TW202340411A - Pressure-sensitive adhesive tape for processing semiconductor - Google Patents

Abstract

The present disclosure provides a pressure-sensitive adhesive tape for processing a semiconductor comprising a substrate and an energy ray curable pressure-sensitive adhesive layer placed on one surface of the substrate, wherein a color difference ΔE ^* _abin L ^*a ^*b ^*color system, determined from the following test, is 2.0 or less. Test: includes the following steps (1) to (5) in sequence. (1) A stacked body is produced by adhering a pressure-sensitive adhesive layer side surface of the pressure-sensitive adhesive tape for processing a semiconductor to a copper foil. (2) The stacked body is stored for 6 days in an environment wherein an energy ray is blocked, at temperature of 25℃ ± 5℃, and humidity of 40%RH or more and 60%RH or less. (3) An energy ray is irradiated to the pressure-sensitive adhesive tape for processing a semiconductor of the stacked body to cure the pressure-sensitive adhesive layer. (4) The pressure-sensitive adhesive tape for processing a semiconductor is peeled off from the stacked body. (5) A color difference ΔE ^* _abbetween an adherend surface of the copper foil before being adhered to the pressure-sensitive adhesive tape for processing a semiconductor, and an adherend surface of the copper foil after the pressure-sensitive adhesive tape for processing a semiconductor is peeled off, in L ^*a ^*b ^*color system is determined.

Description

Adhesive tape for semiconductor processing

The present invention relates to an adhesive tape for semiconductor processing.

In the manufacturing process of semiconductors, in order to fix or protect parts, adhesive tapes for semiconductor processing such as dicing tapes or back grinding tapes are used.

For adhesive tapes used in semiconductor processing, it is required that the parts can be fixed with sufficient adhesion during the processing steps and that the parts can be easily peeled off without damage after the processing steps.

As such adhesive tapes for semiconductor processing, for example, energy ray curable adhesive tapes are actively developed (for example, Patent Documents 1 to 3). Energy ray curable adhesive tape can harden the adhesive layer and reduce the adhesive force by using energy ray irradiation. Therefore, it can have both strong adhesion before energy ray irradiation and easy peelability after energy ray irradiation. [Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2015/133420 [Patent Document 2] Japanese Patent Application Publication No. 2005-23188 [Patent Document 3] Japanese Patent Application Publication No. 2014-154796

[Problem to be solved by the invention]

Since the adhesive tape for semiconductor processing is bonded to the adherend during the processing step, the adhesive tape for semiconductor processing is in contact with the adherend for a long time. Therefore, components contained in the adhesive tape for semiconductor processing may be transferred to the surface of the adherend, resulting in contamination of the adherend. If the surface of the adherend is contaminated, there will be the following problem: in the subsequent steps of the semiconductor manufacturing process, such as the wiring step, the sealing step, etc., it will become a factor of poor adhesion or peeling, thus affecting the performance or reliability of the semiconductor. reduce.

The present invention was completed in view of the above-mentioned circumstances, and its main purpose is to provide a low-pollution adhesive tape for semiconductor processing. [Technical means to solve problems]

The inventors of the present invention conducted intensive research in order to solve the above-mentioned problems, and as a result obtained the following findings. The contamination of the adherend caused by the adhesive tape used for semiconductor processing is due to the change of the surface state of the adherend. The inventors of the present invention have repeatedly conducted intensive research on the evaluation method of the surface condition of the adherend, focusing on the color of the surface of the adherend. Furthermore, in semiconductors, copper wiring is widely used along with miniaturization and high speed, so copper foil is attracting attention as an adherend. Furthermore, it was found that the change in the surface state of the copper foil as the adherend can be evaluated by the color difference ΔE ^* _ab of the adhered surface of the copper foil before and after peeling off the adhesive tape for semiconductor processing, and the color difference ΔE ^* _ab Suitable for evaluating contamination of adherends caused by adhesive tapes used in semiconductor processing. The present invention is based on this finding.

One embodiment of the present invention provides an adhesive tape for semiconductor processing, which has a base material and an energy ray curable adhesive layer disposed on one surface of the base material, and has an L value determined by the following test ^* a ^* b ^* The color difference ΔE ^* _ab in the color expression system is 2.0 or less. Test: There are the following steps (1) to (5) in sequence. (1) The surface of the adhesive layer of the adhesive tape for semiconductor processing is bonded to a copper foil to prepare a laminated body. (2) Store the above laminated body for 6 days in an environment with a temperature of 25°C ± 5°C, a humidity of 40% RH or more and 60% RH or less, and energy lines are blocked. (3) The adhesive tape for semiconductor processing of the laminated body is irradiated with energy rays to harden the adhesive layer. (4) Peel the adhesive tape for semiconductor processing from the laminated body. (5) Find the L ^* a ^* b ^* color system of the adhered surface of the above-mentioned copper foil before laminating the above-mentioned adhesive tape for semiconductor processing and the adhered surface of the above-mentioned copper foil after peeling off the above-mentioned adhesive tape for semiconductor processing. The color difference ΔE ^* _ab . [Effects of the invention]

The adhesive tape for semiconductor processing in the present invention has the effect of suppressing contamination of the adherend.

In the following, embodiments of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in various different aspects and is not limited to the description of the embodiments illustrated below. In addition, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual form in order to make the description clearer. However, these are only examples and do not limit the interpretation of the present invention. In addition, in this specification and each drawing, the same components as those described above in the drawings that have already appeared are sometimes labeled with the same symbols, and detailed descriptions are appropriately omitted.

In this specification, when describing the arrangement of other components on a certain component, it is abbreviated as "on ~ on" or "on ~ below". Unless otherwise specified, it includes those connected to a certain component. There are two ways to arrange other components directly above or below, and to arrange other components above or below a certain component with another component interposed. In addition, in this specification, when describing the arrangement of other members on the surface of a certain member, it is abbreviated as "on the surface". Unless otherwise specified, it includes connecting with a certain member on the front. There are two cases where other members are placed above or directly below, and there are cases where other members are placed above or below a certain member with another member interposed.

Hereinafter, the adhesive tape for semiconductor processing of this invention is demonstrated.

The adhesive tape for semiconductor processing of the present invention has a base material and an energy ray curable adhesive layer disposed on one side of the base material, and is determined by the following test in the L ^* a ^* b ^* color system The color difference ΔE ^* _ab is 2.0 or less. Test: There are the following steps (1) to (5) in sequence. (1) The surface of the adhesive layer of the adhesive tape for semiconductor processing is bonded to a copper foil to prepare a laminated body. (2) Store the above laminated body for 6 days in an environment with a temperature of 25°C ± 5°C, a humidity of 40% RH or more and 60% RH or less, and energy lines are blocked. (3) The adhesive tape for semiconductor processing of the laminated body is irradiated with energy rays to harden the adhesive layer. (4) Peel the adhesive tape for semiconductor processing from the laminated body. (5) Find the L ^* a ^* b ^* color system of the adhered surface of the above-mentioned copper foil before laminating the above-mentioned adhesive tape for semiconductor processing and the adhered surface of the above-mentioned copper foil after peeling off the above-mentioned adhesive tape for semiconductor processing. The color difference ΔE ^* _ab .

FIG. 1 is a schematic cross-sectional view illustrating an adhesive tape for semiconductor processing according to the present invention. The adhesive tape 10 for semiconductor processing in FIG. 1 has a base material 1 and an energy ray curable adhesive layer 2 arranged on one surface of the base material 1 . In the adhesive tape 10 for semiconductor processing, the color difference ΔE ^* _ab determined by the above test is equal to or less than a predetermined value.

In the present invention, the color difference ΔE ^* _ab between the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded and the adhered surface of the copper foil after the adhesive tape for semiconductor processing is peeled off is determined by the above test. Below the predetermined value. This means that the surface condition of the adhered surface of the copper foil changes little before the adhesive tape for semiconductor processing is bonded and after peeling off.

