TW202020094A - Adhesive tape for dicing and method for manufacturing semiconductor chips - Google Patents

Abstract

An adhesive tape for dicing, said adhesive tape comprising a substrate and a silicone adhesive layer laminated on the substrate, to be used in dividing a semiconductor material, which comprises multiple semiconductor elements coated with a coating material, into multiple semiconductor chips, wherein: the silicone adhesive layer comprises an addition reaction-type silicone adhesive as a main agent together with a photoresponsive platinum (Pt) catalyst and a crosslinking agent for the addition reaction-type silicone adhesive; the ratio by mass of a silicone gum to a silicone resin ranges from 35/65 to 50/50; and the content of a silicone gum having an alkenyl group ranges from 35 mass% to 50 mass% inclusive relative to the total mass of the silicone gum and the silicone resin.

Description

Method for manufacturing adhesive tape for dicing and semiconductor wafer

The present invention relates to a dicing adhesive tape used for dicing a semiconductor material and a method for manufacturing a semiconductor wafer using the dicing adhesive tape. The semiconductor material is a material of a semiconductor wafer.

Conventionally, in order to produce an adhesive tape for dicing used for manufacturing semiconductor wafers having LEDs (Light Emitting Diode) and the like, an adhesive tape having an adhesive layer made of acrylic resin has been known (refer to Patent Document 1). In addition, in order to produce an adhesive tape for dicing used for manufacturing semiconductor wafers including LEDs, an adhesive tape having an adhesive layer made of polysiloxane resin is known (refer to Patent Document 2 and Patent Document 3). In addition, as a method of manufacturing a semiconductor wafer using an adhesive tape for dicing, a method of attaching an adhesive tape to the substrate side of a semiconductor element substrate in which a plurality of semiconductor elements are formed on the substrate, and cutting the semiconductor element substrate by a dicing machine is known (Refer to Patent Document 4). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2013-38408 [Patent Document 2] Japanese Unexamined Patent Publication No. 2015-050216 [Patent Document 3] Japanese Patent Laid-Open No. 2016-122812 [Patent Document 4] Japanese Patent Laid-Open No. 2005-93503

[Problems to be solved by the invention]

However, in recent years, in terms of a method of manufacturing a semiconductor chip that has been diced by dicing, a technique has been proposed that applies an adhesive tape to a plurality of semiconductor elements covered with a coating material such as a sealing resin or a phosphor, The material is cut to meet the so-called wafer-level CSP (wafer-level packaging) process. In this way, when the adhesive tape is adhered to the semiconductor material covered with the semiconductor element as the coating material, depending on the composition of the adhesive layer on the adhesive tape, the material of the coating material, etc., the adhesive force may be insufficient, causing penetration The singulated semiconductor wafer is scattered. In addition, in order to suppress the scattering of the semiconductor wafer, when designing a high adhesive ball layer adhesiveness and adhesive force, when the obtained semiconductor wafer is peeled off from the adhesive tape, the adhesive may sometimes be attached under the semiconductor wafer The remaining so-called adhesive residue.

An object of the present invention is to provide a method for manufacturing an adhesive tape for dicing and a semiconductor wafer using the same, which has good adhesion and adhesion to a semiconductor material having a plurality of semiconductor elements coated with a coating material, In the case of peeling of the individualized semiconductor wafers, the adhesive residue to the semiconductor wafers is suppressed. [Technical means to solve the problem]

Based on this objective, the inventors made a rigorous review of the results of the adhesive layer of the adhesive tape for cutting so that the adhesive layer contains at least the addition-reactive polysiloxane-based adhesive and the addition-reactive polysiloxane-based adhesive. Adhesive crosslinking agent When a specific adhesive is added with a photosensitive platinum (Pt) catalyst, it has good adhesion to semiconductor materials with a plurality of semiconductor elements covered by the coating material. In the case where the diced semiconductor wafer is peeled off, the adhesive residue on the semiconductor wafer is suppressed, and the present invention is created. That is, it was found that when the adhesive layer of the dicing adhesive tape is configured as described above, when a semiconductor material having a plurality of semiconductor elements covered with a coating material is divided into a plurality of semiconductor wafers, due to good adhesion and Adhesion, thus suppressing the scattering of individual semiconductor wafers during dicing. On the other hand, when peeling the diced semiconductor wafer from the dicing adhesive tape, the adhesive layer is irradiated with light such as ultraviolet rays to make the photosensitive platinum (Pt) catalyst in the adhesive After being activated, the crosslinking reaction between the addition reaction type silicone adhesive and the crosslinking agent for the addition reaction type silicone adhesive is promoted, so that the cohesive force of the adhesive becomes larger than before light irradiation. As a result, the adhesion of the adhesive layer is appropriately reduced, and the failure mode in the retention test becomes "interfacial failure" or the "non-falling" one in the retention test. With this, it was found that the pick-up property from the dicing adhesive tape for semiconductor wafers was improved, and the adhesive residues on the semiconductor wafers were also suppressed.

The dicing adhesive tape of the present invention is provided with a base material and a polysilicone-based adhesive layer laminated on the base material, and is used to divide a semiconductor material having a plurality of semiconductor elements covered by a covering material into a plurality of semiconductor wafers On the occasion, the polysiloxane-based adhesive layer uses an addition-reactive polysiloxane-based adhesive as a main agent, including a photosensitive platinum (Pt) catalyst and the intersection of the addition-reactive polysiloxane-based adhesive. Combined agent, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the polysiloxane adhesive layer to the total mass (Rw) of the polysiloxane resin (R) ) Is in the range of 35/65 to 50/50, and the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (G) is 35 The range of more than 50% by mass and less than 50% by mass is based on the adhesive properties of JIS Z 0237 (2009) and meets all of the following conditions (a) to (c): (a) The adhesion to the BA-SUS test plate before light irradiation is 2.4N/10mm or more and 5.5N/10mm or less; (b) The value of the number of balls in the tilted ball viscosity test (inclination angle 30°, temperature 23°C, relative humidity 50% RH) before the light irradiation is BN0, after light irradiation When the value of the number of balls is BN1, the relationship is BN0>BN1; (c) Retention test after light irradiation (temperature 40°C, relative humidity 33%RH, storage time 5000 minutes), the failure phenomenon when falling is the interface between the aforementioned polysiloxane adhesive layer and the BA-SUS test board Failure, or do not fall during the retention test. Here, the adhesive tape for dicing can be used by pasting the semiconductor material sealed by the coating material made of polysiloxane on the semiconductor material from the side of the coating material.

In addition, from other viewpoints, the dicing adhesive tape of the present invention is provided with a base material and a polysiloxane-based adhesive layer laminated on the base material, and is used to cover a plurality of semiconductor elements covered with a coating material When the semiconductor material is divided into a plurality of semiconductor chips, the aforementioned polysiloxane-based adhesive layer is mainly composed of a mixture of an addition-reactive polysiloxane-based adhesive and a peroxide-curable polysiloxane-based adhesive. The total mass (Gw) of the polysiloxane (G) containing the photosensitive platinum (Pt) catalyst and the crosslinking agent for the addition reaction type polysiloxane adhesive, and the polysiloxane adhesive (G) contained in the polysiloxane adhesive layer The mass ratio (Gw)/(Rw) to the total mass (Rw) of the silicone resin (R) is in the range of 40/60 to 56/44. The silicone rubber (G) and the silicone resin ( G) The content ratio of the polysiloxane having an alkenyl group (G1) in the total mass is in the range of 14% by mass or more and 42% by mass or less, which is in accordance with the following adhesive properties under JIS Z 0237 (2009) All of conditions (a) to (c): (a) The adhesion to the BA-SUS test plate before light irradiation is 2.4N/10mm or more and 5.5N/10mm or less; (b) The value of the number of balls in the tilted ball viscosity test (inclination angle 30°, temperature 23°C, relative humidity 50% RH) before the light irradiation is BN0, after light irradiation When the value of the number of balls is BN1, the relationship is BN0>BN1; (c) Retention test after light irradiation (temperature 40°C, relative humidity 33%RH, storage time 5000 minutes), the failure phenomenon when falling is the interface between the aforementioned polysiloxane adhesive layer and the BA-SUS test board Failure, or do not fall during the retention test. Here, the adhesive tape for dicing can be used by pasting the semiconductor material sealed by the coating material made of polysiloxane on the semiconductor material from the side of the coating material. In addition, the aforementioned polysiloxane-based adhesive layer may further include an initiator made of peroxide.

In addition, from another point of view, the method for manufacturing a semiconductor wafer of the present invention includes: a pasting process which seals the above-mentioned dicing adhesive tape to a plurality of the foregoing sealed with a sealing resin made of polysiloxane resin A semiconductor element substrate on which a semiconductor element is formed on the substrate and pasted from the sealing resin side; a cutting procedure, which is to cut the semiconductor element substrate pasted with the dicing adhesive tape into a plurality of semiconductor wafers; The irradiation procedure is to irradiate the dicing adhesive tape of the semiconductor element substrate with light; and the peeling procedure is to peel the dicing adhesive tape from the plurality of semiconductor wafers. [Comparing the efficacy of the previous technology]

According to the present invention, a method for manufacturing an adhesive tape for dicing and a semiconductor wafer using the same can be provided. For a semiconductor material covered by a plurality of semiconductor elements as a coating material, it has good adhesion and adhesion at a stage before light irradiation At the same time, when the semiconductor wafer that has been singulated through dicing is peeled off after light irradiation, it has good pickup properties of the semiconductor wafer while suppressing adhesive residues to the semiconductor wafer.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. [Composition of Adhesive Tape] FIG. 1 is a diagram illustrating an example of the configuration of a dicing adhesive tape 1 (hereinafter simply referred to as an adhesive tape 1) to which this embodiment is applied. The adhesive tape 1 of the present embodiment is used for dicing a semiconductor material that forms the basis of a semiconductor wafer, for example, in a process of a semiconductor wafer having semiconductor elements such as LEDs (Light emitting diodes) and power semiconductors.

As shown in FIG. 1, the adhesive tape 1 has a structure in which an adhesive layer 3 as an example of a polysiloxane adhesive layer is laminated on a base material 2. In addition, although the drawing is omitted, the adhesive tape 1 may be provided with an anchor coating layer between the base material 2 and the adhesive layer 3 as needed to improve the adhesion between the base material 2 and the adhesive layer 3. In addition, a surface treatment may be performed on the surface of the base material 2 (the surface opposite to the surface facing the adhesive layer 3). Furthermore, a release film may be provided on the surface of the adhesive layer 3 (the surface on the side opposite to the surface facing the substrate 2).

<Substrate> The base material 2 of this embodiment is made of a material that transmits light such as ultraviolet rays. The material of the base material 2 is not particularly limited as long as it can transmit light such as ultraviolet rays, and for example, plastics that can transmit light such as ultraviolet rays can be used. In addition, here, the transmittance of light such as ultraviolet light, which does not represent light such as ultraviolet light, can be transmitted to 100%, as long as at least the addition reaction type due to the photosensitive platinum (Pt) catalyst described later of the adhesive layer 3 can be promoted The degree of addition reaction between the polysiloxane adhesive and the cross-linking agent may be transmitted.

For the material of the substrate 2, specifically, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxially stretched polypropylene, aliphatic polyimide (transparency) (Polyimide), cycloolefin, fluorine-based resin, polyolefin resin and other resin films. In addition, depending on the application, for the substrate 2, for example, a composite film in which polyethylene terephthalate and a polyolefin resin film are laminated, and a composite film in which these composite films are further laminated with a resin film, Multilayer resin film made by co-extrusion. Among them, it is preferable to use a material mainly composed of polyethylene terephthalate for the base material 2.

