-sensitive adhesive layer is preferably 0.15 to 10.00 atm%, more preferably 0.30 to 9.00 atm%, and even more preferably 0.45 to 8.00 atm%. The OH group concentration on the surface of the pressure-sensitive adhesive layer is also preferably 0.60 to 7.00 atm%, more preferably 0.75 to 6.00 atm%, and even more preferably 1.00 to 5.00 atm%, and is also preferably 1.50 to 4.00 atm%, and is also preferably 0.50 to 4.00 atm%.
When the OH group concentration on the surface of the pressure-sensitive adhesive layer is within the above range, the desired adhesive properties can be sufficiently exhibited.
In the present invention, the term "OH group concentration on the surface of the adhesive layer" means, unless otherwise specified, the OH group concentration on the surface (the first surface S1 in the case of the carrier tape 1) on which semiconductor components, etc. are temporarily fixed in the semiconductor manufacturing process.
It is preferable that the OH group concentration on the surface opposite to the surface to which the semiconductor component is temporarily fixed is also within the above-mentioned preferable OH group concentration range.

<Si atom concentration>
The carrier tape of the present invention has a Si atomic concentration of 5.00 atm% or less on the surface of the pressure-sensitive adhesive layer. The Si atomic concentration on the surface of the pressure-sensitive adhesive layer can be determined by atomic concentration measurement using XPS. Specifically, it can be determined by the method described in the section [Examples] below.
The Si atomic concentration of the adhesive layer surface is preferably 4.50 atm% or less, more preferably 4.00 atm% or less, even more preferably 3.50 atm% or less, even more preferably 3.00 atm% or less, even more preferably 2.50 atm% or less, even more preferably 2.00 atm% or less, even more preferably 1.50 atm% or less, even more preferably 1.00 atm% or less, even more preferably 0.50 atm% or less. It is more preferable that the Si atomic concentration of the adhesive layer surface is at a level that cannot be detected by the above-mentioned detection method (below the detection limit).
In other words, the adhesive layer constituting the carrier tape of the present invention has a different composition from silicone-based adhesive resin crosslinked bodies, and is less likely to cause contamination of the adherend with siloxanes and the like.
In the present invention, the term "Si atomic concentration on the surface of the adhesive layer" means, unless otherwise specified, the Si atomic concentration on the surface (the first surface S1 in the case of the carrier tape 1) on which the semiconductor components are temporarily fixed in the semiconductor manufacturing process.
The Si atomic concentration on the surface opposite to the surface to which the semiconductor component is temporarily fixed is usually the same as the Si atomic concentration on the surface to which the semiconductor component is fixed.

<Glass transition temperature>
In the carrier tape of the present invention, the glass transition temperature (Tg) of the pressure-sensitive adhesive layer is a glass transition temperature measured by differential scanning calorimetry (DSC) at a heating rate of 5° C./min. Specifically, it can be determined by the method described in the section [Examples] below.

In the carrier tape of the present invention, the glass transition temperature of the adhesive layer is preferably low from the viewpoint of developing adhesiveness in the crosslinked body at low temperatures and facilitating lamination. Specifically, it is preferably 30°C or lower, more preferably 25°C or lower, even more preferably 20°C or lower, even more preferably 15°C or lower, even more preferably 10°C or lower, and even more preferably 5°C or lower. In addition, it is practical for the glass transition temperature to be -40°C or higher.