Here, as a factor which changes the surface state of a copper foil, the following three can be mentioned, for example. The first reason is that when the adhesive tape for semiconductor processing is peeled off, paste remains. The second is that the components contained in the adhesive tape for semiconductor processing, especially the low molecular components, are transferred to the surface of the copper foil. The third reason is that the components contained in the adhesive tape for semiconductor processing react with copper. It is considered that when the surface condition of the copper foil changes due to the factors mentioned above, it appears as color difference.

Therefore, in the present invention, it can be said that the component contained in the adhesive tape for semiconductor processing can be suppressed from being transferred to the surface of the adherend by the color difference ΔE ^* _ab being equal to or less than a predetermined value. In addition, it can be said that the reaction between components contained in the adhesive tape for semiconductor processing and copper can be suppressed. Therefore, contamination of the adherend can be suppressed. Furthermore, it can be said that the paste can be suppressed from remaining on the adherend when peeling off the adhesive tape for semiconductor processing. Therefore, the performance and reliability of the semiconductor can be improved.

Furthermore, for example, Patent Document 1 discloses that the water contact angle on the surface of a silicon wafer after peeling off the adhesive tape for semiconductor processing is used to evaluate the adhesion caused by the organic substance contained in the adhesive tape for semiconductor processing. body pollution. However, as mentioned above, the factor that changes the surface state of the adherend is not just the transfer of organic substances contained in the adhesive tape for semiconductor processing to the surface of the adherend.

On the other hand, as mentioned above, it is considered that even when the surface state of the copper foil changes due to any of the above-mentioned factors, chromatic aberration will appear. Therefore, in the present invention, by using the above-mentioned color difference ΔE ^* _ab , the surface state of the adherend can be accurately evaluated, and contamination of the adherend caused by the adhesive tape for semiconductor processing can be appropriately evaluated.

Hereinafter, each structure of the adhesive tape for semiconductor processing of this invention is demonstrated.

1. Characteristics of the adhesive tape for semiconductor processing In the adhesive tape for semiconductor processing of the present invention, the color difference ΔE ^* _ab in the L ^* a ^* b ^* color system determined by the following test is 2.0 or less, which is less than 2.0. Preferably, it is 1.8 or less, and more preferably, it is 1.5 or less. The color difference ΔE ^* _ab is preferably small, and the lower limit is not particularly limited.

Test: There are the following steps (1) to (5) in sequence. (1) The surface of the adhesive layer of the adhesive tape for semiconductor processing is bonded to a copper foil to prepare a laminated body. (2) Store the above laminated body for 6 days in an environment with a temperature of 25°C ± 5°C, a humidity of 40% RH or more and 60% RH or less, and energy lines are blocked. (3) The adhesive tape for semiconductor processing of the laminated body is irradiated with energy rays to harden the adhesive layer. (4) Peel the adhesive tape for semiconductor processing from the laminated body. (5) Find the L ^* a ^* b ^* color system of the adhered surface of the above-mentioned copper foil before laminating the above-mentioned adhesive tape for semiconductor processing and the adhered surface of the above-mentioned copper foil after peeling off the above-mentioned adhesive tape for semiconductor processing. The color difference ΔE ^* _ab .

In the above step (1), first, the adhesive tape for semiconductor processing is cut into a size of 40 mm or more in width and 100 mm or more in length. In addition, as the copper foil, a rolled copper foil "RCF-T5B" with a thickness of 35 μm manufactured by Fukuda Metal Foil Industry Co., Ltd. was used. Then, wipe the glossy surface of the rolled copper foil with isopropyl alcohol (IPA) and dry it thoroughly. Thereafter, the adhesive layer surface of the adhesive tape for semiconductor processing is bonded to the glossy surface of the rolled copper foil. At this time, in an environment where the temperature is 25°C ± 5°C, the humidity is 40% RH or more and 60% RH or less, and the energy lines are blocked, make the 2 kg roller reciprocate twice to bond the adhesive layer surface of the adhesive tape for semiconductor processing. On the glossy side of rolled copper foil. In addition, at this time, when the adhesive tape for semiconductor processing has an isolation film, the isolation film may be peeled off to expose the adhesive layer.

Furthermore, as mentioned above, in the manufacturing steps of semiconductors, the adhesive tape for semiconductor processing is in contact with the adherend for a long time. Therefore, in the above step (1), the storage conditions are set to standard temperature and humidity, and the storage time is set to a slightly longer time.

In the above step (2), the energy rays to be interrupted are the energy rays that can harden the energy ray hardening adhesive layer, and are appropriately selected according to the type of the adhesive layer. Energy lines will be described below.

In the above step (3), the energy rays irradiated are energy rays that can harden the energy ray hardening adhesive layer, and are appropriately selected according to the type of the adhesive layer. In addition, the energy ray irradiation conditions (such as wavelength, accumulated light amount, etc.) only need to be conditions that can harden the energy ray hardenable adhesive layer, and are appropriately selected according to the composition, thickness, etc. of the adhesive layer. Specific irradiation conditions for energy rays include conditions for irradiating ultraviolet rays with a wavelength of 400 nm or less, especially ultraviolet rays with a wavelength of 365 nm, with a cumulative light amount of 200 mJ/cm ² or more, or more.

In the above-mentioned step (4), when peeling off the adhesive tape for semiconductor processing from the laminated body, it is preferable to set the peeling speed to about 100 mm/min or more and 1000 mm/min or less.

In the above step (5), the L ^* a ^* b ^* color system is the color system specified by the International Commission on Illumination (CIE) in 1976 and also specified in JIS Z8781-4. The color difference ΔE ^* _ab is calculated by the following formula. ΔE ^＊ _ab ＝{(ΔL ^＊ ) ² ＋(Δa ^＊ ) ² ＋(Δb ^＊ ) ² } ^1/2 (In the above formula, ΔL ^＊ is the adhered surface of the copper foil before laminating the adhesive tape for semiconductor processing. The difference between the brightness L ^* and the brightness L ^* of the adhered surface of the copper foil after the adhesive tape for semiconductor processing is peeled off. Also, Δa ^* is the chromaticity a of the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded. ^＊ , the difference from the chromaticity a ^＊ of the adhered surface of the copper foil after the adhesive tape for semiconductor processing is peeled off. Also, Δb ^＊ is the chromaticity b ^＊ of the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded. , the difference from the color b ^* of the adhered surface of the copper foil after peeling off the adhesive tape for semiconductor processing)

The brightness L ^＊ , chromaticity a ^＊ , b ^＊ of the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded and the adhered surface of the copper foil after the adhesive tape for semiconductor processing is peeled off can be measured using spectrophotometry in accordance with JIS Z8722 meter to measure. The measurement conditions were set to D65 light source, 10° visual field, and reflectance measurement. As a spectrophotometer, for example, a device capable of reflection measurement such as "Spectrophotometer SE6000" manufactured by Nippon Denshoku Industries Co., Ltd. can be used.

Moreover, in the above-mentioned step (5), when measuring the brightness L ^* and chromaticity a ^* and b ^* of the adhered surface of the copper foil after the adhesive tape for semiconductor processing is laminated, the adhesive tape for semiconductor processing is removed from the laminated body. After peeling off, the measurement was performed directly. On the other hand, when measuring the brightness L ^* and chromaticity a ^* and b ^* of the adhered surface of the copper foil before laminating the adhesive tape for semiconductor processing, wipe the adhered surface of the copper foil with isopropyl alcohol to make it fully Measure after drying.

Furthermore, the energy ray hardenable adhesive layer is hardened by irradiation with energy rays, thereby reducing the adhesive force. Furthermore, in the above step (1), the surface of the adhesive layer of the adhesive tape for semiconductor processing is bonded not to the rough surface of the rolled copper foil, but to the glossy surface of the rolled copper foil. Therefore, the adhesive tape for semiconductor processing can be easily peeled off from the laminated body. Therefore, it is considered that there is almost no deformation of the copper foil due to peeling of the adhesive tape for semiconductor processing. Therefore, it is considered that the above-mentioned color difference ΔE ^* _ab is caused by the change in the surface state of the copper foil caused by the adhesive tape for semiconductor processing, and is not caused by the deformation of the copper foil.

In addition, if there is concern about deformation of the copper foil due to peeling off of the adhesive tape for semiconductor processing, the copper foil can be fixed in advance to a SUS (Steel Use Stainless, Japanese stainless steel standard) plate or glass plate using double-sided tape. Use after straightening the substrate.