<Adhesive layer> The adhesive layer 3 of this embodiment contains a hardening type silicone adhesive. Specifically, the adhesive layer 3 contains the addition reaction type silicone adhesive in the hardening type silicone adhesive. In addition, in the adhesive layer 3, in addition to the addition reaction-type polysiloxane-based adhesive, the hardening-type polysiloxane-based adhesive may also contain a peroxide-curable polysiloxane-based adhesive. Generally speaking, this addition reaction type polysiloxane adhesive and peroxide curing type polysiloxane adhesive both include polysiloxane (G) made of organic polysiloxane and organic polysiloxane Silicone resin (R) made of oxane. In the following, the adhesive layer 3 containing the addition reaction type polysiloxane-based adhesive in the case of the hardening type silicone adhesive is the first form, and the addition reaction type is included in the hardening type polysiloxane-based adhesive. The adhesive layer 3 of the polysiloxane-based adhesive and the peroxide-curable polysiloxane-based adhesive is in the second form, and each component constituting the adhesive layer 3 will be described in detail.

<Adhesive layer of the first form> The adhesive layer 3 of the first aspect includes an addition reaction type silicone adhesive and a crosslinking agent as an example of a hardener that crosslinks the addition reaction type silicone adhesive. In addition, the adhesive layer 3 of the first aspect includes a photosensitive platinum (Pt) catalyst that promotes the reaction of the addition reaction type polysiloxane-based adhesive and the crosslinking agent by irradiation with light such as ultraviolet rays. In addition, the adhesive layer 3 of the first aspect does not contain a peroxide-curable silicone adhesive. In addition, the adhesive layer 3 of the first aspect may contain other additives such as reinforcing fillers, cohesiveness enhancers, colorants, etc. as needed.

(Addition reaction type polysiloxane adhesive) Although addition reaction type polysiloxane-based adhesives can be used, it is generally known to be an organic polymer containing polydimethylsiloxane containing at least two silicon-bonded alkenyl groups in an average of 1 molecule. Adhesive for polysiloxane (G1) made of silicone and polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane. Here, the polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane does not contain a silicon-bonded alkenyl group.

The following is a polysilicon composed of an organic polysiloxane such as polydimethylsiloxane containing an average of at least two silicon-bonded alkenyl groups per molecule contained in an addition reaction type polysiloxane-based adhesive. The oxygen gum (G1) and the polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane are described in further detail. In addition, in the following description, a polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing at least two silicon-bonded alkenyl groups in an average molecule may be described as Polysiloxane (G1) made of organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl group, or simply described as polysiloxane having alkenyl group (G1).

[Polysiloxane (G1) made of organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl group] The polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl groups in this embodiment is an addition reaction type polysiloxane-based adhesive It is sufficient if it contains at least two silicon-bonded alkenyl groups per molecule, and it is not particularly limited. The molecular structure of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group includes, for example, a linear structure composed of a repeating diorganosiloxane unit in the main chain portion, and the molecule A part of the structure includes a branched structure, a branched structure, or a ring structure. Among them, the organic polysiloxane having a linear structure is preferred from the viewpoints of mechanical strength and the like of the adhesive after irradiation of light such as ultraviolet rays.

The polysiloxane (G1) made of organic polysiloxane containing a silicon-bonded alkenyl group may be oily or raw, but raw rubber is preferred. In the case of oil, it is preferable that the viscosity of the polysiloxane (G1) made of organic polysiloxane is at least 1000 mPa·s at 25°C. When the viscosity is less than 1000 mPa·s, the adhesive before and after light irradiation may not be able to find the desired adhesive properties, and the adhesiveness between the adhesive layer 3 and the base material 2 may be deteriorated. In the case of raw colloid, it is preferable that the viscosity of polysiloxane (G1) made of organopolysiloxane dissolved in toluene at a concentration of 30% by mass is 100,000 mPa·s or less at 25°C. When the viscosity exceeds 100,000 mPa·s, the stirring during preparation of the adhesive composition may become difficult. In addition, the above viscosity can be measured using a BM type rotary viscometer.

The polysiloxane (G1) made of an organic polysiloxane containing a silicon-bonded alkenyl group is, for example, represented by the following general formula (1) or general formula (2), but it is not limited thereto.

…通式(1)【Chemistry 1】

…Formula (1)

…通式(2)【Chemical 2】

…Formula (2)

Here, in the above general formula (1) and general formula (2), R ¹ is a monovalent hydrocarbon group independently having no aliphatic unsaturated bond, and X is an alkenyl group-containing organic group. a is an integer of 0 to 3, m is an integer of 0 or more, and n is an integer of 100 or more, where a and m do not become 0 at the same time. m+n is the value at which the viscosity of the above-mentioned organopolysiloxane at 25° C. becomes 1000 mPa·s or more.

R ¹ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms and preferably having 1 to 7 carbon atoms, which does not have an aliphatic unsaturated bond. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and aromatic groups such as tolyl groups. In particular, methyl or phenyl groups are preferred.

In terms of X, it is preferable that the alkenyl group having 2 to 10 carbon atoms contains an organic group. For example, vinyl, propenyl, hexenyl, octenyl, propenyl propyl, propenyl methyl, methacryl propyl, propenyl oxypropyl, propenyl oxymethyl, methacrylic Acyloxypropyl, methacryloxymethyl, cyclohexenylethyl, vinyloxypropyl, etc. Among them, lower alkenyl groups such as vinyl and allyl are preferred, and vinyl is particularly preferred from an industrial point of view. The binding position of the above alkenyl group is not particularly limited, and may be the molecular chain end, the molecular chain side chain, or both the molecular chain end and the molecular chain side chain.

The number of the above alkenyl groups is appropriate, and the range depends on the polysiloxane resin (R1) made of an organic polysiloxane such as polydimethylsiloxane, which is an addition reaction type polysiloxane-based adhesive. The content, the amount of the cross-linking agent added, and the balance of other added components vary, so it is impossible to generalize, but for example, for 100 organic groups of the organopolysiloxane, the range of 0.1 to 3.0 is generally preferred. Then, within the range of this ratio, it is preferable to adjust the molecular weight so as to be within the above-mentioned viscosity range, and to adjust so that the number of the above-mentioned alkenyl groups per molecule of the organic polysiloxane becomes at least two. When the number of the above alkenyl groups is less than 0.1 with respect to 100 organic groups of the organic polysiloxane, when the adhesive tape 1 is irradiated with light, the adhesive is hard to harden and cohesion is difficult to improve. In this case, the desired adhesion reduction and failure mode in the retention test cannot be obtained. After the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, the obtained semiconductor wafer or the like is peeled from the adhesive tape 1 The pickability of the sliced semiconductor wafer may deteriorate, and the adhesive residue may be easily generated on the semiconductor wafer or the like. On the other hand, when the number of the above-mentioned alkenyl groups exceeds 3.0 with respect to 100 organic groups of the organic polysiloxane, a release film provided with a release treatment of a fluoroalkyl-modified silicone polymer on the adhesive tape 1 is provided In this case, the peeling force of the peeling film of the adhesive layer 3 may increase.

[Polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane] In this embodiment, it is made of organic polysiloxane such as polydimethylsiloxane. The polysiloxane resin (R1) is an organic polysiloxane having R ² ₃ SiO _0.5 units (M units) and SiO ₂ units (Q units), and is a so-called MQ resin. The polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane does not basically have an alkenyl group in the molecule, and it can be used by a publicly known person. R ² is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and exemplified above for R ¹ is exemplified. It is preferable that the organic polysiloxane contains R ² ₃ SiO _0.5 units and SiO ₂ units so that the molar ratio of R ² ₃ SiO _0.5 units/SiO ₂ units is in the range of 0.5 or more and 1.7 or less. When the molar ratio of R ² ₃ SiO _0.5 unit/SiO ₂ unit is less than 0.5, the adhesive force and adhesive force of the obtained adhesive layer 3 may decrease. On the other hand, when the molar ratio of R ² ₃ SiO _0.5 unit/SiO ₂ unit exceeds 1.7, the adhesive force and the holding force of the obtained adhesive layer 3 may decrease. In addition, the above-mentioned organic polysiloxane may have an OH group. In this case, the content of the OH group is preferably 4.0% by mass or less relative to the total mass of the above-mentioned organic polysiloxane. When the OH group exceeds the above upper limit, the curability of the adhesive may decrease.

Two or more of the above organic polysiloxanes can be used in combination. In addition, the above-mentioned organic polysiloxane may have R ² SiO _1.5 units (T units) and/or R ² ₂ SiO units (D units) within a range that does not impair the characteristics of the present invention.

The above-mentioned polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group and an organic polysiloxane such as polydimethylsiloxane The resulting polysiloxane resin (R1) can also be used simply by mixing. In addition, the polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group contains an organic polysiloxane represented by the above general formula (2) In the case of alkane, as long as the characteristics of the present invention are not impaired, it can also be used as a polysiloxane (G1) composed of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group and A polysiloxane resin (R1) made of an organic polysiloxane such as polydimethylsiloxane is used as a (partial) condensation reaction product obtained by reacting in advance.

(The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the adhesive layer of the first form to the total mass (Rw) of the polysiloxane (R), and (The content ratio of polysiloxane (G1) with alkenyl group in the total mass of polysiloxane (G) and polysiloxane resin (R)) In terms of the polysiloxane adhesive constituting the adhesive layer 3 of the first form, the total mass (Gw) of the polysiloxane adhesive (G) is the same as that of the addition reaction type polysiloxane adhesive containing silicon bonding The mass (G1w) of polysiloxane (G1) made of organic polysiloxane such as alkenyl polydimethylsiloxane. Similarly, in terms of the polysiloxane adhesive constituting the adhesive layer 3 of the first form, the total mass (Rw) of the polysiloxane resin (R) is the same as that of the addition reaction type polysiloxane adhesive. The mass (R1w) of polysiloxane resin (R1) made of organic polysiloxane such as dimethylsiloxane.

The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the adhesive layer 3 of the first form to the total mass (Rw) of the polysiloxane (R) (= (G1w)/(R1w)) is preferably in the range of 35/65 to 50/50. In addition, in this case, the content ratio of polysiloxane (G1) having an alkenyl group in the total mass of polysiloxane (G) and polysiloxane resin (R) is {G1w)/((Gw)+ (Rw))}×100 Of course, as described above, it is preferably in the range of 35% by mass or more and 50% by mass or less.

The mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) contained in the adhesive layer 3 of the first form to the total mass (Rw) of the silicone (R), and When the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) is less than the lower limit of the above range, the adhesive tape 1 is irradiated with light At this time, the adhesive is hard to harden and the cohesion is difficult to improve. In this case, the desired adhesion reduction and failure mode in the retention test cannot be obtained. After the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, the obtained semiconductor wafer or the like is peeled from the adhesive tape 1 The pickability of the sliced semiconductor wafer may deteriorate, and the adhesive residue may be easily generated on the semiconductor wafer or the like.

On the other hand, the mass ratio (Gw) of the total mass (Gw) of the silicone (G) contained in the adhesive layer 3 of the first form to the total mass (Rw) of the silicone (R)/( Rw), and the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) exceeds the upper limit of the above range, before the light is irradiated In the uncured state of the adhesive, the adhesive layer 3 becomes too soft due to the silicone (G) component. In this case, during cutting of the semiconductor element substrate or the like, the vibration of the cutting is easily transmitted to the adhesive layer 3 and the amplitude becomes large. For example, the semiconductor element substrate may deviate from the reference position. Then, along with this, chipping (cutting) may occur in the singulated semiconductor wafer, and the size deviation may occur for each semiconductor wafer.

On the other hand, the mass ratio (Gw) of the total mass (Gw) of the polysiloxane (G) contained in the adhesive layer 3 of the first aspect to the total mass (Rw) of the polysiloxane resin (R)/ (Rw), and the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) is within the above range, and the following effects can be achieved . That is, in the stage before the irradiation of light such as ultraviolet rays, the adhesive layer 3 in an uncured state can be imparted with appropriate adhesive force and adhesion that do not occur when the semiconductor wafers, etc., which are diced pieces are scattered at the time of dicing. force. On the other hand, after the irradiation of light, the adhesive layer 3 is hardened to increase the cohesive force, so the desired reduction in adhesion and failure mode in the retention test are obtained. As a result, after the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, good pick-up properties can be achieved when the obtained semiconductor wafer or the like is peeled from the adhesive tape 1, while suppressing adhesive residues on the semiconductor wafer or the like .