<Changes in characteristics before and after heat treatment>
- Change in the amount of glycidyl groups -
When the pressure-sensitive adhesive layer constituting the carrier tape of the present invention is subjected to a heat treatment at 260° C. for 5 minutes (300 seconds), it is preferable that the peak area at 910 cm ⁻¹ measured by Fourier transform infrared spectroscopy (hereinafter referred to as FTIR (Fourier Transform Infrared Spectroscopy)) before and after this heat treatment satisfies the following formula (A):

(A) 0.70≦peak area after heat treatment/peak area before heat treatment≦1.30

The peak area at 910 cm ⁻¹ in FTIR indicates the presence of glycidyl groups. Therefore, when the pressure-sensitive adhesive layer satisfies the above formula (A), the curing reaction (three-dimensional crosslinking reaction) has already progressed sufficiently in the pressure-sensitive adhesive layer, and no further curing reaction substantially occurs even at temperatures exceeding 200° C., indicating excellent heat resistance.
The peak area at 910 cm ⁻¹ by FTIR can be determined by the method described in the section [Examples] below.
The pressure-sensitive adhesive layer constituting the carrier tape of the present invention preferably has a peak area at 910 cm ⁻¹ measured by FTIR before and after heat treatment at 260° C. for 5 minutes that satisfies the following formula (A1), and more preferably satisfies the following formula (A2).

(A1) 0.80≦peak area after heat treatment/peak area before heat treatment≦1.20
(A2) 0.90≦peak area after heat treatment/peak area before heat treatment≦1.20

- Peel strength and its change -
The peel strength (at 25° C.) of the surface of the pressure-sensitive adhesive layer constituting the carrier tape of the present invention before being subjected to a heat treatment at 260° C. for 5 minutes (300 seconds) is preferably within the range of 0.3 to 10.0 N/10 mm. The peel strength can be determined by the method described in the section [Examples] below.
The peel strength of the surface of the pressure-sensitive adhesive layer constituting the carrier tape of the present invention before being subjected to heat treatment (25°C) is more preferably 0.4 to 5.0 N/10 mm, even more preferably 0.5 to 4.0 N/10 mm, and even more preferably 0.5 to 3.0 N/10 mm.
When the pressure-sensitive adhesive layer constituting the carrier tape of the present invention is subjected to a heat treatment at 260°C for 5 minutes (300 seconds), the change in peel strength obtained by the following formula (B) before and after the heat treatment preferably falls within the range of 70 to 130%.

(B) Change in peel strength (%) = {(P2 - P1) / P1} x 100
P1: Peel strength before heat treatment P2: Peel strength after heat treatment

The change in peel strength is more preferably from 90 to 130%, even more preferably from 95 to 130%, and even more preferably from 100 to 130%.

[Method of forming heat-resistant adhesive layer]
The method for forming the adhesive layer constituting the carrier tape of the present invention is not particularly limited as long as the adhesive layer specified in the present invention can be obtained. The adhesive layer containing the reaction product of an epoxy compound and its curing agent can have the desired characteristics of both high heat resistance and adhesiveness. For example, the desired adhesive layer can be obtained by preparing a mixture containing a polyfunctional epoxy compound, a polyfunctional active hydrogen compound, and a monoepoxy compound, and curing the mixture to form a highly three-dimensional crosslinked structure. Taking this form as an example, the method for forming the adhesive layer will be described below.

<Polyepoxy Compound>
The polyepoxy compound is a compound having a plurality of epoxy groups in the molecule. The epoxy equivalent of the polyepoxy compound is not particularly limited and can be appropriately set, for example, within the range of 100 to 1500 g/eq depending on the purpose.
Examples of the skeleton of the polyfunctional epoxy compound include phenol novolac type, orthocresol novolac type, cresol novolac type, dicyclopentadiene type, biphenyl type, fluorene type, fluorene bisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, trimethylolmethane type, etc. These can also be used in combination to obtain the desired pressure-sensitive adhesive layer.

From the viewpoint of improving heat resistance, it is preferable that the polyepoxy compound has an aromatic ring (aromatic hydrocarbon ring or aromatic heterocycle) in its molecular structure. The aromatic ring of the polyepoxy compound may be a single ring, and it is also preferable that it forms a condensed ring (in the case of a condensed ring, at least one of the rings constituting the condensed ring is an aromatic ring. Examples of the form of the condensed ring include a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a thiophene ring, or a biphenylene ring. Among them, it is preferable that the polyepoxy compound has a fluorene ring.