Examples of methods for controlling the above-mentioned color difference ΔE ^* _ab include: a method of adjusting the composition of the base material, a method of adjusting a formation method of the base material, a method of adjusting the composition of the adhesive layer, a method of adjusting the cross-linking degree of the adhesive, Methods of arranging a primer layer between the substrate and the adhesive layer, etc.

As a method of adjusting the composition of the base material, for example, a method of adjusting the content and molecular weight of additives can be cited. For example, by reducing the content of additives, the components contained in the base material can be inhibited from being transferred to the surface of the adherend through the adhesive layer. As a result, the above-mentioned color difference ΔE ^* _ab can be reduced. In addition, for example, by increasing the molecular weight of the additive, the components contained in the base material can be inhibited from being transferred to the surface of the adherend through the adhesive layer. As a result, the above-mentioned color difference ΔE ^* _ab can be reduced. Specifically, by using polymer-type additives, components contained in the substrate can be inhibited from being transferred to the surface of the adherend through the adhesive layer.

An example of a method for adjusting the formation method of the base material is a method of sufficiently melting the resin composition when the resin composition is melted and formed. By sufficiently melting the resin composition, the dispersibility of the additives contained in the resin composition is improved, so that the additives are stably present in the base material. This can prevent components contained in the base material from being transferred to the surface of the adherend through the adhesive layer, and as a result, the above-mentioned color difference ΔE ^* _ab can be reduced.

Examples of methods for adjusting the composition of the adhesive layer include: adjusting the molecular weight of the main adhesive agent or additives, adjusting the glass transition temperature of the main adhesive agent or additives, and adjusting the compatibility of the main adhesive agent and additives. , Methods of adding cross-linking agents, methods of adjusting the type or quantity of functional groups of the main adhesive agent or energy ray curable compound.

For example, in the method of adjusting the molecular weight of the main adhesive agent, by increasing the molecular weight of the main adhesive agent, the components contained in the adhesive layer can be inhibited from being transferred to the surface of the adherend. As a result, the above-mentioned color difference ΔE ^* _ab can be reduced. . For example, in the method of adjusting the molecular weight of an additive, by increasing the molecular weight of the additive, components contained in the adhesive layer can be inhibited from being transferred to the surface of the adherend. As a result, the above-mentioned color difference ΔE ^* _ab can be reduced. Specifically, by using polymer-type additives or using additives capable of cross-linking, the components contained in the adhesive layer can be inhibited from being transferred to the surface of the adherend.

In addition, for example, in the method of adjusting the glass transition temperature of the main adhesive agent, by increasing the glass transition temperature of the main adhesive agent, the components contained in the adhesive layer can be inhibited from being transferred to the surface of the adherend. As a result, the The above-mentioned color difference ΔE ^* _ab . For example, in the method of adjusting the glass transition temperature of an additive, by increasing the glass transition temperature of the additive, the components contained in the adhesive layer can be inhibited from being transferred to the surface of the adherend. As a result, the above-mentioned color difference ΔE ^* can be reduced. _ab .

In addition, for example, in the method of adjusting the compatibility of the adhesive main agent and additives, by improving the compatibility of the adhesive main agent and additives, the components contained in the adhesive layer can be inhibited from being transferred to the surface of the adherend. As a result, , can reduce the above-mentioned color difference ΔE ^* _ab . Specifically, by adjusting the polarity, molecular weight, composition ratio, mixing method, etc. of the main adhesive agent and additives, the compatibility of the main adhesive agent and additives can be adjusted.

For example, in the method of adding a cross-linking agent, by reacting the functional groups of the main adhesive agent with the cross-linking agent, the unreacted functional groups that have not reacted with the cross-linking agent can be reduced, for example, the reaction between the metal surface and the functional groups can be inhibited. . Thereby, the above-mentioned color difference ΔE ^* _ab can be reduced. In addition, the main adhesive agent is cross-linked by a cross-linking agent, thereby improving the cohesion force, thereby inhibiting the transfer of components contained in the adhesive layer to the surface of the adherend. As a result, the above-mentioned color difference ΔE ^* _ab can be reduced.

Also, for example, in the method of adjusting the type of functional groups of the adhesive main agent, the functional groups that can react with the cross-linking agent are set to functional groups that are difficult to react with copper, so that even unreacted ones that do not react with the cross-linking agent The remaining functional groups can also inhibit the reaction between copper and functional groups. As a result, the above-mentioned color difference ΔE ^* _ab can be reduced.

For example, in a method of adjusting the type of functional group of an energy ray curable compound, the functional group that can react with the energy ray curable functional group or the cross-linking agent can be made into a functional group that is difficult to react with copper. The reaction between copper and functional groups is inhibited, and as a result, the above-mentioned color difference ΔE ^* _ab can be reduced. Furthermore, for example, in a method for adjusting the number of functional groups in an energy ray curable compound, by reducing the number of functional groups that can react with the energy ray curable functional group or the cross-linking agent, the interaction between copper and the functional group can be suppressed. reaction. Thereby, the above-mentioned color difference ΔE ^* _ab can be reduced.

In the method of adjusting the cross-linking degree of the adhesive, by increasing the cross-linking degree of the adhesive, the cohesion force is increased, thereby inhibiting the transfer of components contained in the adhesive layer to the surface of the adherend. As a result, Reduce the above-mentioned color difference ΔE ^* _ab .

In the method of arranging a primer layer between the base material and the adhesive layer, the primer layer can inhibit the components contained in the base material from being transferred to the surface of the adherend through the adhesive layer. As a result, the above-mentioned color difference can be reduced. ΔE ^* _ab .

Furthermore, in the adhesive tape for semiconductor processing of the present invention, the adhesion force to the SUS plate before energy ray irradiation is, for example, preferably 1 N/25 mm or more, more preferably 3 N/25 mm or more, and still more preferably 5 N /25 mm or more. By setting the adhesive force to the SUS board within the above range, the adherend can be sufficiently fixed to the adhesive tape for semiconductor processing before irradiation with energy rays. On the other hand, the upper limit of the adhesive force of the SUS board is not particularly limited.

Here, the adhesion of the SUS board can be measured according to the test method 1 of JIS Z0237:2009 (Adhesive tape-adhesive sheet test method) (at a temperature of 23°C and a humidity of 50% RH, the tape and the sheet are opposite to each other) (Test method of peeling off a stainless steel test plate at 180°). Under the conditions of a width of 25 mm, a peeling angle of 180°, and a peeling speed of 300 mm/min, the test piece is peeled along the length direction of the test piece and measured. SUS boards can use SUS304, surface finishing BA (Bright Annealing, bright annealing), thickness 1.5 mm, width 100 mm, length 150 mm.

In addition, in the adhesive tape for semiconductor processing of the present invention, the adhesive force to the SUS plate after energy ray irradiation is preferably 2 N/25 mm or less, and more preferably 1 N/25 mm or less. By setting the adhesive force to the SUS plate after energy ray irradiation to the above range, the adherend can be easily peeled off from the adhesive tape for semiconductor processing after energy ray irradiation. On the other hand, there is no particular limit to the lower limit of the adhesive force of the SUS board after irradiation with the energy rays. For example, it can be set to 0.01 N/25 mm or more.

Here, the adhesion to the SUS board after energy ray irradiation can be measured by the following method. First, the adhesive layer of the adhesive tape for semiconductor processing is irradiated with energy rays to harden it. At this time, for example, energy rays can be irradiated from the base material side surface of the adhesive tape for semiconductor processing. Then, the test method 1 according to JIS Z0237:2009 (Test method for adhesive tape-adhesive sheet) (at a temperature of 23°C and a humidity of 50%RH, place the tape and sheet at 180° relative to the stainless steel test plate) Peeling test method), under the conditions of width 25 mm, peeling angle 180°, peeling speed 300 mm/min, peel along the length direction of the test piece, and measure the adhesion to the SUS board after energy ray irradiation. SUS boards can use SUS304, surface finish BA, thickness 1.5 mm, width 100 mm, length 150 mm.