In addition, for the addition reaction type silicone adhesive of the present invention, a commercially available addition reaction type silicone adhesive can also be used. Specifically, for example, KR3700, KR3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40-3270, manufactured by Shin-Etsu Chemical Industry Co., Ltd. X-40-3306 (both trade names), TSR1512, TSR1516, XR37-B9204 (both trade names) manufactured by Mitu Hi-Tech Materials Co., Ltd., SD4580, SD4584, SD4585, SD4560, SD4564, SD4565, manufactured by Dow Corning Toray Co., Ltd. For models such as SD4570, SD4574, SD4575, SD4600PFC, SD4593, and DC7651ADHESIVE (all trade names), types of platinum (Pt) catalysts and cross-linking agents described below can be used.

(Crosslinking agent) The crosslinking agent is used to crosslink the alkenyl group contained in the addition reaction type polysiloxane-based adhesive. For the crosslinking agent, an organic polysiloxane (organic hydrogen polysiloxane) having at least two, preferably three or more silicon-bonded hydrogen atoms (SiH) in one molecule is used. Examples of the molecular structure of the organohydrogenpolysiloxane used as a cross-linking agent include straight chains, linear chains partially branched, branched chains, and nets. The organic hydrogen polysiloxane preferably has a viscosity at 25°C of 1 to 5000 mPa·s. In addition, the above viscosity can be measured using a BM type rotary viscometer.

The organic hydrogen polysiloxane used as the cross-linking agent can be conventionally known. For example, although this organic hydrogen polysiloxane is exemplified by the following general formula (3) or general formula (4), it is not limited thereto.

…通式(3)【Chemical 3】

…Formula (3)

…通式(4)【Chemical 4】

…Formula (4)

Here, in the general formula (3) and the general formula (4), R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, b is 0 or 1, p and q are integers, and 25 of the organic hydrogen polysiloxane The viscosity at ℃ becomes a value of 1 to 5000 mPa·s. r is an integer of 2 or more, s is an integer of 0 or more, and r+s≧3, preferably 8≧r+s≧3. Organic hydrogen polysiloxane can be a mixture of two or more.

R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms and preferably 1 to 7 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, aromatic groups such as phenyl and tolyl, and alkenyl groups such as vinyl and allyl. In particular, methyl or phenyl is preferred.

The content of the organic hydrogen polysiloxane used as the cross-linking agent in the adhesive layer 3 of the first aspect is preferably an organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl groups. The total amount of alkenyl groups in the polysiloxane (G1) made of alkanes The total amount of silicon-bonded hydrogen atoms (SiH) in the organohydrogen polysiloxane is 0.15 mol equivalent or more and 15.0 mol equivalent or less The amount is more preferably 1.0 mol equivalent or more and 10.0 mol equivalent or less.

When the content of the organic hydrogen polysiloxane is less than the above lower limit, when the adhesive tape 1 is irradiated with light, the adhesive is hard to harden and cohesion is difficult to improve. In this case, the desired adhesion reduction and failure mode in the retention test cannot be obtained. After the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, the obtained semiconductor wafer or the like is peeled from the adhesive tape 1 The pickability of the sliced semiconductor wafer may deteriorate, and the adhesive residue may be easily generated on the semiconductor wafer or the like.

On the other hand, if the content of the organic hydrogen polysiloxane exceeds the above upper limit, unreacted organic hydrogen polysiloxane may contaminate the semiconductor wafer. In addition, the silicon-bonded hydrogen atoms (SiH) in the unreacted organic hydrogen polysiloxane react with oxygen and moisture in the air to change to SiOH, and the adhesive force of the adhesive layer 3 to the adherend becomes larger, The pickability of individualized semiconductor wafers may deteriorate.

The content of the cross-linking agent in the adhesive layer 3 of the first form is as described above for the polysiloxane composed of organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl group The total amount of alkenyl groups in (G1) may be adjusted such that the total amount of silicon-bonded hydrogen atoms (SiH) in the organic hydrogen polysiloxane is within the above range. Although the content of the crosslinking agent within this range varies depending on the number of silicon-bonded hydrogen atoms (SiH) possessed by the crosslinking agent, for example, the solid content of the addition reaction type polysiloxane-based adhesive is 100 mass Parts, the crosslinking agent may be added so that the solid content becomes 0.2 mass parts or more and 20.0 mass parts or less.

The content of the crosslinking agent for the addition reaction type polysiloxane-based adhesive is within the above range, so that when the semiconductor wafer is peeled from the dicing adhesive tape, ultraviolet light or the like is irradiated to the adhesive layer 3, thereby The photosensitive platinum (Pt) catalyst in the polysiloxane-based adhesive is activated, and the addition reaction type polysiloxane-based adhesive is crosslinked with the crosslinking agent for the addition reaction type polysiloxane-based adhesive. The reaction is promoted, so that the cohesive force of the adhesive becomes larger than before the light irradiation. As a result, the adhesive force of the adhesive layer 3 is appropriately reduced, and a good pick-up property when peeling a semiconductor wafer or the like from the adhesive tape 1 can be achieved, and at the same time, adhesive residue to the semiconductor wafer or the like can be suppressed.

As for the crosslinking agent, as long as it is a crosslinking agent of an addition reaction type polysiloxane-based adhesive, that is, as long as it is an organic having at least two silicon-bonded hydrogen atoms (SiH) in one molecule Polysiloxane (organic hydrogen polysiloxane) is sufficient, and is not particularly limited. Specific examples include X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and BY24-741 (trade name) manufactured by Dow Corning Toray Co., Ltd. and the like.

(Photosensitive platinum (Pt) catalyst) The photosensitive platinum (Pt) catalyst is used to irradiate light such as ultraviolet rays to promote the addition reaction (hydrosilylation) of the addition reaction type polysiloxane-based adhesive constituting the adhesive layer 3 and the crosslinking agent. hardening. The wavelength of light that can be used to promote the hardening due to the addition reaction of the addition reaction type silicone adhesive and the crosslinking agent is preferably in the range of 240 nm or more and 400 nm or less. For the photosensitive platinum (Pt) catalyst, from the viewpoint of good photosensitivity and reaction speed, it is preferable to use a photoactive cyclopentadienyl platinum (IV) compound.

The photoactive cyclopentadienyl platinum (IV) compound is not particularly limited, and examples thereof include (cyclopentadiene) dimethyltrimethylsilylmethyl platinum, (cyclopentadiene) diethyl Trimethylsilylmethylplatinum, (cyclopentadiene) dipropyltrimethylsilylmethylplatinum, (cyclopentadiene) diisopropyltrimethylsilylmethylplatinum, ( (Cyclopentadiene) diallyl trimethylsilyl methyl platinum, (cyclopentadiene) dibenzyl trimethyl silyl methyl platinum, (cyclopentadiene) dimethyl triethyl Silylmethylplatinum, (cyclopentadiene) dimethyltripropylsilylmethylplatinum, (cyclopentadiene) dimethyltriisopropylsilylmethylplatinum, (cyclopentadiene) (Ene) dimethyltriphenylsilylmethylplatinum, (cyclopentadiene) dimethyldimethylphenylsilylmethylplatinum, (cyclopentadiene) dimethylmethyldiphenyl Silylmethyl platinum, (cyclopentadiene) dimethyl dimethyl (trimethylsilyloxy) silyl methyl platinum, (cyclopentadiene) dimethyl dimethyl (dimethyl Vinylvinylsilyloxy)silylmethylplatinum, [(1'-naphthyl)cyclopentadiene] trimethylsilylmethylplatinum, [(2'-naphthyl)cyclopentadiene ]Trimethylsilylmethylplatinum, [1-methyl-3-(1'-naphthyl)cyclopentadiene]trimethylsilylmethylplatinum, [1-methyl-3-( 2'-naphthyl)cyclopentadiene]trimethylsilylmethylplatinum, [(4'-biphenyl)cyclopentadiene]trimethylsilylmethylplatinum,[1-(4' -Biphenyl)-3-methylcyclopentadiene]trimethylsilylmethylplatinum, [(9'-phenanthrene)cyclopentadiene]trimethylsilylmethylplatinum,[1- Methyl-3-(9'-phenanthrene)cyclopentadiene]trimethylsilylmethylplatinum, [1-(2'-anthryl)-3-methylcyclopentadiene]trimethyl Silylmethylplatinum, [(2'-anthracenyl)cyclopentadiene]trimethylsilylmethylplatinum, [(1'-pyrene)cyclopentadiene]trimethylsilylmethyl Platinum, [1-methyl-3-(1'-pyrene)cyclopentadiene]trimethylsilylmethyl platinum, etc.

The cyclopentadiene ring in the above compounds can also use methyl, chloro, fluoro, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, methyldiphenyl Silyl group, triphenylsilyl group, phenyl group, fluorophenyl group, chlorophenyl group, methoxy group, naphthyl group, biphenyl group, anthracenyl group, pyrenyl group, 2-benzylnaphthalene, thioxanthone, 2 -Chlorothioxanthone, 2-isopropylthioxanthone, anthraquinone, 1-chloroanthraquinone, acetophenone, benzophenone, 9,10-dimethylanthracene, 9,10-dichloroanthracene and One or more groups selected from these are substituted with a substituted cyclopentadiene ring. In addition, in the above-mentioned compound, the cyclopentadiene ring may be substituted with η5-fluorenyl.

In terms of the cyclopentadiene ring in the above compounds, those who are not substituted, those substituted with one or more aromatic organic groups, those substituted with one or more aliphatic organic groups, and those substituted with one or more aromatic groups It is preferable that the organic group is substituted with one or more aliphatic organic groups. In addition, naphthyl, biphenyl, anthryl, phenanthryl, and pyrenyl are preferred as the organic group substituted with a cyclopentadiene ring.

The content of the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the first form is as long as it can be irradiated with light such as ultraviolet rays to promote the addition reaction type polysiloxane-based adhesive and the crosslinking agent. There is no particular limitation. The content of the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the first aspect is preferably, for example, the solid content of the addition reaction type polysiloxane-based adhesive is 100 parts by mass, and the solid content is 0.1 parts by mass or more and 3.0 parts by mass or less.

(Cohesion enhancer) The cohesiveness enhancer is used as needed to improve the cohesiveness of the adhesive layer 3. For the cohesiveness enhancer, for example, a polyfunctional thiol is used without limitation. Examples of the cohesiveness enhancer made of polyfunctional thiol include Karenz (registered trademark) MT-PE1, Karenz MT-NR1 manufactured by Showa Denko Corporation.

Among them, multifunctional thiol is not compatible with addition reaction type polysiloxane adhesive, so to use multifunctional thiol as cohesiveness enhancer, it is necessary to use addition reaction type polysiloxane adhesive and multifunctional thiol Compatibilizer. In terms of the compatibilizer, those not particularly limited include, for example, KBM-802, KBM-803 (both trade names) manufactured by Shin-Etsu Chemical Co., Ltd. having a silane coupling agent having a mercapto group, and SH6062 (manufactured by Dow Corning Toray Co., Ltd.). Trade name) etc. When the cohesiveness enhancer is used for the adhesive layer 3, the addition amount of the cohesiveness enhancer is preferably 100 parts by mass of the solid content of the addition reaction type polysiloxane-based adhesive, and the range of 6 parts by mass or less at the solid content is preferable. The addition amount of the cohesiveness enhancer is 100 parts by mass of the solid content of the addition reaction type polysiloxane adhesive. When the solid content exceeds 6 parts by mass, even if the compatibilizer is added, the addition reaction type polysiloxane adhesive The agent is separated from the multifunctional thiol which is a cohesiveness enhancer.