The polyfunctional epoxy compound reacts with the polyfunctional active hydrogen compound described below to form a highly three-dimensional structure. In the method for producing the pressure-sensitive adhesive layer of the present invention, one or more polyfunctional epoxy compounds can be used.

<Polyvalent active hydrogen compounds>
The polyvalent active hydrogen compound is a compound having a plurality of active hydrogen-containing groups in the molecule, and acts as a curing agent for polyvalent epoxy compounds. Examples of the active hydrogen-containing group include a hydroxyl group (-OH), an amino group (-NH ₂ ), and a thiol group (-SH), and a compound containing one or more of these groups can be used. The number of active hydrogen-containing groups in the polyvalent active hydrogen compound is preferably 2 to 20, more preferably 3 to 10, even more preferably 3 to 8, and even more preferably 3 to 6. Among them, the polyvalent active hydrogen compound preferably contains a polyamine compound and/or a polyhydric phenol compound, and more preferably the polyvalent active hydrogen compound is a polyamine compound and/or a polyhydric phenol compound. In addition, the polyvalent active hydrogen compound preferably contains a polyamine compound, and even more preferably is a polyamine compound.
The polyvalent active hydrogen compound preferably has an aromatic ring (aromatic hydrocarbon ring or aromatic heterocyclic ring) in the molecule.
In forming the pressure-sensitive adhesive layer, one or more polyvalent active hydrogen compounds can be used.

<Other hardeners>
In forming the pressure-sensitive adhesive layer, in addition to the polyvalent active hydrogen compound, or instead of the polyvalent active hydrogen compound, a curing agent other than the polyvalent active hydrogen compound may be included. As such a curing agent, a tertiary amine compound, an acid anhydride compound, an imidazole compound, etc. may also be used.

<Monoepoxy Compound>
A monoepoxy compound is a compound having one epoxy group in the molecule. In a monoepoxy compound, a reaction product of a polyfunctional epoxy compound and a polyfunctional active hydrogen compound acts as a catalyst to cause a polymerization reaction. By the polymerization reaction of a monoepoxy compound, the crosslinked body obtained is more complicatedly entangled to form a highly advanced three-dimensional crosslinked structure. Preferred examples of the monoepoxy compound include phenyl glycidyl ether, alkylphenyl glycidyl ether, alkyl glycidyl ether, alkyl glycidyl ester, glycidyl ether of an alkylphenol alkylene oxide adduct, α-olefin oxide, and monoepoxy fatty acid alkyl ester, and one or more of these can be used.

<Other ingredients>
In forming the pressure-sensitive adhesive layer, the mixture before the curing reaction may further contain, in addition to the above-mentioned components, additives such as an organic solvent (MEK (methyl ethyl ketone), PGMAC (propylene glycol methyl acetate), etc.), an ion trapping agent (ion capturing agent), a viscosity modifier, an antioxidant, a flame retardant, a colorant, and a stress relaxation agent such as butadiene rubber or silicone rubber, within a range that does not impair the effects of the present invention.

In the above mixture before the curing reaction, the amount of each of the above components can be appropriately set in consideration of the degree of adhesion and according to the type of compound. For example, 1 to 100 parts by mass of the polyfunctional active hydrogen compound can be used, preferably 2 to 80 parts by mass, preferably 5 to 60 parts by mass, or preferably 10 to 40 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound. Also, 1 to 100 parts by mass of the monoepoxy compound can be used, preferably 2 to 60 parts by mass, preferably 3 to 40 parts by mass, preferably 3 to 30 parts by mass, or preferably 4 to 20 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound.

The above mixture before the curing reaction can be placed in a mold or formed into a coating film to obtain the desired shape, and reacted at about 100 to 200°C for several minutes to several hours to obtain the adhesive layer of the present invention. It is preferable to carry out this curing reaction thoroughly. By carrying out the curing reaction thoroughly, it is possible to obtain an adhesive layer with high heat resistance.