2.Adhesive layer The adhesive layer in the present invention is arranged on one side of the base material and has energy ray curability. The energy ray-hardenable adhesive layer is hardened by irradiation with energy rays, thereby reducing the adhesive force. In the energy ray-hardenable adhesive layer, the adherend can be fixed by its initial adhesive force. In addition, in the energy ray curable adhesive layer, by irradiating energy rays to harden it, the adhesive force is reduced and the peelability is improved, so the adherend can be peeled off or transferred.

Examples of energy rays include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and gamma rays, electron beams, proton beams, and neutron rays. Among them, from the viewpoint of versatility and the like, ultraviolet rays and electron beams are preferred, and ultraviolet rays are more preferred.

The adhesive layer is not particularly limited as long as it satisfies the above-mentioned adhesive force. For example, it may contain at least a resin (adhesive main agent) and an energy ray curable compound. By making the adhesive layer contain an energy ray curable compound and hardening the energy ray curable compound by irradiation with energy rays, the adhesion force can be reduced, and the cohesion force is increased at this time, so peeling becomes easy.

(1) Resin (adhesive main agent) Examples of the resin (adhesive main agent) include acrylic resin, polyester resin, polyimide resin, silicone resin, and other resins commonly used as the main agent of adhesives. Among them, acrylic resin is preferred. By using acrylic resin, paste residue on the adherend can be reduced.

Therefore, the adhesive layer preferably contains at least an acrylic resin, an energy ray curable compound, and a cross-linking agent. In the adhesive layer, the acrylic resin usually exists as a cross-linked body in which acrylic resins are cross-linked by a cross-linking agent. The acrylic resin may also be included together with the cross-linked body as a single component.

(Acrylic resin) The acrylic resin is not particularly limited, and examples thereof include (meth)acrylate polymers obtained by homopolymerizing (meth)acrylate; and (meth)acrylate as the main component. (Meth)acrylate copolymer obtained by copolymerizing acrylic acid ester with other monomers. Among them, a (meth)acrylate copolymer is preferred. Specific examples of (meth)acrylate and other monomers include those disclosed in Japanese Patent Application Laid-Open No. 2012-31316. Other monomers can be used individually or in combination of 2 or more types.

Among them, as the acrylic resin, (meth)acrylic acid ester is preferably used as the main component, and the (meth)acrylic acid ester is obtained by the copolymerization of the above-mentioned (meth)acrylic acid ester and a copolymerizable hydroxyl-containing monomer. Acrylate copolymer; or (meth)acrylate as the main component, obtained by copolymerization of the above-mentioned (meth)acrylate and copolymerizable hydroxyl-containing monomers and carboxyl-containing monomers Acrylic copolymer.

In addition, in this specification, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid.

The copolymerizable hydroxyl group-containing monomer and carboxyl group-containing monomer are not particularly limited, and for example, the hydroxyl group-containing monomer and carboxyl group-containing monomer disclosed in Japanese Patent Application Laid-Open No. 2012-31316 can be used.

By adjusting the molecular weight of the acrylic resin, the above ΔE ^* _ab can be controlled. Specifically, as described above, by increasing the molecular weight of the acrylic resin, the above ΔE ^* _ab can be reduced. The weight average molecular weight of the acrylic resin is, for example, preferably from 100,000 to 2 million, more preferably from 200,000 to 1 million. By setting the weight average molecular weight of the acrylic resin within the above range, paste residue or contamination on the adherend can be reduced.

Here, in this specification, the weight average molecular weight is a polystyrene-converted value when measured by gel permeation chromatography (GPC). The weight average molecular weight can be measured, for example, by using HLC-8220GPC manufactured by Tosoh Corporation as a measuring device, TSKGEL-SUPERMULTIPORE-HZ-M manufactured by Tosoh Corporation as a column, THF (Tetrahydrofuran, tetrahydrofuran) as a solvent, and using molecular weight Standard polystyrenes of 1050, 5970, 18100, 37900, 96400, and 706000 were used as standards for measurement.

In addition, by adjusting the glass transition temperature of the acrylic resin, the above-mentioned ΔE ^* _ab can be controlled. Specifically, as mentioned above, by increasing the glass transition temperature of the acrylic resin, the above ΔE ^* _ab can be reduced. The glass transition temperature of acrylic resin can be adjusted appropriately.

Furthermore, the acrylic resin may have energy ray curability, for example, it may have an energy ray curable functional group in a side chain. The energy ray curable functional group preferably has an ethylenically unsaturated bond, for example. Specific examples thereof include (meth)acrylyl group, vinyl group, allyl group, and the like.

(2) Energy ray hardening compounds The energy ray curable compound is not particularly limited as long as it polymerizes upon being irradiated with energy rays. Examples thereof include compounds having an energy ray curable functional group.

Examples of the energy ray curable compound include energy ray curable monomers, energy ray curable oligomers, and energy ray curable polymers. In addition, the energy ray curable polymer is a polymer different from the above-mentioned resin (adhesive main agent). Among them, from the viewpoint of the balance of adhesive force before and after energy ray irradiation, an energy ray curable oligomer is preferred. Moreover, an energy ray curable monomer, an energy ray curable oligomer, and an energy ray curable polymer can be used in combination. For example, when an energy ray curable monomer is used in addition to an energy ray curable oligomer, when energy rays are irradiated, the adhesive layer can be hardened by three-dimensional crosslinking to reduce the adhesive force and increase the cohesive force. Do not allow it to turn toward the adherend.

Examples of the energy ray curable compound include radical polymerizable compounds, cationic polymerizable compounds, anionic polymerizable compounds, and the like. Among them, radically polymerizable compounds are preferred. The hardening speed is fast, and the physical properties such as adhesion before and after energy ray irradiation can be easily controlled by selecting from a variety of compounds.

In the energy ray curable compound, the number of energy ray curable functional groups is preferably 2 or more per molecule, more preferably 3 or more per molecule, further preferably 4 or more per molecule, and particularly preferably More than 5 in 1 molecule. If the number of energy ray curable functional groups is within the above range, the crosslinking density of the adhesive layer after energy ray irradiation becomes sufficient, so that the required peelability can be achieved. In addition, it can suppress the generation of contamination and paste residue caused by the reduction of cohesive force. In addition, the upper limit of the number of energy ray hardenable functional groups is not particularly limited.

Moreover, the energy ray curable compound may further have a functional group capable of reacting with the crosslinking agent. Examples of such functional groups include hydroxyl group, carboxyl group, and the like. By reacting the energy ray curing compound with the cross-linking agent and cross-linking with the resin (adhesive main agent), the generation of contamination or paste residue can be suppressed.

The energy ray curable compound is preferably a radical polymerizable oligomer, more preferably a radical polymerizable polyfunctional oligomer. Examples of the radically polymerizable oligomer include those disclosed in Japanese Patent Application Laid-Open No. 2012-31316.

Furthermore, as the energy ray curable compound, radical polymerizable oligomers and radical polymerizable monomers can be used, and among these, radical polymerizable polyfunctional oligomers and radical polymerizable polyfunctional monomers can be used. Examples of radically polymerizable monomers include those disclosed in Japanese Patent Application Laid-Open No. 2010-173091.

Examples of the energy ray curable compound include (meth)acrylate monomers, (meth)acrylate oligomers, (meth)acrylate polymers, and the like. Moreover, as an energy ray curable compound, for example, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, etc. can also be used.

In addition, commercially available products can be used as the energy ray curable compound. Examples include: urethane acrylate "Ultraviolet UV7620EA (molecular weight: 4100)" manufactured by Mitsubishi Chemical Co., Ltd.; urethane acrylate "Artresin UN-905 (molecular weight: 50000 to 210000) manufactured by Negami Industrial Co., Ltd. )", "Artresin UN-905DU1 (molecular weight: 26000)", "Artresin UN-951SC (molecular weight: 12500)", "Artresin UN-952 (molecular weight: 6500~9500)", "Artresin UN-953 (molecular weight: 14000) ~40000)", "Artresin UN-954 (molecular weight: 4200)", "Artresin H-219 (molecular weight: 25000 ~ 50000)", "Artresin H-315M (molecular weight: 6600)", "Artresin H-417M (molecular weight : 4000)"; acrylic urethane polymer "8BR-600 (molecular weight: 100000)" manufactured by Taisei Fine Chemical Co., Ltd.; polymer acrylate "UNIDIC V-6850" manufactured by DIC Co., Ltd.; Kyoeisha Chemical Co., Ltd. Manufactured acrylic polymers "SMP-250AP (molecular weight: 20,000 to 30,000)" and "SMP-360A (molecular weight: 20,000 to 30,000)"; acrylic resin acrylate "HA7975" manufactured by Showa Denko Materials Co., Ltd., etc.