(Reinforcing filler) The reinforcing filler is used as needed to improve the strength of the adhesive layer 3. Regarding the reinforcing filler, non-limiting examples include pyrolytic silica (registered trademark) 130, pyrolytic silica 200, pyrolytic silica 300 manufactured by Japan Aerosil Corporation, REOLOSIL (produced by Tokuyama Corporation). Registered trademark) QS-102, REOLOSILQS-30, CARPLEX (registered trademark) 80 manufactured by DSL. JAPAN Corporation, Hi-Sil (registered trademark) -233-D manufactured by PPG, etc.

<Adhesive layer of the second form> The second embodiment of the adhesive layer 3 includes a peroxide-curable polysiloxane adhesive, a crosslinking agent, and a photosensitive platinum (Pt) catalyst in addition to the addition reaction type polysiloxane-based adhesive contained in the first embodiment of the adhesive layer 3. Silicone adhesive. In addition, the adhesive layer 3 of the second aspect may contain an initiator that starts the polymerization reaction of the peroxide-curable polysiloxane adhesive. Furthermore, the adhesive layer 3 of the second aspect is similar to the adhesive layer 3 of the first aspect, and may contain other additives such as reinforcing fillers, cohesiveness enhancers, colorants, etc. as needed.

(Peroxide-curing polysiloxane-based adhesive) Peroxide-curable polysiloxane-based adhesives can be used, but generally speaking, they are polysiloxanes (G2) composed of organic polysiloxanes such as polydimethylsiloxane. , Adhesive of polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane. In addition, the polysiloxane adhesive (G2) made of organic polysiloxane contained in the peroxide-curing polysiloxane adhesive and the polysiloxane adhesive contained in the addition reaction type polysiloxane adhesive (G1) is different. Generally speaking, it does not contain a silicon-bonded alkenyl group.

The following is a polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane which does not contain silicon-bonded alkenyl group, contained in peroxide-curing polysiloxane adhesive (G2) , And polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane, which will be described in further detail. In addition, in the following description, the polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane that does not contain a silicon-bonded alkenyl group may be described only as polydimethyl Polysiloxane (G2) made of organic polysiloxane such as silicone.

[Polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane that does not contain silicon-bonded alkenyl groups] The polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane in this embodiment may be used for peroxide-curing polysiloxane-based adhesives, that is, There is no particular limitation as long as it does not contain a silicon-bonded alkenyl group. The molecular structure of such an organic polysiloxane includes, for example, a linear structure formed by repeating diorganosiloxane units in the main chain portion, a structure in which a part of the molecular structure includes a branched structure, a branched structure, or Ring structure.

The polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane that does not contain a silicon-bonded alkenyl group may be in the form of an oil or a raw gum, but the raw gum is preferred. In the case of oil, the viscosity of the polysiloxane (G2) made of organic polysiloxane is preferably 1000 mPa·s or more at 25°C. When the viscosity is less than 1000 mPa·s, the adhesive before and after light irradiation may not be able to find the desired adhesive properties, and the adhesiveness between the adhesive layer 3 and the base material 2 may be deteriorated. In the case of a raw colloid, the viscosity of the polysiloxane (G2) formed of the organic polysiloxane in which toluene is dissolved to a concentration of 30% by mass is preferably 100,000 mPa·s or less at 25°C. When the viscosity exceeds 100,000 mPa·s, the stirring during preparation of the adhesive composition may become difficult. In addition, the above viscosity can be measured using a BM type rotary viscometer.

A polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane which does not contain a silicon-bonded alkenyl group is represented by, for example, the following general formula (5) or general formula (6) However, it is not limited to this.

…通式(5)【Chemical 5】

…Formula (5)

…通式(6)【Chemical 6】

…Formula (6)

Here, in the above general formula (5) and general formula (6), R ⁴ is a monovalent hydrocarbon group independently having no aliphatic unsaturated bond, and t is an integer of 100 or more, which is that of the above diorganopolysiloxane The viscosity at 25°C becomes a value of 1000 mPa·s or more.

R ⁴ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms and preferably having 1 to 7 carbon atoms which does not have an aliphatic unsaturated bond. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, and aromatic groups such as phenyl groups and tolyl groups. In particular, methyl groups are preferred.

[Polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane] In this embodiment, it is made of organic polysiloxane such as polydimethylsiloxane. The polysiloxane resin (R2) can be the same as the polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane used in the above addition reaction type polysiloxane adhesive. ) Same. That is, the polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane is an organic having R ² ₃ SiO _0.5 unit (M unit) and SiO ₂ unit (Q unit) Polysiloxane is called MQ resin. The polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane does not basically have an alkenyl group in the molecule, and it can be used by a publicly known person. R ² is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and exemplified above for R ¹ is exemplified. It is preferable that the organic polysiloxane contains R ² ₃ SiO _0.5 units and SiO ₂ units so that the molar ratio of R ² ₃ SiO _0.5 units/SiO ₂ units becomes 0.5 or more and 1.7 or less. When the molar ratio of R ² ₃ SiO _0.5 unit/SiO ₂ unit is less than 0.5, the adhesive force and adhesive force of the obtained adhesive layer 3 may decrease. On the other hand, when the molar ratio of R ² ₃ SiO _0.5 unit/SiO ₂ unit exceeds 1.7, the adhesive force and holding force of the obtained adhesive layer 3 may decrease. In addition, the above-mentioned organic polysiloxane may have an OH group. In this case, the content of the OH group is preferably 4.0% by mass or less relative to the total mass of the organic polysiloxane. When the OH group exceeds the above upper limit, the curability of the adhesive may sometimes decrease.

In this case, in order to make the adhesive force 2.4N/10mm or more and 5.5N/10mm or less, it is preferable to use MQ resin for the polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane . Among the impurities when synthesizing the MQ resin, R ² SiO _1.5 units (T units) and/or R ² ₂ SiO units (D units) may also be included.

The above-mentioned polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane that does not contain a silicon-bonded alkenyl group and an organic polysiloxane made of polydimethylsiloxane or the like The polysiloxane resin (R2) made of alkanes can also be used by simply mixing them. In addition, the polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane which does not contain a silicon-bonded alkenyl group contains the organic polysilicon represented by the general formula (6) In the case of oxane, as long as the characteristics of the present invention are not impaired, it can also be used as a polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane which does not contain a silicon-bonded alkenyl group. ) It is used as a (partial) condensation reaction product obtained by reacting a polysiloxane resin (R2) made of an organic polysiloxane such as polydimethylsiloxane in advance.

(The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the adhesive layer of the second form to the total mass (Rw) of the polysiloxane (R), and (The content ratio of polysiloxane (G1) with alkenyl group in the total mass of polysiloxane (G) and polysiloxane resin (R)) As described above, the polysiloxane-based adhesive constituting the adhesive layer 3 of the second aspect includes the addition reaction type polysiloxane-based adhesive and the peroxide-curable polysiloxane-based adhesive. Therefore, in terms of the polysiloxane adhesive that constitutes the adhesive layer 3 of the second aspect, the total mass (Gw) of the polysiloxane adhesive (G) is the addition reaction type polysiloxane adhesive that contains silicon bonds. The quality (G1w) of polysiloxane (G1w) made of organic polysiloxanes such as alkenyl-based polydimethylsiloxane and peroxide curing type silicone adhesives are not included The total mass of the mass (G2w) of the polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane, which is a silicon-bonded alkenyl group. In addition, in terms of the polysiloxane adhesive that constitutes the adhesive layer 3 of the second aspect, the total mass (Rw) of the polysiloxane resin (R) is made of polydimethylene in the addition reaction type polysiloxane adhesive. The quality (R1w) of polysiloxane resin (R1w) made of organic polysiloxane based on silicones, and polydimethylsiloxane etc. in peroxide-curable polysiloxane adhesive The total mass of the mass (R2w) of the polysiloxane resin (R2) made of the organic polysiloxane.

The mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) contained in the adhesive layer 3 of the second form to the total mass (Rw) of the silicone (R) (= (G1w+G2w)/(R1w+R2w)) is preferably in the range of 40/60 to 56/44. In addition, in this case, the content ratio of polysiloxane (G1) having an alkenyl group in the total mass of polysiloxane (G) and polysiloxane resin (R) is {G1w)/((Gw)+ (Rw))}×100 is preferably in the range of 14% by mass or more and 42% by mass or less.

The mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) contained in the adhesive layer 3 of the second form to the total mass (Rw) of the silicone (R) is less than the above At the lower limit of the range, the adhesive force and adhesive force of the adhesive layer 3 may decrease. In this case, when the adhesive tape 1 is used for dicing a semiconductor element substrate, a fluorescent substrate, or the like, which will be described later, a semiconductor wafer or the like that is a cut piece may be scattered.

On the other hand, the mass ratio (Gw) of the total mass (Gw) of the silicone (G) contained in the adhesive layer 3 of the second aspect to the total mass (Rw) of the silicone (R)/( Rw) When the upper limit of the above range is exceeded, when the mass of the polysiloxane (G1) in the addition reaction type polysiloxane adhesive is extremely high, and the adhesive before irradiation is not cured, The adhesive layer 3 becomes too soft due to the silicone (G) component. In this case, during cutting of the semiconductor element substrate or the like, the vibration of the cutting is easily transmitted to the adhesive layer 3 and the amplitude becomes large. For example, the semiconductor element substrate may deviate from the reference position. Then, along with this, chipping (cutting) may occur in the singulated semiconductor wafer, and the size deviation may occur for each semiconductor wafer. In addition, in the case where the quality of the polysiloxane (G2) in the peroxide-curable polysiloxane adhesive is extremely high, the hardening of the peroxide-curable polysiloxane adhesive caused by the initiator easily progresses Therefore, the adhesion and adhesion of the adhesive layer 3 may decrease. In this case, when the adhesive tape 1 is used for dicing a semiconductor element substrate, a fluorescent substrate, or the like, which will be described later, a semiconductor wafer or the like that is a cut piece may be scattered.

The content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) in the adhesive layer 3 of the second aspect is less than the lower limit of the above range At the time of exposure, when the adhesive tape 1 is irradiated with light, the adhesive is hard to harden and cohesion is difficult to improve. In this case, the desired adhesion reduction and failure mode in the retention test cannot be obtained. After the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, the obtained semiconductor wafer or the like is peeled from the adhesive tape 1 The pickability of the sliced semiconductor wafer may deteriorate, and the adhesive residue may be easily generated on the semiconductor wafer or the like.

On the other hand, the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) in the adhesive layer 3 of the second aspect exceeds the above At the upper limit of the range, the adhesive layer 3 becomes too soft due to the polysiloxane (G) component in the state where the adhesive before irradiation is not hardened. In this case, when cutting the semiconductor element substrate or the like, the vibration of the cutting is easily transmitted to the adhesive layer 3 and the amplitude becomes large. For example, the semiconductor element substrate may deviate from the reference position. Then, along with this, chipping (cutting) may occur in the singulated semiconductor wafer, and the size deviation may occur for each semiconductor wafer.

The content of the peroxide-curable polysiloxane-based adhesive in the adhesive layer 3 of the second form is included in the adhesive layer of the second form when it is mixed with the addition reaction-type polysiloxane-based adhesive The mass ratio (Gw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R), and the polysiloxane (G) and polysiloxane The polysiloxane (G2) containing an alkenyl group-containing polysiloxane (G1) in the total mass of the resin (R) in consideration of the peroxide curable polysiloxane adhesive (G2) The ratio with the silicone resin (R2) can be adjusted. The content of the peroxide polysiloxane-based adhesive in the adhesive layer 3 of the second aspect is within the above range, so that when the adhesive tape 1 is used for cutting a semiconductor element substrate, a fluorescent substrate, etc., The adhesive residue when peeling off the adhesive tape 1 when suppressing the scattering of the semiconductor wafer etc. of a dicing sheet.