[Method of manufacturing carrier tape]
The carrier tape of the present invention can be obtained by applying the mixture before the curing reaction for forming the adhesive layer described above onto one side of a sheet substrate, and then heat curing the mixture. As a method for forming the adhesive layer on one side of the sheet substrate, a known method can be appropriately adopted, and for example, a method using a roll knife coater, a gravure coater, a die coater, a reverse coater, etc. can be adopted.

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Preparation of carrier tape]
Carrier tape 1 shown in FIG. 1 was prepared as follows.

Example 1
100 parts by mass of a fluorene-skeleton epoxy resin (polyvalent epoxy compound, trade name: EG280, manufactured by Osaka Gas Chemicals Co., Ltd.), 10 parts by mass of a monoglycidyl ether (alkyl monoglycidyl ether, trade name: M1230, manufactured by Kyoeisha Chemical Co., Ltd.), and 25 parts by mass of an amine-based epoxy curing agent (polyamine compound, trade name: EH-5057 PK, manufactured by ADEKA Corporation) were stirred/kneaded at room temperature, and the mixture was applied to one side of a polyimide film (trade name: 100EN, thickness: 25 μm, manufactured by Toray Industries, Inc.) with a coating thickness of 30 μm using an applicator to form an adhesive layer 10. Next, the adhesive layer 10 was subjected to a curing reaction at 150° C. for 10 minutes. Then, the adhesive layer was aged for 24 hours or more under milder heating conditions. In this way, a carrier tape 1 was obtained in which a sheet-like adhesive layer 10 having a thickness of 30 μm, a length of 300 mm, and a width of 100 mm was formed on a polyimide film.

Example 2
Carrier tape 1 of Example 2 was obtained in the same manner as in Example 1, except that the blending amount of monoglycidyl ether was 30 parts by mass and the blending amount of the amine-based epoxy curing agent was 27 parts by mass.

Example 3
Carrier tape 1 of Example 3 was obtained in the same manner as in Example 1, except that the blending amount of monoglycidyl ether was 5 parts by mass and the blending amount of the amine-based epoxy curing agent was 23 parts by mass.

Example 4
Carrier tape 1 of Example 4 was obtained in the same manner as in Example 1, except that the thickness of pressure-sensitive adhesive layer 10 was 40 μm.

Example 5
Carrier tape 1 of Example 5 was obtained in the same manner as in Example 1, except that the thickness of pressure-sensitive adhesive layer 10 was 5 μm.

Example 6
A carrier tape 1 of Example 6 was obtained in the same manner as in Example 1, except that the amount of the fluorene skeleton epoxy resin was 70 parts by mass, the amount of the amine-based epoxy curing agent was 26 parts by mass, and 30 parts by mass of a bisphenol A type epoxy resin (product name: RE310S, manufactured by Nippon Kayaku Co., Ltd.) was further added.

Example 7
Carrier tape 1 of Example 7 was obtained in the same manner as in Example 1, except that the thickness of pressure-sensitive adhesive layer 10 was 50 μm.

<Comparative Example 1>
Carrier tape 1 of Comparative Example 1 was obtained in the same manner as in Example 1, except that the aging treatment was omitted.