The energy ray curable compound can be used alone or in combination of two or more types.

The weight average molecular weight of the energy ray curable compound is not particularly limited, but for example, it is preferably 30,000 or less, more preferably 10,000 or less, and still more preferably 8,000 or less. If the weight average molecular weight of the energy ray curable compound is within the above range, it will show sufficient compatibility with the acrylic resin (adhesive main agent), and the adhesive layer will show the required adhesive force before energy ray irradiation and after energy ray irradiation. The generation of paste residue is suppressed and it can be easily peeled off. On the other hand, the weight average molecular weight of the energy ray curable resin composition can be, for example, 100 or more.

The content of the energy ray curable compound is, for example, preferably from 5 parts by mass to 150 parts by mass, more preferably from 20 parts by mass to 150 parts by mass, and further preferably from 30 parts by mass to 100 parts by mass of the resin (adhesive main agent) More than 100 parts by mass. If the content of the energy ray curable compound is within the above range, the crosslinking density of the adhesive layer after energy ray irradiation becomes sufficient, so that the required peelability can be achieved. In addition, it can suppress the generation of contamination and paste residue caused by the reduction of cohesive force.

(3)Polymerization initiator The adhesive layer may contain a polymerization initiator in addition to the resin (adhesive main agent) and the energy ray curable compound.

As the polymerization initiator, a common photopolymerization initiator can be used. Specific examples include acetophenones, benzophenones, α-hydroxyketones, benzyl methyl ketals, α-aminoketones, and bisylphosphine oxides. When using urethane acrylate as the energy ray curable compound, the polymerization initiator is preferably a biscarboxyphosphine-based polymerization initiator. This polymerization initiator has heat resistance, so when the adhesive composition is applied to a base material and irradiated with energy rays, energy rays can be hardened reliably even when the base material is irradiated with energy rays. Sexual compounds harden.

The polymerization initiator preferably has absorption at a wavelength of 230 nm or more, and preferably has absorption at a wavelength of 300 nm or more and 400 nm or less. This kind of polymerization initiator can absorb a wide range of energy rays with wavelengths above 300 nm and efficiently generate active species that induce the polymerization reaction of energy ray curing compounds. Therefore, even with a small amount of energy ray irradiation, the energy ray curable compound can be hardened efficiently and can be easily peeled off. In addition, resins and the like can be used as the base material as described below. Most of the resins absorb energy rays with a wavelength of up to about 300 nm, but transmit energy rays with a wavelength of about 300 nm or more. Furthermore, in recent years, LED (Light Emitting Diode) lamps with a wavelength of 300 nm or above are often used in energy beam irradiation devices. Therefore, by using a polymerization initiator that has absorption at a wavelength of 230 nm or more, the energy rays that pass through the base material can be used to harden the energy ray curable compound.

The content of the polymerization initiator is, for example, preferably not less than 0.01 parts by mass and not more than 10 parts by mass, more preferably not less than 0.3 parts by mass and not more than 6 parts by mass, based on 100 parts by mass of the total of the resin (adhesive main agent) and the energy ray curable compound. . If the content of the polymerization initiator does not satisfy the above range, the polymerization reaction of the energy ray curable compound may not occur sufficiently, and the adhesive force of the adhesive layer after energy ray irradiation may become too high, making it impossible to achieve peelability. On the other hand, if the content of the polymerization initiator exceeds the above range, the cohesion force may decrease, resulting in contamination or paste residue.

(4) Cross-linking agent The adhesive layer may contain a cross-linking agent in addition to the resin (adhesive main agent) and the energy ray curable compound.

The cross-linking agent is not particularly limited as long as it at least cross-links resins (adhesive main agents), and can be appropriately selected according to the type of resin (adhesive main agent), etc., for example, an isocyanate-based cross-linking agent can be used , epoxy cross-linking agent, metal chelate cross-linking agent, etc. Specific examples of the isocyanate cross-linking agent and the epoxy cross-linking agent include those disclosed in Japanese Patent Application Laid-Open No. 2012-31316. A cross-linking agent can be used individually or in combination of 2 or more types.

The content of the cross-linking agent can be appropriately set according to the type of cross-linking agent. For example, based on 100 parts by mass of the resin (adhesive main agent), it is preferably not less than 0.01 parts by mass and not more than 15 parts by mass, and more preferably not less than 0.01 parts by mass. 10 parts by mass or less. If the content of the cross-linking agent does not meet the above range, the adhesion may be poor, or the adhesive layer may be agglomerated and broken when the adherend is peeled off or transferred, resulting in paste residue. On the other hand, if the content of the cross-linking agent exceeds the above range, the cross-linking agent will remain as an unreacted monomer in the adhesive layer after energy ray irradiation, resulting in contamination or paste residue due to reduced cohesion. condition.

(5)Additives The adhesive layer may optionally contain various additives. Examples of additives include adhesion-imparting agents, antistatic agents, plasticizers, silane coupling agents, metal chelating agents, surfactants, antioxidants, ultraviolet absorbers, colorants, preservatives, defoaming agents, moisturizers, etc. Moisture adjuster, adhesion adjuster, etc.

By adjusting the glass transition temperature of the additive, the above ΔE ^* _ab can be controlled. Specifically, as mentioned above, by increasing the glass transition temperature of the additive, the above ΔE ^* _ab can be reduced. The glass transition temperature of the additive is not particularly limited, but for example, it is preferably 5°C or more and 150°C or less, and more preferably 10°C or more and 120°C or less. By setting the glass transition temperature of the additive within the above range, it can be easily adjusted so that the above ΔE ^* _ab falls within a predetermined range. When the adhesive layer contains additives, it is preferable that the glass transition temperature of at least one additive is within the above range.

Furthermore, by adjusting the molecular weight of the additive, the above ΔE ^* _ab can be controlled. Specifically, as mentioned above, by increasing the molecular weight of the additive, the above ΔE ^* _ab can be reduced. The weight average molecular weight of the additive is not particularly limited, and may be, for example, 100 to 200,000, or 500 to 300,000.

Moreover, as mentioned above, the adhesive layer may contain an adhesive force modifier. Examples of the adhesion modifier include acrylic block copolymers, polyester resins, and the like. Examples of the acrylic block copolymer include the KURARITY series manufactured by Kuraray Corporation (for example, "LA4285 (Mw: approximately 65000)", "LA2250 (Mw: approximately 67000)", "LA2140 (Mw: approximately 125000)" , "LA3320 (Mw: about 115000)", etc.). Examples of the polyester resin include Vylon series manufactured by Toyobo Corporation (for example, "Vylon200 (Mn: approximately 17000)", "Vylon600 (Mn: approximately 16000)", etc.), and Elitel series manufactured by Unitika Corporation (" Elitel UE3210 (Mw: approximately 20,000)", "Elitel UE9200 (Mw: approximately 15,000)", etc.).

In addition, by adjusting the content of the additive, the above-mentioned ΔE ^* _ab can be controlled. Specifically, when the molecular weight of the additive is large, the above-mentioned ΔE ^* _ab can be reduced by reducing the content of the additive. The content of additives can be adjusted appropriately.

(6) Thickness and formation method of adhesive layer The thickness of the adhesive layer is sufficient as long as sufficient adhesion is obtained and energy rays can penetrate to the inside. For example, it is 3 μm or more and 50 μm or less, preferably 5 μm or more and 40 μm or less.

Examples of methods for forming the adhesive layer include: coating an adhesive composition on a base material; or coating an adhesive composition on a release film to form an adhesive layer, and bonding the adhesive layer and the base material. method.