In addition, in the peroxide-curable silicone adhesive of the present invention, a commercially available peroxide-curable silicone adhesive can also be used. Specifically, for example, KR100, KR101-10 (all brand names) manufactured by Shin-Etsu Chemical Industry Co., Ltd., YR3340, YR3286, PSA610-SM, XR37-B6722 (all brand names) manufactured by Mitu Hi-Tech Materials Co., Ltd., Dow Corning East SH4280, SH4282, SE4200, BY24-717, BY24-715, Q2-7735 (all trade names) manufactured by Rei Corporation.

(Initiator) For the initiator, peroxides are used, more specifically organic peroxides. The organic peroxide used as an initiator is not particularly limited, and examples thereof include benzoyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-bis(t-peroxide ) Hexane, 1,1´-di-t-peroxy-3,3,5-trimethylenecyclohexane, 1,3-di-(t-peroxy)-dicumyl, etc., commercially available Examples of products include NYPERK40 manufactured by NOF Corporation.

The content of the initiator in the adhesive layer 3 of the second aspect is 100 parts by mass of the solid content of the peroxide-curable polysiloxane-based adhesive, and preferably 10 parts by mass or less at the upper solid content. The content of the initiator in the adhesive layer 3 of the second form is 100 parts by mass of the solid content of the peroxide-curing polysiloxane-based adhesive, and when the solid content exceeds 10 parts by mass, there is in the adhesive layer 3 The hardening reaction of the peroxide-curing polysiloxane-based adhesive may progress excessively. In this case, the adhesive layer 3 becomes hard, and the adhesive force of the adhesive tape 1 tends to be low. Then, when this adhesive tape 1 is used for dicing a semiconductor element substrate or the like, when the semiconductor element substrate or the like is cut, a semiconductor wafer or the like which is a dicing sheet may be easily peeled off from the adhesive tape 1 and be scattered.

＜Thickness＞ The thickness of the adhesive layer 3 is preferably in the range of 10 μm or more and 100 μm or less, and more preferably in the range of 20 μm or more and 40 μm or less. When the thickness of the adhesive layer 3 is less than 10 μm, the thickness of the polysiloxane adhesive contained in the adhesive layer 3 becomes thinner, so the adhesive force of the adhesive tape 1 tends to decrease. On the other hand, when the thickness of the adhesive layer 3 is thicker than 100 μm, the cohesive force of the adhesive layer 3 may easily fail. Then, after the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, when the obtained semiconductor wafer or the like is peeled from the adhesive tape 1, there is a possibility that adhesive residue may be generated on the semiconductor wafer or the like. In addition, when cutting a semiconductor element substrate or the like, the vibration of the cutting is easily transmitted to the adhesive layer 3 and the amplitude becomes large. For example, the semiconductor element substrate may deviate from the reference position. Then, along with this, chipping (cutting) may occur in the singulated semiconductor wafer, and the size deviation may occur for each semiconductor wafer.

<Anchor coating> As described above, in the adhesive tape 1 of the present embodiment, a matching base material may be provided between the base material 2 and the adhesive layer 3 according to the manufacturing conditions of the adhesive tape 1, the use conditions of the adhesive tape 1 after manufacturing, and the like. The anchor coating under the type 2 is subjected to surface treatment such as corona treatment. Thereby, the adhesion between the base material 2 and the adhesive layer 3 can be improved.

<Surface treatment> The surface of the base material 2 (the surface on the opposite side to the surface facing the adhesive layer 3) may be subjected to surface treatment such as peelability improvement treatment. The treatment agent used for the surface treatment of the substrate 2 is not particularly limited, and for example, long-chain alkyl vinyl monomer polymer, fluorinated alkyl vinyl monomer polymer, polyvinyl alcohol urethane can be used , Non-silicone peeling treatment agent such as amino alkyd resin. Examples of such a non-polysiloxane-based release treatment agent include PEELOIL1050 and PEELOIL1200 manufactured by IPPOSHA OIL INDUSTRIES Co., Ltd.

<Release film> In addition, a peeling film may be provided on the surface of the adhesive layer 3 (the surface on the side opposite to the surface facing the substrate 2) as required. For the release film, a film such as paper, polyethylene, polypropylene, polyethylene terephthalate, etc. can be used to perform release for improving the releasability with the silicone adhesive contained in the adhesive layer 3 Processor. The material used for the peeling treatment of the peeling film is not particularly limited. For example, materials such as a fluoroalkyl modified silicone polymer, a long-chain alkyl vinyl monomer polymer, and an amino alkyd resin can be used.

<Thickness of adhesive tape> The entire thickness of the adhesive tape 1 having the configuration described above is preferably in the range of 20 μm or more and 200 μm or less. When the thickness of the adhesive tape 1 is less than 20 μm, when the adhesive tape 1 is used for dicing a semiconductor element substrate or the like, it may be difficult to peel off the formed semiconductor wafer or the like from the adhesive tape 1. On the other hand, when the thickness of the adhesive tape 1 exceeds 200 μm, when the adhesive tape 1 is adhered to a semiconductor element substrate or the like, it is difficult for the adhesive tape 1 to follow the irregularities formed on the adhesion surface of the semiconductor element substrate. In this case, the bonding area between the adhesive tape 1 and the semiconductor element substrate becomes smaller, and the semiconductor wafer or the like may be easily scattered during dicing.

[Manufacturing method of adhesive tape] Next, a method of manufacturing the adhesive tape 1 of this embodiment will be described. In addition, the manufacturing method of the adhesive tape 1 described below is an example, and the manufacturing method of the adhesive tape 1 is not limited to this. Here, the adhesive layer 3 contains the adhesive tape 1 of the first form of the addition reaction type polysiloxane-based adhesive in the hardening type polysiloxane-based adhesive, and the adhesive layer 3 is in the hardening type polysiloxane The second type of adhesive tape 1 including the addition reaction type polysiloxane-based adhesive and the peroxide-curing polysiloxane-based adhesive can be manufactured by the same manufacturing method.

When manufacturing the adhesive tape 1, first, a general-purpose organic solvent such as toluene and ethyl acetate is used to dissolve other components such as a hardening type silicone adhesive and a crosslinking agent to obtain an adhesive solution. Next, this adhesive solution is applied to the surface of the base material 2 after surface treatment and anchor coating formation as required using a comma blade coater or the like to a predetermined thickness. Next, the base material 2 coated with the adhesive solution is heated at a temperature of 60° C. to 160° C. for a few minutes to several tens of minutes to dry and harden the adhesive solution to form the adhesive layer 3. Through the above procedure, as shown in FIG. 1, the adhesive tape 1 with the adhesive layer 3 laminated on the substrate 2 is obtained.

[How to use the adhesive tape] The adhesive tape 1 of the present embodiment is used for dicing a semiconductor material that forms the basis of a semiconductor wafer in a process of manufacturing a semiconductor wafer including semiconductor elements such as LEDs (Light emitting diodes) and power semiconductors.

Specifically, the adhesive tape 1 is used to obtain a semiconductor wafer in which a semiconductor element substrate in which a plurality of semiconductor elements such as LED elements and power semiconductor elements are formed on a substrate made of resin, ceramics, or the like is cut into individual pieces. Here, in terms of a semiconductor element substrate in which a plurality of semiconductor elements are formed on the substrate, generally, in order to protect the semiconductor element from the outside such as temperature and humidity, a sealing resin as an example of a covering material may be provided so as to cover the semiconductor element . The adhesive tape 1 of the present embodiment is preferably particularly suitable for cutting a semiconductor element substrate provided with a sealing resin.

In order to obtain a plurality of semiconductor wafers by cutting a semiconductor element substrate provided with a sealing resin, for example, the following methods have been known. First, the adhesive tape for dicing is stuck from the substrate side of the semiconductor element substrate, and the semiconductor element substrate is cut from the side where the semiconductor element is formed by a dicing machine or the like. Then, the individual semiconductor wafers formed by cutting are peeled from the adhesive tape to obtain a plurality of semiconductor wafers.

However, when the semiconductor element substrate is cut by sticking an adhesive tape for dicing from the substrate side of the semiconductor element substrate in this way, there is a so-called sag that occurs on the cut surface (side surface of the substrate of the semiconductor wafer). Or roughened cut surfaces. Therefore, in recent years, in order to solve such a problem, the following method has been proposed: for the semiconductor element substrate, not only the substrate side, but also the side from which the semiconductor element is formed, that is, the sealing resin that seals the semiconductor element is adhered for cutting The tape cuts the semiconductor element substrate.

Here, the sealing resins for semiconductor elements such as LEDs and power semiconductors have historically used epoxy resins that are excellent in electrical characteristics and heat resistance. Epoxy resins are used when used in high-output LEDs and power semiconductors. In the case of short-wavelength LEDs, or due to the use environment of semiconductor wafers, etc., there is a problem that they are easily discolored.

On the other hand, for the reason that discoloration due to heat and light is less likely to occur than epoxy resins, in recent years, polysilicone resins are often used as sealing resins for semiconductor elements such as LEDs and power semiconductors. More specifically, a polysiloxane resin containing both or one of methyl and phenyl groups in terms of functional groups is used, that is, a polysiloxane resin containing methyl groups, a polysiloxane resin containing phenyl groups, and a polysiloxane resin containing methyl groups and benzene There are many cases of silicone resin on both sides.

Silicone resin is used for the sealing resin of the semiconductor element, so that the discoloration of the sealing resin caused by heat and light can be suppressed. In addition, the silicone resin has a light transmittance of over 88% (wavelength 400-800nm) and a refractive index of up to 1.41. For this reason, when the semiconductor element is an LED, silicone resin is used for the sealing resin, so that the radiation light from the LED can be efficiently taken out of the package. Among the above-mentioned polysiloxane resins, the use of a phenyl group-containing polysiloxane resin makes it possible to achieve more efficient light emission than the case of using a methyl group-containing polysiloxane resin.

The silicone-containing polysiloxane resins are not particularly limited, for example, KER-2300, KER-2460, KER-2500N, KER-2600, KER-2700, KER-2900, X- manufactured by Shin-Etsu Chemical Co., Ltd. 32-2528, IVS4312, IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG0810, IVSG5778, XE13-C2479, IVSM4500, Dow Corning Toray Co., Ltd. OE-6351, OE-6336, OE-6301, etc. The silicone resin containing a methyl group and a phenyl group is not particularly limited, and examples thereof include KER-6075, KER-6150, and KER-6020 manufactured by Shin-Etsu Chemical Co., Ltd. As for the silicone resin containing phenyl group, there are no particular limitations, for example, KER-6110, KER-6000, KER-6200, ASP-1111, ASP-1060, ASP-1120, ASP-1050P manufactured by Shin-Etsu Chemical Co., Ltd. , XE14-C2508 manufactured by Maitu High-tech Materials Co., Ltd., OE-6520, OE-6550, OE-6663, OE-6636, OE-6635, OE-6630 manufactured by Dow Corning Toray Co., Ltd.

However, conventionally, for the adhesive tape for dicing used for cutting a semiconductor element, for example, an adhesive tape made of an acrylic adhesive is used as an adhesive layer. However, when such a conventional adhesive tape is pasted from the side of the semiconductor element substrate where the semiconductor element is formed (sealing resin side) to cut the semiconductor element substrate, for example, when the adhesive force between the sealing resin and the adhesive tape is insufficient, During dicing, there may be problems such as the scattering of semiconductor wafers.

In particular, the above-mentioned polysiloxane resin has properties of high releasability compared to, for example, epoxy resins that have been conventionally used as sealing resins. Therefore, in the case of a semiconductor device substrate using polysiloxane resin as the sealing resin, for example, when an adhesive tape made of an acrylic resin adhesive is attached to the adhesive tape, it is the polysiloxane resin of the sealing resin and the adhesive tape. The adhesive force tends to decrease. As a result, problems such as scattering of semiconductor wafers are more likely to occur during the dicing of the semiconductor element substrate.