[Measurement and Analysis]
<Measurement of Surface OH Group Concentration>
The OH group concentration on the first surface S1 of the carrier tape 1 obtained in Examples 1 to 7 and Comparative Example 1 was measured. Specifically, the hydrogen atoms of the OH groups on the first surface S1 of the carrier tape 1 according to each Example and Comparative Example were replaced with trifluoroacetyl groups, and the OH group concentration on the first surface S1 was determined by measuring by X-ray photoelectron spectroscopy (XPS). More specifically, the hydrogen atoms of the OH groups on the first surface S1 of each carrier tape 1 were replaced with trifluoroacetyl groups by vapor-phase modification, and the F atom concentration was calculated from the F1s spectrum observed by XPS measurement (incident X-ray: monochromatic or Al-Kα (hν=1486.6 eV), measurement area: 100 μmφ, escape angle: 45°, product name: PHIQuantes, manufactured by ULVAC-PHI, Inc.). Next, the OH group concentration before replacement was calculated based on the calculated F atom concentration. In the treatment of replacing the hydrogen atoms of the OH groups with trifluoroacetyl groups, the first surface S1 of the carrier tape 1 was allowed to react sufficiently with trifluoroacetic anhydride in a sealed glass container. Thereafter, the glass container was evacuated for a predetermined period of time to remove trifluoroacetic anhydride remaining in the glass container.
The OH group concentration is shown as atomic %, assuming that an OH group is one atom (all OH groups are one atom).

<Measurement of Si Atomic Concentration>
The Si atomic concentration of the first surface S1 of the carrier tape 1 obtained in Examples 1 to 7 and Comparative Example 1 was determined by XPS measurement. Specifically, the first surface S1 of the carrier tape 1 according to each Example and Comparative Example was irradiated with X-rays, and the Si atomic concentration was determined from the number of electrons emitted by the photoelectric effect and the energy spectrum. More specifically, the peaks of the Si atoms were identified from the positions and intensities of the peaks in the spectrum, and the number of electrons of the Si atoms (C1) was calculated by integrating the identified peaks. Then, the ratio (C1/C2) of the number of electrons of the Si atoms (C1) to the total number of electrons (C2) obtained by integrating all the peaks in the spectrum was calculated as the Si atomic concentration.

<Measurement of Glass Transition Temperature>
The glass transition temperature was measured using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation). More specifically, the temperature was raised from -100°C to 100°C at a heating rate of 5°C/min, and the extrapolated glass transition onset temperature according to JIS K 121:2012 "Method for measuring transition temperature of plastics" was used as the glass transition temperature.

<Heat resistance test>
-FTIR measurement (change in amount of glycidyl groups)-
For the carrier tapes 1 obtained in Examples 1 to 7 and Comparative Example 1, the change in the peak area at 910 cm ⁻¹ indicating a glycidyl group obtained by FTIR was examined before and after heat treatment at 260° C. for 5 minutes. This peak area was calculated as the ratio (E2/E1) of the peak area (E2) ^{at 910 cm −1 obtained} after heat treatment to the peak area (E1) at 910 cm ⁻¹ obtained before heat treatment (25° C.) after normalizing the FTIR spectrum based on the peak at 2850 cm ⁻¹ indicating an ethylene group. The peak area was determined as the region between the peak and the baseline, with a baseline set based on the inflection point at the bottom of the 910 cm −1 peak.

- Peel strength test (change in peel strength) -
For the carrier tapes 1 obtained in Examples 1 to 7 and Comparative Example 1, a 90° peel test based on JIS Z 0237:2009 "Testing Methods for Adhesive Tapes and Adhesive Sheets" was carried out before and after a heat treatment at 260°C for 5 minutes, and the change in peel strength before and after the heat treatment was examined. In this peel test, a glass plate was used as the adherend to be attached to the adhesive layer 10 (the adherend to be attached to the surface opposite to the polyimide film side of the carrier tape 1), the unit of peel strength was N/10 mm, and the peel speed was 50 mm/min. The change in peel strength was calculated by the following formula (1) when the peel strength of the first surface S1 before the heat treatment was P1 and the peel strength of the first surface S1 after the heat treatment was P2. The peel strength was measured at 25°C both before and after the heat treatment.

Change in peel strength (%) = {(P2 - P1) / P1} x 100 (1)

- Air bubbles and glue residue -
The carrier tape 1 obtained in Examples 1 to 7 and Comparative Example 1 was attached to a slide glass on the side opposite to the polyimide film side, and heat-treated at 260° C. for 5 minutes, and the heat resistance was evaluated based on the following evaluation criteria. In addition, after this heat treatment, the adhesive residue on the slide glass surface after peeling off the carrier tape 1 was also visually evaluated.