3.Substrate The base material in the present invention is a member that supports the above-mentioned adhesive layer.

The base material is not particularly limited, but it is preferable that the adhesive layer is hardened by irradiating energy rays from the base material side of the adhesive tape for semiconductor processing, thereby reducing the adhesive force of the adhesive layer. Therefore, the base material is preferably energy-transmitting liners.

The Young's modulus of the base material may be, for example, 2000 MPa or less, 1000 MPa or less, or 700 MPa or less. Moreover, the Young's modulus of the base material is, for example, preferably 20 MPa or more, more preferably 30 MPa or more, and still more preferably 40 MPa or more. Among them, the base material is preferably expandable. If the Young's modulus of the base material is too low, the base material may become extremely soft, making it difficult to spread the adhesive tape for semiconductor processing uniformly.

Here, the Young's modulus of the base material can be measured in accordance with JIS K7127. Specific measurement conditions are shown below. ・Test piece: Test piece type 5 ・Distance between chucks: 60 mm ・Stretching speed: 100 mm/min As a tensile testing machine, "Tensilon RTF1150" manufactured by A&D Co., Ltd. can be used, for example.

The material of the base material is preferably one that satisfies the above characteristics. Examples include: low density polyethylene, high density polyethylene, polypropylene, polybutylene, polymethylpentene, polybutadiene, and ethylene-acetic acid. Vinyl ester copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer and other olefin resins; polyvinyl chloride, vinyl chloride copolymer and other vinyl chloride resins; polyvinyl chloride Polyester resins such as ethylene phthalate and polybutylene terephthalate; urethane resins; polystyrene resins; polycarbonate resins; fluorine resins, etc. In addition, examples of the material of the base material include: olefin elastomer, vinyl chloride elastomer, polyester elastomer, styrene elastomer, urethane elastomer, acrylic elastomer, Thermoplastic elastomers such as amide elastomers; isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, butyl rubber, halogenated butyl rubber, Acrylic rubber, urethane rubber, polysulfide rubber and other rubber-based materials. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Among them, olefin resins, polyester resins, and vinyl chloride resins are preferred. That is, the base material preferably contains an olefin resin, a polyester resin, or a vinyl chloride resin. Vinyl chloride resin is softened by adding a plasticizer, so by using so-called soft vinyl chloride resin, a base material without a sinking point can be produced as follows. On the other hand, olefin-based resins or polyester resins do not add a large amount of plasticizers like vinyl chloride resins, so the content of additives can be reduced, and the above-mentioned ΔE ^* _ab tends to become smaller.

Examples of the vinyl chloride resin include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride- Propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-propylene Nitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chlorine Chlorine-containing resins such as ethylene-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers; mixtures of these chlorine-containing resins; etc. Mixtures of chlorine-containing resins and other chlorine-free resins, block copolymers, graft copolymers, etc. Examples of other chlorine-free resins include: acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth)acrylate Ester copolymer, polyester, etc.

The base material may also contain various additives such as plasticizers, fillers, antioxidants, light stabilizers, antistatic agents, lubricants, dispersants, flame retardants, colorants and the like as necessary.

Furthermore, by adjusting the molecular weight of the additive, the above ΔE ^* _ab can be controlled. Specifically, by increasing the molecular weight of the additive, the above ΔE ^* _ab can be reduced. The molecular weight of the additives can be adjusted appropriately.

In addition, by adjusting the content of the additive, the above-mentioned ΔE ^* _ab can be controlled. Specifically, when the molecular weight of the additive is small, the above-mentioned ΔE ^* _ab can be reduced by reducing the content of the additive. The content of additives can be adjusted appropriately. For example, when the base material contains vinyl chloride resin, the above ΔE ^* _ab can be reduced by reducing the content of the plasticizer.

The base material may be a single layer or multiple layers, for example.

Surface treatment can be performed on the adhesive layer side of the base material in order to improve the adhesion with the adhesive layer. The surface treatment is not particularly limited, and examples thereof include corona treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, alkali treatment, and the like.

The thickness of the base material is not particularly limited, but may be, for example, 20 μm or more and 500 μm or less, 40 μm or more and 350 μm or less, or 50 μm or more and 200 μm or less. If the thickness of the base material is within the above range, the base material can be easily expanded and have sufficient strength to prevent breakage.

4.Other components The adhesive tape for semiconductor processing of the present invention may, in addition to the above-mentioned base material and adhesive layer, have other structures as necessary.

The adhesive tape for semiconductor processing of the present invention may have an isolation film on the surface of the adhesive layer opposite to the base material. The adhesive layer can be protected by the isolation film.

Furthermore, the adhesive tape for semiconductor processing of the present invention may have a primer layer between the base material and the adhesive layer. Through the primer, the adhesion between the substrate and the adhesive layer can be improved. In addition, the primer layer can inhibit the components contained in the base material from being transferred to the adherend through the adhesive layer. As a result, the above-mentioned ΔE ^* _ab can be reduced. Among them, when the base material contains vinyl chloride resin, it is preferable to arrange a primer layer between the base material and the adhesive layer.

5.Use The adhesive tape for semiconductor processing of the present invention can be suitably used as an adhesive tape for temporarily fixing or protecting parts, such as a dicing tape and a back polishing tape.

2(a) to 2(e) are step diagrams showing an example of a semiconductor manufacturing method using an adhesive tape for semiconductor processing, and are an example in which the adhesive tape for semiconductor processing is used as a dicing tape. First, as shown in FIG. 2(a) , the wafer 11 on which the circuit is formed is attached to the adhesive tape 10 for semiconductor processing. Then, as shown in FIG. 2(b) , the wafer 11 on which the circuit is formed is cut. (Cutting) into the cutting step of wafer 12. Next, as shown in FIG. 2(c) , an expansion step is performed in which the adhesive tape 10 for semiconductor processing is stretched to expand the distance between the wafers 12 . Next, although not shown in the figure, the energy ray curable adhesive layer 2 of the adhesive tape 10 for semiconductor processing is irradiated with energy rays to harden it, thereby reducing the adhesive force, as shown in FIG. 2(d) . The wafer 12 is peeled off from the adhesive tape 10 for semiconductor processing, and the wafer 12 is picked up. Then, as shown in FIG. 2(e) , a mounting (wafer bonding) step of attaching the picked chip 12 to the substrate 30 is performed.

3 (a) to (d) are step diagrams showing another example of a semiconductor manufacturing method using an adhesive tape for semiconductor processing, and are an example in which the adhesive tape for semiconductor processing is used as a dicing tape. First, as shown in FIG. 3(a) , the wafer 11 on which the circuit is formed is attached to the adhesive tape 10 for semiconductor processing. Then, as shown in FIG. 3(b) , the wafer 11 on which the circuit is formed is cut. (Cutting) into the cutting step of wafer 12. Next, as shown in FIG. 3(c) , after the transfer tape 40 is attached to the surface of the wafer 12 opposite to the adhesive tape 10 for semiconductor processing, although not shown in the figure, the energy of the adhesive tape 10 for semiconductor processing is applied. The linearly curable adhesive layer 2 is irradiated with energy rays to harden it, thereby reducing the adhesive force. As shown in FIG. 3(d) , the adhesive tape 10 for semiconductor processing is peeled off from the wafer 12, and the wafer 12 is transferred to The transfer step of the transfer belt 40 .

In addition, this invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are examples, and any embodiments that have substantially the same configuration as the technical ideas described in the patent claims of the present invention and exhibit the same functions and effects are included in the technical scope of the present invention. [Example]

Hereinafter, Examples and Comparative Examples will be shown to further explain the present invention.