In contrast, the adhesive tape 1 of the present embodiment is as described above, and the adhesive layer 3 is configured to include a polysiloxane-based adhesive in which a silicone rubber (G) and a silicone resin (R) are mixed in a suitable ratio. Agent, so that in the case of cutting the semiconductor element substrate, when used from the side of the sealing resin made of polysiloxane resin, it can be used to maintain good adhesion to the sealing resin of the semiconductor element substrate and Adhesion. Then, compared with the conventional adhesive tape, when the semiconductor element substrate is diced, occurrence of scattering of the semiconductor wafer and the like can be suppressed. On the other hand, the adhesive layer 3 contains a photosensitive platinum (Pt) catalyst and a crosslinking agent together with the above-mentioned polysiloxane-based adhesive, so that light such as ultraviolet rays is irradiated to make the photosensitive platinum in the polysiloxane-based adhesive ( Pt) The catalyst is activated, and the crosslinking reaction between the addition reaction type polysiloxane-based adhesive and the crosslinking agent for the addition reaction type polysiloxane-based adhesive is promoted, so that the cohesive force of the adhesive becomes lighter than light. Big before irradiation. As a result, the adhesion of the adhesive layer 3 is appropriately lowered, and the failure mode in the retention test becomes "interface failure" or the "non-drop" in the retention test. With this, it is possible to realize a good pick-up property when peeling off the semiconductor wafer or the like from the adhesive tape 1 while suppressing adhesive residues to the semiconductor wafer or the like.

Hereinafter, a method of using the adhesive tape 1 of this embodiment and a method of manufacturing a semiconductor wafer using the adhesive tape 1 of this embodiment will be described in detail. 2(a) to (e) are diagrams illustrating a method of manufacturing a semiconductor wafer using the adhesive tape 1 of this embodiment. In addition, a case where a semiconductor wafer having an LED element as a semiconductor element is manufactured using the adhesive tape 1 will be described as an example. In addition, the method described below is an example of a method of using the adhesive tape 1 and a method of manufacturing a semiconductor wafer using the adhesive tape 1, and is not limited to the following method.

In this embodiment, first, for example, a plurality of semiconductor elements 102 are mounted on a substrate 101 made of a resin material, ceramics, or the like, and a semiconductor element substrate 100 is produced. In addition, the semiconductor element 102 is, for example, an LED element, and although the illustration is omitted, for example, a plurality of semiconductor layers including a light-emitting layer that emits light when energized is stacked, and an electrode is formed on the upper portion. Next, a plurality of semiconductor elements formed on the substrate 101 of the semiconductor element substrate 100 are sealed with a sealing resin 103 made of polysiloxane-based resin (sealing procedure). In this example, although a plurality of semiconductor elements 102 are sealed together by the sealing resin 103, each semiconductor element 102 may be individually sealed by the sealing resin 103.

Next, as shown in FIG. 2( a ), the adhesive tape 1 and the semiconductor element substrate 100 are adhered in such a manner that the adhesive layer 3 of the adhesive tape 1 and the sealing resin 103 of the semiconductor element substrate 100 face each other (adhesion procedure). Next, as shown in FIGS. 2(b) and (c), in a state where the adhesive tape 1 is attached to the semiconductor element substrate 100, the semiconductor element substrate 100 is cut along a line X to be cut by a dicing machine or the like ( Cut off procedure). In this example, the semiconductor element substrate 100 to which the adhesive tape 1 is attached is cut from the substrate 101 side. In addition, as shown in FIG. 2(c), in this example, so-called full dicing in which the entire semiconductor element substrate 100 is cut in the thickness direction is performed.

Next, as shown in FIG. 2(d), the adhesive tape 1 adhered to the semiconductor device substrate 100 is irradiated with ultraviolet rays from the base 2 side (ultraviolet irradiation procedure). As described above, the base material 2 is made of a material that transmits ultraviolet rays. Therefore, the adhesive tape 1 is irradiated with ultraviolet rays from the substrate 2 side, so that the ultraviolet rays penetrate the substrate 2 and are irradiated to the adhesive layer 3. In the adhesive tape 1 of the present embodiment, since the adhesive layer 3 has a photosensitive platinum (Pt) catalyst, the ultraviolet ray is irradiated to the adhesive layer 3 to promote the addition reaction type polysiloxane based in the adhesive layer 3 Addition reaction of adhesive and cross-linking agent. As a result, the cohesive force of the cross-linking density of the adhesive layer 3 increases, and the adhesive force of the adhesive layer 3 decreases compared with before the ultraviolet irradiation.

Next, the semiconductor wafer 200 formed by cutting the semiconductor element substrate 100 is peeled (picked up) from the adhesive tape 1 so that as shown in FIG. 2(e), a semiconductor wafer 200 that is divided into pieces can be obtained (stripping procedure) .

As described above, in the adhesive tape 1 of the present embodiment, the adhesive layer 3 is configured to include the silicone adhesive in which the silicone rubber (G) and the silicone resin (R) are mixed at an appropriate ratio. Thereby, when the adhesive tape 1 is used for dicing, the adhesive force and the adhesive force to the adhesive tape 1 of the semiconductor element substrate 100 can be maintained well. In particular, in recent years, in the sealing resin 103 that seals the semiconductor element 102, a silicone resin with high releasability is often used. On the other hand, since the adhesive tape 1 of this embodiment has the above-mentioned configuration, it still has good adhesion and adhesion to the sealing resin 103 made of polysiloxane resin. As a result, when the adhesive tape 1 of the present embodiment is used for dicing the semiconductor element substrate 100, it is possible to suppress the scattering of the semiconductor wafer 200.

In addition, the polysiloxane adhesive contained in the adhesive layer 3 of the adhesive tape 1 of the present embodiment has good adhesion to the sealing resin 103 as described above, and has high releasability. Furthermore, the adhesive tape 1 of the present embodiment includes a photosensitive platinum (Pt) catalyst that accelerates the addition reaction of an addition reaction type polysiloxane-based adhesive and a crosslinking agent, for example, by irradiation with light such as ultraviolet rays. Then, after the cutting process, the adhesive layer 3 is irradiated with light through the substrate 2 before the peeling process, so that the addition reaction type polysiloxane-based adhesive and the crosslinking agent can be promoted in the adhesive layer 3 To improve cohesion and reduce the adhesion of the adhesive layer 3. Thereby, in the peeling process, when the semiconductor wafer 200 obtained by dicing the semiconductor element substrate 100 is peeled (picked up) from the adhesive tape 1, the occurrence of the so-called adhesive residue that the adhesive adheres to the semiconductor wafer 200 can be suppressed . In addition, it is possible to realize a good pick-up property when peeling the semiconductor wafer 200 from the adhesive tape 1.

In addition, in the above, a method of obtaining a singulated semiconductor wafer by dicing the adhesive tape 1 from the sealing resin side and cutting the semiconductor element substrate on which a plurality of semiconductor elements are formed on the substrate will be described. However, the use of the adhesive tape 1 of this embodiment is not limited to this. The adhesive tape 1 of the present embodiment can also be used, for example, in the manufacture of wafer-level packaged LEDs to obtain wafers in which a plurality of LED elements are cut into semiconductor materials covered with phosphors as an example of a covering material and diced. LED package. In addition, the phosphor is a structure in which a fluorescent material is dispersed in a resin material, ceramic, or the like.

In recent years, with the miniaturization of wafer-level packaged LEDs, there has been a tendency for wafer-level packaged LEDs that are divided into pieces at the time of dicing to be easily scattered. On the other hand, by using the adhesive tape 1 of the present embodiment having the above-described configuration, the adhesive force between the phosphor and the adhesive layer 3 can be maintained well, and the scattering of the individual chip-scale packaged LEDs can be suppressed. In addition, after dicing, the adhesive layer 3 is irradiated with ultraviolet rays to reduce the adhesion, making it easy to peel off the wafer-level packaged LED from the adhesive tape into one piece, while suppressing the adhesive residue on the peeled wafer-level packaged LED The generation of things. [Example]

Next, the present invention will be further specifically described using Examples and Comparative Examples. In addition, the present invention is not limited to the following examples.

The present inventor has the first aspect that the adhesive layer 3 contains an addition-reactive polysiloxane-based adhesive as a hardening type polysiloxane-based adhesive, and the adhesive layer 3 contains an addition-reactive polysiloxane-based adhesive. The second form of the peroxide-curable polysiloxane-based adhesive as the hardening type polysiloxane-based adhesive is to prepare the adhesive tape 1 by differentiating the components of the adhesive layer 3 and the thickness of each layer, etc. Evaluation of the produced adhesive tape 1. In addition, among the following examples, Examples 1 to 8 correspond to the first aspect, and Examples 9 to 15 correspond to the second aspect. Hereinafter, each example and each comparative example will be described in detail.

1. Making Adhesive Tape 1 (Example 1) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4584 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 5.33 parts by mass of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK) diluted with toluene to a solid content concentration of 15% by mass was added. , Mix and stir, and adjust the adhesive solution of the first form. Next, this adhesive solution was applied to a substrate 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 120° C. for 3 minutes to form a dried product. Adhesive layer 3 with a thickness of 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

(Example 2) For the adjustment of the adhesive solution in the first form, an addition reaction type polysiloxane-based adhesive (Dow Corning) composed of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule is used Toray Co., Ltd. SD4584 (trade name) without addition of crosslinking agent type, solid content concentration of 60% by mass), the thickness of the adhesive layer 3 after drying was 30 μm except that it was made as in Example 1, and the total after drying was obtained. Adhesive tape 1 with a thickness of 68 μm.

(Example 3) For the base material 2, a PET film with a thickness of 12 μm was used, and the thickness of the adhesive layer 3 after drying was 10 μm except that it was made as in Example 2 to obtain an adhesive tape 1 with a total thickness of 22 μm after drying.

(Example 4) For the adjustment of the adhesive solution in the first form, an addition reaction type polysiloxane-based adhesive (Dow Corning) composed of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule is used Toray Co., Ltd.'s SD4585 (trade name) (without added crosslinking agent type, solid content concentration 60% by mass), for the base material 2, a PET film with a thickness of 50 μm is used, and the thickness of the adhesive layer 3 after drying is other than 40 μm As in Example 1, an adhesive tape 1 with a total thickness of 90 μm after drying was obtained.

(Example 5) In the adjustment of the adhesive solution of the first aspect, the addition amount of the crosslinking agent (BY24-741 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 20% by mass) was 1.65 parts by mass, and was prepared as in the example. 1. Obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

(Example 6) In the adjustment of the adhesive solution of the first aspect, the addition amount of the crosslinking agent (by Dow Corning Toray Co., Ltd. BY24-741 (trade name), solid content concentration 20% by mass) was 8.25 parts by mass, and it was prepared as in the example. 1. Obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

(Example 7) In the adjustment of the adhesive solution of the first aspect, a photosensitive platinum (Pt) catalyst (manufactured by Sigma-Aldrich Japan KK) trimethyl (methylcyclopentadiene) platinum diluted with toluene to a solid content concentration of 15% by mass (IV)) The addition amount of the solution was 2.00 parts by mass, and it was made as in Example 1 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

(Example 8) In the adjustment of the adhesive solution of the first aspect, a photosensitive platinum (Pt) catalyst (manufactured by Sigma-Aldrich Japan KK) trimethyl (methylcyclopentadiene) platinum diluted with toluene to a solid content concentration of 15% by mass (IV)) The addition amount of the solution was 20.00 parts by mass, and it was made as in Example 1 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

(Example 9) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4584 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 5.33 parts by mass of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK) diluted with toluene to a solid content concentration of 15% by mass was added. , Mix and stir to prepare the addition reaction type polysiloxane adhesive solution.