(Evaluation criteria)
◯: No air bubbles were generated between the carrier tape 1 and the slide glass, and the carrier tape 1 was not peeled off from the slide glass.
×: Air bubbles were generated between the carrier tape 1 and the slide glass, and the carrier tape 1 was peeled off from the slide glass.

The physical properties and evaluation results of carrier tape 1 of Examples 1 to 7 and Comparative Example 1 are shown in the table below.

Notes for the table:
"ND" means not measurable.

The carrier tape 1 of Comparative Example 1 has a surface OH group concentration that satisfies the requirements of the present invention, but when exposed to high temperatures exceeding 200°C, a curing reaction occurs, and the adhesive layer 10 of the carrier tape 1 does not function as an adhesive. In addition, after heat treatment at 260°C for 5 minutes, air bubbles were confirmed between the carrier tape 1 according to Comparative Example 1 and the slide glass, and the carrier tape 1 was peeled off from the slide glass. The reason why the "adhesive residue" of the carrier tape 1 of Comparative Example 1 is "ND" is that the carrier tape 1 cannot be peeled off from the slide glass after heat treatment at 260°C for 5 minutes, making it meaningless to evaluate the adhesive residue.
On the other hand, the carrier tapes 1 of Examples 1 to 7, which satisfy the provisions of the present invention, showed excellent heat resistance, with no air bubbles between the carrier tapes and the slide glass after heat treatment for 5 minutes at 260° C., and therefore no peeling from the slide glass occurred. Furthermore, the carrier tapes 1 of Examples 1 to 7 showed little change in adhesive properties even after heat treatment for 5 minutes at 260° C., and maintained adhesive properties even at this high temperature.

Although the present invention has been described in conjunction with its embodiments, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the appended claims should be interpreted broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

1: Transport tape for semiconductor manufacturing process 10: Heat-resistant adhesive layer 20: Sheet substrate S1: First surface S2: Second surface

Claims (7)

The sheet substrate and the heat-resistant adhesive layer provided on the sheet substrate are provided.
the heat-resistant adhesive layer is composed of a crosslinked reaction product of an epoxy compound and a curing agent for the epoxy compound, and the peak area at 910 cm ⁻¹ obtained by Fourier transform infrared spectroscopy before and after heat treatment at 260° C. for 5 minutes satisfies the following formula (A):
A carrier tape for semiconductor manufacturing processes, wherein the surface of the heat-resistant adhesive layer has an OH group concentration of 0.15 atm % or more and an Si atom concentration of 5.00 atm % or less.
(A) 0.70≦peak area after heat treatment/peak area before heat treatment≦1.30 The semiconductor manufacturing process carrier tape according to claim 1, wherein the heat-resistant adhesive layer has a thickness of 1 to 50 μm. The semiconductor manufacturing process transport tape according to claim 1 or 2, wherein the glass transition temperature of the heat-resistant adhesive layer is 20°C or lower. The semiconductor manufacturing process carrier tape according to any one of claims 1 to 3, wherein the sheet substrate contains a polyimide compound. The semiconductor manufacturing process transport tape according to any one of claims 1 to 4, wherein the thickness of the sheet substrate is 30 μm or less. The carrier tape for semiconductor manufacturing process according to any one of claims 1 to 5, wherein the heat-resistant adhesive layer has a peel strength of 0.3 to 10.0 N/10 mm at 25°C, and a change in peel strength obtained by the following formula (B) before and after heat treatment at 260°C for 5 minutes is 70 to 130%.
(B) Change in peel strength (%) = {(P2 - P1) / P1} x 100
P1: Peel strength before heat treatment P2: Peel strength after heat treatment The carrier tape for use in a semiconductor manufacturing process according to any one of claims 1 to 6 , which is used in a reflow process in semiconductor manufacturing.

Images