[Material] Materials used in adhesive compositions are shown below. ・Adhesive main agent A (acrylate copolymer, weight average molecular weight about 500,000, solid content 23%) ・Adhesive main agent B (acrylate copolymer, weight average molecular weight about 800,000, solid content 20%) ・Urethane acrylate A (ultraviolet curable compound, 10 functions, molecular weight 500 to 1300) ・Urethane acrylate B (UV curable compound, 9 functions, molecular weight 4100, active ingredient 65%) ・Urethane acrylate C (UV curable compound, 6 functions, molecular weight 4200, active ingredient 60%) ・Urethane acrylate D (UV curable compound, 10 functional, molecular weight 2000) ・Pentaerythritol triacrylate (a mixture containing pentaerythritol triacrylate as the main component and pentaerythritol tetraacrylate) (ultraviolet curable compound, 3 to 4 functional, molecular weight 280 to 360) ・Polymerization initiator ("Omnirad 819" manufactured by IGM Resins) ・Crosslinking agent A (isocyanate hardener (toluene diisocyanate (TDI) adduct type (trimethylolpropane adduct)), solid content 75%) ・Crosslinking agent B (epoxy hardener) ・Crosslinking agent C (metal chelate hardener) ・Adhesion modifier A (acrylic block copolymer (triblock copolymer of methyl methacrylate-butyl acrylate-methyl methacrylate), weight average molecular weight approximately 65,000) ・Adhesion adjuster B (acrylic copolymer)

[Example 1] Based on the solid content ratio, mix 100 parts by mass of adhesive main agent A, 50 parts by mass of urethane acrylate A, 3 parts by mass of cross-linking agent A, and 1.5 parts by mass of polymerization initiator with methyl A mixed solvent of ethyl ketone and toluene (mixing ratio 1:1) was diluted to a solid content of 25% and fully dispersed to prepare an adhesive composition.

On the release-treated polyethylene terephthalate (PET) isolation film, apply the above-mentioned adhesive composition so that the thickness after drying becomes 10 μm, and dry it in an oven at 110°C for 3 minutes to form Adhesive layer.

Then, the base material (polyethylene terephthalate (PET) film, "TA051" manufactured by Toyobo Co., Ltd., thickness 50 μm) was laminated on the above-mentioned adhesive layer, and then aged at 50°C for 3 days. , and make adhesive tapes for semiconductor processing.

[Example 2] The adhesive composition was prepared in the following manner, the thickness of the adhesive layer was set to 20 μm, and the following base material was used. Except for this, an adhesive tape for semiconductor processing was produced in the same manner as in Example 1.

Based on the solid content ratio, mix 100 parts by mass of adhesive main agent B, 40 parts by mass of urethane acrylate B, 30 parts by mass of urethane acrylate C, and 0.35 parts by mass of cross-linking agent B. , 0.2 parts by mass of cross-linking agent C, 6 parts by mass of polymerization initiator, and 0.5 parts by mass of adhesion adjuster A were diluted with a mixed solvent of methyl ethyl ketone and toluene (mixing ratio 1:1). The solid content is 25%, and the adhesive composition is prepared by fully dispersing it.

In addition, as the base material, a resin composition containing 70 parts by mass of vinyl chloride resin, 25 parts by mass of plasticizer, and 0.3 parts by mass of nonylphenol was used, and a film was formed by a calendering method to produce polyvinyl chloride with a thickness of 90 μm. (PVC) membrane.

[Example 3] The adhesive composition was prepared in the following manner, the thickness of the adhesive layer was set to 20 μm, and the following base material was used. Except for this, an adhesive tape for semiconductor processing was produced in the same manner as in Example 1.

Based on the solid content ratio, 100 parts by mass of adhesive main agent B, 75 parts by mass of urethane acrylate A, 0.35 parts by mass of cross-linking agent B, 7.5 parts by mass of polymerization initiator, 40 parts by mass The adhesion adjuster A and 40 parts by mass of the adhesion adjuster B were diluted with a mixed solvent of methyl ethyl ketone and toluene (mixing ratio 1:1) to a solid content of 25% to fully disperse to prepare an adhesive composition.

In addition, as the base material, a resin composition containing 70 parts by mass of vinyl chloride resin, 25 parts by mass of plasticizer, and 0.3 parts by mass of nonylphenol was used, and a film was formed by a calendering method to produce polyvinyl chloride with a thickness of 70 μm. (PVC) membrane.

[Example 4] The same procedure as in Example 1 was performed except that the thickness of the adhesive layer was set to 30 μm and a polyethylene (PE) film ("Esmer VPM-S" manufactured by Japan Matai Co., Ltd., thickness 100 μm) was used as the base material. method to produce adhesive tapes for semiconductor processing.

[Example 5] The adhesive composition was prepared in the following manner. The thickness of the adhesive layer was set to 20 μm, and the same polyvinyl chloride (PVC) film with a thickness of 90 μm as in Example 2 was used. Otherwise, the same method was used as in Example 1. Method to produce adhesive tape for semiconductor processing.

Based on the solid content ratio, mix 100 parts by mass of adhesive main agent A, 50 parts by mass of pentaerythritol triacrylate, 3 parts by mass of cross-linking agent A, and 5 parts by mass of polymerization initiator with methyl ethyl ketone and A mixed solvent of toluene (mixing ratio 1:1) was diluted to a solid content of 25% and fully dispersed to prepare an adhesive composition.

[Example 6] The adhesive composition was prepared in the following manner. The thickness of the adhesive layer was set to 20 μm, and the same polyvinyl chloride (PVC) film with a thickness of 90 μm as in Example 2 was used. Otherwise, the same method was used as in Example 1. Method to produce adhesive tape for semiconductor processing.

Based on the solid content ratio, mix 100 parts by mass of adhesive main agent A, 75 parts by mass of pentaerythritol triacrylate, 3 parts by mass of cross-linking agent A, and 7.5 parts by mass of polymerization initiator with methyl ethyl ketone and A mixed solvent of toluene (mixing ratio 1:1) was diluted to a solid content of 25% and fully dispersed to prepare an adhesive composition.

[Example 7] The adhesive composition was prepared in the following manner. The thickness of the adhesive layer was set to 20 μm, and the same polyvinyl chloride (PVC) film with a thickness of 90 μm as in Example 2 was used. Otherwise, the same method was used as in Example 1. Method to produce adhesive tape for semiconductor processing.

Based on the solid content ratio, mix 100 parts by mass of adhesive main agent A, 50 parts by mass of urethane acrylate D, 3 parts by mass of cross-linking agent A, and 5 parts by mass of polymerization initiator with methyl A mixed solvent of ethyl ketone and toluene (mixing ratio 1:1) was diluted to a solid content of 25% and fully dispersed to prepare an adhesive composition.

[Example 8] Except for preparing the adhesive composition in the following manner, an adhesive tape for semiconductor processing was produced in the same manner as in Example 1.

Based on the solid content ratio, mix 100 parts by mass of adhesive main agent A, 50 parts by mass of urethane acrylate D, 3 parts by mass of cross-linking agent A, and 5 parts by mass of polymerization initiator with methyl A mixed solvent of ethyl ketone and toluene (mixing ratio 1:1) was diluted to a solid content of 25% and fully dispersed to prepare an adhesive composition.

[Comparative example 1] The adhesive composition was prepared in the following manner, the thickness of the adhesive layer was set to 20 μm, and the following base material was used. Except for this, an adhesive tape for semiconductor processing was produced in the same manner as in Example 1.

Based on the solid content ratio, 100 parts by mass of adhesive main agent B, 75 parts by mass of urethane acrylate A, 0.35 parts by mass of cross-linking agent B, 7.5 parts by mass of polymerization initiator, 40 parts by mass The adhesion adjuster A and 40 parts by mass of the adhesion adjuster B were diluted with a mixed solvent of methyl ethyl ketone and toluene (mixing ratio 1:1) to a solid content of 25% to fully disperse to prepare an adhesive composition.

Furthermore, as the base material, a resin composition containing 70 parts by mass of vinyl chloride resin, 40 parts by mass of plasticizer, and 0.5 parts by mass of stabilizer was used, and a film was formed by a casting method to produce polyvinyl chloride with a thickness of 70 μm. (PVC) membrane.

[Comparative example 2] An adhesive tape for semiconductor processing was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was 20 μm and the following base material was used.

As the base material, a resin composition containing 70 parts by mass of vinyl chloride resin, 40 parts by mass of plasticizer, and 0.5 parts by mass of stabilizer was used to form a film by a casting method to produce a polyvinyl chloride (PVC) with a thickness of 70 μm. )membrane.