On the other hand, 166.67 parts by mass of toluene and a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (SH4280 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 60% by mass) 、Mixed with 5.00 parts by mass of an initiator (NYPERK40 (trade name) manufactured by NOF Corporation, solid content concentration 40% by mass) made of methylbenzoic acid peroxide, to prepare peroxide-curing polysiloxane Department of adhesive solution.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide-curing polysiloxane-based adhesive solution are mixed and stirred to prepare a second form of adhesive solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 100 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted. Next, this adhesive solution was applied to a substrate 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 160° C. for 3 minutes to form a dried product. Adhesive layer 3 with a thickness of 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

(Example 10) In the adjustment of the adhesive solution in the second form, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass (solid content) of the adhesive contains 63.70 parts by mass (solid content), except that the method of adjusting the peroxide-curing polysiloxane-based adhesive is adjusted, as in Example 9, a total thickness of 58 μm after drying is obtained Adhesive tape 1.

(Example 11) In the adjustment of the adhesive solution in the second form, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass of the adhesive (solid content) contains 150 parts by mass (solid content) of the peroxide-curable polysiloxane-based adhesive, except that the method is adjusted, as in Example 9, to obtain a total thickness of 58 μm after drying Adhesive tape 1.

(Example 12) The adjustment of the addition reaction type polysiloxane-based adhesive solution in the second form of the adhesive solution consists of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule. For the reaction-type polysiloxane-based adhesive, the non-crosslinking agent type (solid content concentration 60% by mass) manufactured by Dow Corning Toray Co., Ltd. SD4580 (trade name) was used, and it was prepared as in Example 9 to obtain the total Adhesive tape 1 with a thickness of 58 μm.

(Example 13) The adjustment of the addition reaction type polysiloxane-based adhesive solution in the second form of the adhesive solution consists of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule. For the reaction-type polysiloxane-based adhesive, except for the unadded crosslinking agent type (solid content concentration 60% by mass) manufactured by Dow Corning Toray Co., Ltd. SD4586 (trade name), it was prepared as in Example 9 to obtain the total Adhesive tape 1 with a thickness of 58 μm.

(Example 14) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4585 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 5.33 parts by mass of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK) diluted with toluene to a solid content concentration of 15% by weight was added. , Mix and stir to prepare the addition reaction type polysiloxane adhesive solution.

On the other hand, toluene and a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (BY24-717 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 60% by mass) Mix and stir 166.67 parts by mass to adjust the peroxide-curing polysiloxane-based adhesive solution.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide-curing polysiloxane-based adhesive solution are mixed and stirred to prepare a second form of adhesive solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 20 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted. Next, this adhesive solution was applied on a base material 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 160° C. for 3 minutes to form a dried product. The thickness of the adhesive layer 3 is 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

(Example 15) First, an adhesive solution as in the first form of Example 4 was prepared, and the addition reaction type polysiloxane-based adhesive solution was adjusted.

On the other hand, 250.00 parts by mass of toluene, a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (SE4200 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 40% by mass) 、Mixed with 5.00 parts by mass of an initiator (NYPERK40 (trade name) manufactured by NOF Corporation, solid content concentration 40% by mass) made of methylbenzoic acid peroxide, to prepare peroxide-curing polysiloxane Department of adhesive solution.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide-curing polysiloxane-based adhesive solution are mixed and stirred to prepare a second form of adhesive solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 150 parts by mass (solid content) of peroxide curing polysiloxane-based adhesive is adjusted. Next, after applying this adhesive solution to the base material 2 made of polyethylene terephthalate (PET) film with a thickness of 125 μm, it was heated at a temperature of 160° C. for 3 minutes to form a thickness after drying Adhesive layer 3 for 20 μm. By this, the adhesive tape 1 having a total thickness of 145 μm after drying was obtained.

(Comparative example 1) Instead of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK, a platinum metal catalyst (NC-25 manufactured by Dow Corning Toray Corporation) was used (Brand name), solid content 25% by mass) 6 parts by mass, except that the thickness of the adhesive layer 3 after drying was 35 μm, and the adhesive tape 1 having a total thickness of 73 μm after drying was obtained as in Example 1.

(Comparative example 2) The adhesive solution of Example 1 was further added as a linear polyorganosiloxane having a silanol group at both ends as a polysiloxane resin (R3) for addition reaction type polysiloxane-based adhesive. Figure YF3897 (trade name) manufactured by Hi-Tech Materials Co., Ltd., solid content 100% by mass) 10.00 parts by mass, except that the thickness of the adhesive layer 3 after drying is 30 μm, made as in Example 1, and the total thickness after drying is 68 μm Adhesive tape 1.

(Comparative example 3) For the addition reaction type polysiloxane-based adhesive composed of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group, SD4586 (trade name) manufactured by Dow Corning Toray Co., Ltd. is used. The non-added cross-linking dosage form (solid content concentration 60% by mass) was used to make the thickness of the adhesive layer 3 after drying to be 40 μm. As in Example 1, an adhesive tape 1 with a total thickness of 78 μm after drying was obtained.

(Comparative example 4) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4584 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 6.00 parts by mass of a platinum metal catalyst (NC-25 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content 25% by mass) was added, mixed and stirred, and an addition reaction type polysiloxane-based adhesive solution was prepared.

On the other hand, as in Example 9, the peroxide-curing polysiloxane-based adhesive solution was adjusted.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 50 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted. Next, after applying this adhesive mixture solution to the substrate 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, it was heated at a temperature of 160° C. for 3 minutes to form a dried product. Adhesive layer 3 with a thickness of 30 μm. With this, the adhesive tape 1 having a total thickness of 68 μm after drying was obtained.

(Comparative example 5) First, an adhesive solution as in the first form of Example 2 was prepared, and the addition reaction type polysiloxane-based adhesive solution was adjusted.

On the other hand, toluene, a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (BY241-717 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 60% by mass) 166.67 Mass parts and 5.00 parts by mass of an initiator (NYPERK40 (trade name) manufactured by NOF Corporation, solid content concentration 40% by mass) and an initiator made of methylbenzoyl peroxide are mixed and stirred to prepare a peroxide-curable polymer Silicone adhesive solution.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 100 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted. Next, this adhesive mixed solution was applied to a base material 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 160° C. for 3 minutes to form a dried product. The thickness of the adhesive layer 3 is 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

(Comparative example 6) First, for the addition reaction type polysiloxane-based adhesive composed of an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group, SD4587 (product of Dow Corning Toray Co., Ltd.) was used. Except for the cross-linking agent type (solid content concentration 60% by mass) without addition, it was prepared as in Example 1, and an addition reaction type polysiloxane-based adhesive was prepared.

On the other hand, as in Example 15, a peroxide-curing polysiloxane-based adhesive solution was prepared.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 100 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted. Next, this adhesive mixed solution was applied to a base material 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 160° C. for 3 minutes to form a dried product. The thickness of the adhesive layer 3 is 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

(Comparative example 7) First, as in Comparative Example 2, an addition reaction type polysiloxane-based adhesive solution was adjusted. On the other hand, as in Comparative Example 5, a peroxide-curing polysiloxane-based adhesive solution was adjusted.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive and the peroxide curing type silicone adhesive is 150 parts by mass for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. Parts (solid content) of peroxide curing polysiloxane-based adhesive to adjust. Next, this adhesive mixed solution was applied to a base material 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 160° C. for 3 minutes to form a dried product. The thickness of the adhesive layer 3 is 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

(Comparative Example 8) First, as in Example 13, the addition reaction type polysiloxane-based adhesive solution was adjusted. On the other hand, as in Comparative Example 6, a peroxide-curing polysiloxane-based adhesive solution was adjusted.

Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive and the peroxide curing type silicone adhesive is 30 parts by mass for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. Parts (solid content) of peroxide curing polysiloxane-based adhesive to adjust. Next, this adhesive mixed solution was applied to a base material 2 made of polyethylene terephthalate (PET) film with a thickness of 38 μm, and then heated at a temperature of 160° C. for 3 minutes to form a dried product. The thickness of the adhesive layer 3 is 20 μm. By this, the adhesive tape 1 with a total thickness of 58 μm after drying was obtained.

The content of each component of the adhesive layer 3 in Examples 1-15 and Comparative Examples 1-8, and the thickness of each layer are shown in Table 1-Table 3. In addition, in Tables 1 to 3, the terms "polysiloxane" and "polysiloxane resin" are omitted and described as "glue" and "resin", respectively.

2. Evaluation method Next, the evaluation method of the adhesive tape 1 is demonstrated. (1) Adhesion test The adhesive tape 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8 was tested according to the method described in the adhesive tape adhesive sheet test method (JIS Z 0237 (2009)) for the BA-SUS adhesion test ( Peel adhesion test). Specifically, the adhesive tape 1 was attached to a stainless steel plate (SUS304) with a surface roughness (Ra) of 50±25 nm subjected to bright surface annealing (BA) treatment, and a roller with a mass of 2000 g was reciprocated at a speed of 5 mm/s For crimping. Next, after standing for 20 to 40 minutes, the stainless steel plate was peeled at a speed of 5 mm/s in the direction of 180° using a tensile tester, and the adhesion to the polished SUS plate was measured. In addition, the adhesion test was performed on the adhesive tape 1 before the ultraviolet irradiation. In addition, regarding the results of the adhesion test, when considering the fixing force when the adhesive tape 1 is used for cutting a semiconductor material, 2.4 N/10 mm or more and 5.5 N/10 mm or less are preferable.

(2) Rolling ball viscosity test (2-1) Determination of initial ball viscosity With respect to the adhesive tape 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8, the rolling ball tack test was performed according to the method described in the adhesive tape adhesive sheet test method (JIS Z 0237 (2009)).

(2-2) Measurement of roller ball viscosity after UV irradiation The adhesive layer 3 of the individual adhesive tape 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8 was adhered to a fluorine-based release film (Nippa Corporation) SS1A, thickness 75μm). Next, after irradiating ultraviolet rays from the side of the base material 2 of the adhesive tape 1 at a temperature of 23 degrees and a humidity of 50 ± 5% RH for 20 to 40 minutes, the test method described in the adhesive tape adhesive sheet (JIS Z 0237 The method of 2009)) was made as the initial rolling ball viscosity, and the rolling ball viscosity test was conducted. Irradiation of ultraviolet rays is performed using a high-pressure mercury lamp, adjusted so that the wavelength 365 nm becomes 1200 mJ/cm ² under the accumulated light amount. In addition, the ball viscosity when the accumulated light amount is 3000mJ/cm ² is also measured in the same way, but there is no difference from the case where the accumulated light amount is 1200mJ/cm ² , so here the accumulated light amount is 1200mJ/cm ² was evaluated.

In terms of the results of the ball tack test, when considering the pick-up properties of semiconductor chips, etc. that have been diced by dicing, the ball tack (ball No.) is compared to the initial ball tack (ball No.) after UV irradiation. ) Low is preferred.

(3) Retention test (3-1) Measurement of initial retention Regarding the adhesive tape 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8, the retention test was conducted according to the method described in the adhesive tape adhesive sheet test method (JIS Z 0237 (2009)). Specifically, it was adhered to a stainless steel plate (SUS304) polished with water-resistant sandpaper, held under a condition of a predetermined weight, at a temperature of 40°C and a humidity of 33% RH, and measured until the adhesive tape 1 was peeled off from the stainless steel plate. Elapsed time until falling (falling time (minutes)). Furthermore, the failure mode when the adhesive tape 1 peeled from the stainless steel plate was observed (the failure mode between the adhesive layer 3 and the stainless steel plate was interface failure or cohesive failure). In addition, the measurement of the drop time in the retention test is performed for 5000 points. In addition, the results of the retention test shown in Tables 4 to 6 described below show the fall time (minutes) and the failure mode of the adhesive tape 1. In addition, when the adhesive tape 1 is not peeled (dropped) up to 5000 minutes, "hold" is displayed.

(3-2) Determination of holding power after UV irradiation The adhesive ball 1 was irradiated with ultraviolet rays as described in the above-mentioned conditions for measuring the viscosity of the roller ball after the UV irradiation, and after being left, the retention force test was performed as the initial retention force.