[Evaluation] (1) Color difference ΔE ^* _ab First, cut the adhesive tape for semiconductor processing into a size of 40 mm or more in width and 100 mm or more in length. Furthermore, the glossy surface of the copper foil ("RCF-T5B" manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., thickness 35 μm) was wiped with isopropyl alcohol (IPA) and dried sufficiently. Then, in an environment with a temperature of 25°C ± 5°C, a humidity of 40% RH or more and a range of 60% RH or more, and blocking ultraviolet rays, peel off the isolation film of the adhesive tape for semiconductor processing to expose the adhesive layer, and run the 2 kg roller back and forth twice. The surface of the adhesive layer of the adhesive tape for semiconductor processing is bonded to the glossy surface of the copper foil to obtain a laminated body. Then, the laminated body was stored for 6 days in an environment with a temperature of 25°C ± 5°C, a humidity of 40% RH or more and 50% RH or less, and ultraviolet rays. Then, the surface of the laminated body on the adhesive tape side for semiconductor processing is irradiated with ultraviolet rays so that the cumulative light intensity is 500 mJ/cm ² to harden the adhesive layer. Then, the adhesive tape for semiconductor processing was peeled off from the laminated body at a peeling speed of 300 mm/min.

According to JIS Z8722, use a spectrophotometer ("Spectrophotometer SE6000" manufactured by Nippon Denshoku Industries Co., Ltd.) to measure the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded and the copper foil after the adhesive tape for semiconductor processing is peeled off. Calculate ΔE ^* _ab based on the brightness L ^* and chromaticity a ^* and b ^* of the adhered surface. The measurement conditions were set to D65 light source, 10° visual field, and reflectance measurement. At this time, when measuring the color of the adhered surface of the copper foil before laminating the adhesive tape for semiconductor processing, the adhered surface of the copper foil is wiped with isopropyl alcohol and dried sufficiently before measurement.

(2) Hygroscopicity The wettability of the adhered surface of the copper foil before lamination of the above-mentioned adhesive tape for semiconductor processing and the adhered surface of the copper foil after the adhesive tape for semiconductor processing was peeled off was confirmed. Specifically, a Dyne pen ("EnerDyne Dyne Pen Variety" manufactured by Enercon Co., Ltd.) was used to draw lines on the adhered surface of the above-mentioned copper foil and left to stand for 5 seconds. The case where the ink is retained is judged as having wettability, and the case where the ink is repelled is judged as having no wettability. The Dyne numbers of the Dyne pen are set to 30, 38, and 48.

Regarding the adhesive surface of the copper foil before laminating the adhesive tape for semiconductor processing, all three types of dyne pens were judged to be wettable.

The wettability of the adhered surface of the copper foil after peeling off the adhesive tape for semiconductor processing was evaluated based on the following criteria. A: All three types of dyne pens are judged to be moisturizing. B: Among the three types of dyne pens, 2 types of dyne pens were judged to have hygroscopicity, and 1 type of dyne pen was judged to have no hygroscopicity. C: Among the three types of dyne pens, two or more types of dyne pens are judged to be non-humidifying.

(3) Adhesion to SUS board The adhesion force of the SUS board is tested according to the test method 1 of JIS Z0237:2009 (Adhesive tape-adhesive sheet test method) (at a temperature of 23°C and a humidity of 50% RH, the tape and sheet are tested against stainless steel (Test method of peeling off the test piece at 180°). Under the conditions of width 25 mm, peeling angle 180°, and peeling speed 300 mm/min, the test piece is peeled along the length direction and measured. The SUS board uses SUS304, surface finish BA, thickness 1.5 mm, width 100 mm, length 150 mm.

(4) Adhesion to the SUS board after energy ray irradiation First, irradiate ultraviolet rays from the substrate side of the adhesive tape for semiconductor processing at a cumulative light intensity of 500 mJ/cm ² to harden the adhesive layer. The adhesion of the adhesive tape for semiconductor processing to the SUS board after ultraviolet irradiation is tested according to the test method 1 of JIS Z0237:2009 (Adhesive tape-adhesive sheet test method) (at a temperature of 23°C and a humidity of 50%RH, Test method of peeling the strip and sheet at 180° relative to the stainless steel test plate), peeling off the test piece along the length direction of the test piece under the conditions of width 25 mm, peeling angle 180°, peeling speed 300 mm/min, and measuring . The SUS board uses SUS304, surface finish BA, thickness 1.5 mm, width 100 mm, length 150 mm.

[Table 1] ΔE ^* _ab Hygroscopicity Adhesion (N/25 mm) initial After UV irradiation Example 1 1.46 A 3.40 0.10 Example 2 1.66 A 9.64 0.66 Example 3 1.18 B 1.50 0.70 Example 4 0.90 A 6.40 0.50 Example 5 0.75 A 1.87 0.51 Example 6 1.48 A 1.89 0.35 Example 7 0.56 A 1.83 0.16 Example 8 0.42 A 4.86 0.02 Comparative example 1 2.72 C 2.18 0.30 Comparative example 2 2.18 C 3.10 0.60

In the adhesive tapes for semiconductor processing of Examples 1 to 8, the color difference ΔE ^* between the adhered surface of the copper foil before the adhesive tape for semiconductor processing was bonded and the adhered surface of the copper foil after the adhesive tape for semiconductor processing was peeled off was confirmed. _ab is a predetermined range, and the wettability of the adhered surface of the copper foil after the adhesive tape for semiconductor processing is peeled off is almost unchanged from the wettability of the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded. On the other hand, in the adhesive tapes for semiconductor processing of Comparative Examples 1 to 2, the color difference between the adhered surface of the copper foil before the adhesive tape for semiconductor processing was bonded and the adhered surface of the copper foil after the adhesive tape for semiconductor processing was peeled off ΔE ^* _ab does not satisfy the predetermined range, and the wettability of the adhered surface of the copper foil after the adhesive tape for semiconductor processing is peeled off changes compared to the wettability of the adhered surface of the copper foil before the adhesive tape for semiconductor processing is bonded.

Furthermore, according to Examples 2 and 3, the above-mentioned ΔE ^* _ab is not necessarily related to the wettability. According to this, it is suggested that the change in the surface state of the copper foil that is not captured by the wettability can be obtained by the above ΔE ^* _ab .

1:Substrate 2:Adhesive layer 10: Adhesive tape for semiconductor processing 11:wafer 12:wafer 30:Substrate 40:Transfer belt

FIG. 1 is a schematic cross-sectional view showing an example of an adhesive tape for semiconductor processing in the present invention. 2(a)-(e) are step diagrams illustrating a semiconductor manufacturing method. 3(a) to (d) are step diagrams illustrating a semiconductor manufacturing method.

1:Substrate

2:Adhesive layer

10: Adhesive tape for semiconductor processing

Claims (3)

An adhesive tape for semiconductor processing, which has a base material and an energy ray hardening adhesive layer disposed on one side of the base material, and has an L ^* a ^* b ^* color determined by the following test The color difference ΔE ^* _ab in the system is less than 2.0. Test: The following steps (1) to (5) are performed in sequence. (1) Laminate the above-mentioned adhesive layer surface of the above-mentioned semiconductor processing adhesive tape to the copper foil, and Preparation of a laminated body; (2) Store the above-mentioned laminated body for 6 days in an environment with a temperature of 25°C ± 5°C, a humidity of 40% RH or more and less than 60% RH, and an energy line blocking environment; (3) The above-mentioned semiconductor of the above-mentioned laminated body The adhesive tape for processing is irradiated with energy rays to harden the adhesive layer; (4) The adhesive tape for semiconductor processing is peeled off from the laminate; (5) The ratio of the copper foil before the adhesive tape for semiconductor processing is bonded is determined. The color difference ΔE ^* _ab in the L ^* a ^* b ^* color system of the adhered surface of the above-mentioned copper foil after peeling off the above-mentioned adhesive tape for semiconductor processing. For example, the adhesive tape for semiconductor processing in claim 1 must have an adhesion force of 1 N/25 mm or more to the SUS board before energy ray irradiation. For example, if the adhesive tape for semiconductor processing in claim 1 or 2 is used, its adhesion to the SUS board after irradiation with energy rays is 2 N/25 mm or less.