(3-3) Regarding the relationship between retention and failure mode Here, the relationship between the holding force of the adhesive tape 1 and the failure mode will be described. FIG. 3 is a schematic diagram illustrating the relationship between the crosslink density of the addition reaction type polysiloxane-based adhesive in the adhesive layer 3 and the result (fall time) of the retention test of the adhesive tape 1. As shown in FIG. 3, with respect to the adhesive tape 1, as the crosslink density of the addition reaction type polysiloxane-based adhesive in the adhesive layer 3 rises, the destruction of the stainless steel plate by the adhesive tape 1 according to the retention test The mode change is [Cohesive failure of adhesive layer 3 (falling)] → [Keep (not falling)] → [Interface failure of adhesive layer 3 and stainless steel plate (falling)].

In addition, as shown in FIG. 3, in the region where the failure mode of the adhesive tape 1 is the failure of cohesion, the holding force (fall time) of the adhesive tape 1 follows the addition reaction type polysiloxane-based adhesive in the adhesive layer 3 The crosslink density rises and rises. On the other hand, as shown in FIG. 3, in the region where the failure mode of the adhesive tape 1 is the interface failure, the holding force (fall time) of the adhesive tape 1 adheres with the addition reaction type polysiloxane based in the adhesive layer 3 The crosslink density of the agent increases and decreases. The reason for this is presumed that as the crosslinking density of the addition reaction type polysiloxane-based adhesive increases, the cohesive force of the adhesive layer 3 increases, and the adhesive force of the adhesive tape 1 decreases. As a result, the adhesive tape 1 easily peels off from the stainless steel plate And fall.

Regarding the results of the retention test, it is preferable that the failure mode after at least UV irradiation is retention or interface failure, and it is more preferable that the failure mode after at least UV irradiation is interface failure, and still more preferably the initial (before UV irradiation) and after UV irradiation The destruction modes are all interface destruction. In addition, when both the initial (before UV irradiation) and the failure modes after UV irradiation are interface failure, it is preferable that the retention force (fall time) after UV irradiation is lower than the initial (before UV irradiation). In this case, after the adhesive tape 1 is used for dicing of a semiconductor element substrate or the like, when the obtained semiconductor wafer or the like is peeled from the adhesive tape 1, the adhesive tape 1 is irradiated with UV so that adhesive residues are not easily generated on the semiconductor wafer or the like.

(4) Test on residue of polysiloxane resin adhesive With respect to the adhesive tapes 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8, an adhesive residue test for silicone resins was conducted. First, agent A and agent B for methyl silicone-containing polysiloxane resin (KER-2500N (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) for polysiloxane resin for LED devices are mixed at a mixing ratio of 1:1. Make a mixed solution. This mixed liquid was applied to a stainless steel plate, and heat-cured at 100° C.×1 hour and further at 150° C.×2 hours to produce a polysiloxane test piece A. Similarly, agent A and agent B for phenyl group-containing polysiloxane resin (KER-6110 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), which is a polysiloxane resin for LED devices, are mixed at a mixing ratio of 3:7 And make mixed liquid. This mixed liquid was applied to a stainless steel plate, and heat-cured at 100° C.×2 hours and further at 150° C.×5 hours to produce a polysiloxane test piece B.

Next, the adhesive layer 3 of the adhesive tape 1 was adhered to the polysiloxane test pieces A and B, respectively, and a roller with a mass of 2000 g was reciprocated once at a speed of 5 mm/s to perform pressure bonding. Next, the conditions for the measurement of the ball viscosity after UV irradiation were created, and after irradiation of ultraviolet rays from the substrate 2 side of the adhesive tape 1, it was left for 120 hours in an environment at a temperature of 40° C. and a humidity of 90% RH. After adjusting to room temperature, the adhesive tape 1 was peeled off at a speed of 800 mm/s to 1200 mm/s for the polysiloxane test pieces A and B in the 90° direction, and the polysiloxane test pieces A and B were visually confirmed. Of adhesive residue.

(5) Test on the residue of epoxy resin adhesive With respect to the adhesive tape 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8, an adhesive residue test for epoxy resins was conducted. The adhesive layer 3 of the adhesive tape 1 is adhered to an epoxy test piece made of an epoxy resin plate (NL-EG-23 (trade name) manufactured by Nikko Chemical Co., Ltd.) in which a glass cloth substrate is impregnated with epoxy resin. The roller with a mass of 2000 g was reciprocated once at a speed d of 5 mm/s to perform pressure bonding. Next, the conditions for the measurement of the ball viscosity after UV irradiation were created, and after irradiation of ultraviolet rays from the substrate 2 side of the adhesive tape 1, it was left for 120 hours in an environment at a temperature of 40° C. and a humidity of 90% RH. Thereafter, the temperature was adjusted to room temperature, and the adhesive tape 1 was peeled off at a speed of 800 mm/s to 1200 mm/s in the 90° direction to the epoxy test piece to visually confirm the adhesive residue on the epoxy test piece.

The silicone resin adhesive residue test and the epoxy resin adhesive residue test are evaluated according to the following criteria. In addition, the evaluation of A or B was passed. A: There is no adhesive residue within 100% of the unit area of the test piece B: Adhesive residue was found within the range of less than 2% of the unit area of the test piece C: Adhesive residue was found in the range of more than 2% and less than 5% per unit area of the test piece D: Adhesive residues are found in the range of more than 5% of the unit area of the test piece, or adhesive residues are found on the edge of the test piece

(6) Cutting test The adhesive tape 1 produced in Examples 1 to 15 and Comparative Examples 1 to 8 was subjected to a cutting test. Specifically, first, an epoxy resin for molds (CEL-400ZHF40-W75G (trade name) manufactured by Hitachi Chemical Co., Ltd.) is put into a metal mold, and the sealing pressure is 50 kgf/cm ² (491 N/cm ² ). Thickness of 0.3 mm and heating temperature of 150° C.×300 seconds were subjected to heating and hardening to produce disc-shaped (200 mm (8 inch) diameter) cutting test pieces. In addition, the adhesive layer 3 of the adhesive tape 1 was adhered to the cutting ring, and the portion protruding from the ring was cut off, and then further adhered to a fluorine-based release film (SS1A (trade name) manufactured by Nippa Corporation, thickness 75 μm). Next, a roller having a mass of 2000 g was reciprocated, and the adhesive tape 1 and the ring portion were pressure-bonded. Next, the fluorine-based peeling film was peeled off, and the dicing test piece was adhered to the adhesive layer at the central portion of the ring to perform pressure bonding.

Furthermore, using a dicing device (A-WD-100A (trade name)) manufactured by Tokyo Precision Co., Ltd., a dicing blade manufactured by DISCO Co., Ltd. was used to cut the dicing test piece together with the adhesive tape 1 into 10 mm×10 mm wafers. At this time, the number of scattered wafers was measured, and the fixing force in the dicing test was evaluated. Next, the adhesive tape 1 adhered to the individual wafers having a size of 10 mm×10 mm was irradiated with ultraviolet rays under the conditions described in the measurement of the roller ball viscosity after UV irradiation. After that, a wafer pieced from the adhesive tape was picked up, and the presence or absence of adhesive residue on the wafer was visually confirmed, and evaluation of the adhesive residue in the dicing test was performed. In addition, when picking up a wafer, the number of wafers that failed to pick up was measured, and the pickability in the dicing test was evaluated.

The fixing force in the cutting test was evaluated according to the following criteria. In addition, the evaluation of A or B was passed. A: The number of scattered chips is 0 out of 100 B: The number of scattered chips is 1 out of 100 C: The number of scattered chips is 2 out of 100 D: The number of scattered chips is more than 3 out of 100

The adhesive residue in the cutting test was evaluated according to the following criteria. In addition, the evaluation of A was passed. A: No adhesive residue was found on the wafer D: Adhesive residue found on the wafer, or the filament of the adhesive found on the side of the wafer

The pickability in the cutting test was evaluated according to the following criteria. In addition, the evaluation of A or B was passed. A: The number of wafers that failed to be picked is 0 out of 100 B: The number of failed wafers is 1 out of 100 C: The number of failed wafers is 2 out of 100 D: The number of failed pick-up wafers is more than 3 out of 100

3. Test results The evaluation results of the adhesive tapes 1 of Examples 1 to 15 and Comparative Examples 1 to 8 are shown in Tables 4 to 6.

As shown in Tables 4 to 6, with the adhesive layer 3, an addition reaction type polysiloxane-based adhesive is used as a main agent and contains a photosensitive platinum (Pt) catalyst and the addition reaction type polysiloxane-based adhesive. The adhesive tape 1 of Examples 1 to 8 corresponding to the first form of the crosslinking agent, and a mixture of the addition reaction type polysiloxane-based adhesive and the peroxide-curing polysiloxane-based adhesive to the adhesive layer 3 The adhesive tapes of Examples 9 to 15 corresponding to the second form of the main agent and containing the photosensitive platinum (Pt) catalyst and the cross-linking agent for the addition reaction type polysiloxane-based adhesive 1 aspect, the adhesion test, Any one of the ball adhesion test, the retention test, the silicone resin adhesive residue test, the epoxy resin adhesive residue test, and the cutting test (fixing force, adhesive residue and pick-up) All of them confirmed that good results were obtained.

Thereby, the first layer of the addition reaction type polysiloxane-based adhesive with the adhesive layer 3 containing the photosensitive platinum (Pt) catalyst and the crosslinking agent for the addition reaction type polysiloxane-based adhesive The adhesive tape 1 of Examples 1 to 8 corresponding to the form 1 and the adhesive layer 3 are mainly composed of a mixture of an addition-reactive polysiloxane-based adhesive and a peroxide-curable polysiloxane-based adhesive and include The photosensitive platinum (Pt) catalyst and the cross-linking agent for the addition reaction type polysiloxane-based adhesive according to the second form of the adhesive tapes of Examples 9 to 15 are confirmed to be used as an adhesive for cutting semiconductor materials The tape is more specifically used as a dicing adhesive tape used for dicing as a sticking from the sealing resin side of the semiconductor element substrate.

In contrast, Comparative Examples 1 to 3 where the adhesive layer 3 does not meet the conditions of the adhesive layer 3 of the first form and Comparative Examples 4 to 8 where the adhesive layer 3 does not meet the conditions of the adhesive layer 3 of the second form For the silicone resin adhesive residue test, the epoxy resin adhesive residue test and the cutting test (fixing force, adhesive residue and pick-up), it was confirmed that any one of the test results was worse than Examples 1 to 15. result.

Specifically, the adhesive tape 1 of Comparative Example 1 that does not include the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the first aspect, although it includes a general platinum (Pt) catalyst, rolls before and after UV irradiation. There was no change in the results of the ball adhesion test and the retention test, and the cohesion was not sufficiently improved. Therefore, many residues of adhesive were found in the residue test of polysiloxane resin adhesive and the residue test of epoxy resin adhesive. Thing. In addition, during the dicing test, the wafer of the dicing test piece was also poorly picked up, and adhesive residue was found on the wafer.

In addition, the adhesive tape 1 of Comparative Example 4 excluding the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the second aspect also had the same results as Comparative Example 1.

Furthermore, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) to the total mass (Rw) of the silicone (R) and the silicone (G) and poly The content ratio of the polysiloxane having an alkenyl group (G1) in the total mass of the silicone resin (R) is less than the lower limit of the adhesive layer 3 of the first aspect, the adhesive tape 1 of the comparative example 2 The adhesion is high. Before and after UV irradiation, there is little change in the results of the ball adhesion test and the retention test, and the cohesive strength is slightly insufficient. To this end, in the silicone resin adhesive residue test and epoxy resin adhesive residue test, found many adhesive residues. In addition, during the dicing test, the wafer of the dicing test piece was also poorly picked up, and adhesive residue was found on the wafer surface.

In addition, the mass ratio (Gw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) and the polysiloxane (G) and poly The adhesive tape 1 of Comparative Example 3 in which the content ratio of the polysiloxane having an alkenyl group (G1) in the total mass of the silicone resin (R) exceeds the upper limit of the adhesive layer 3 of the first aspect, respectively, Before and after UV irradiation, although the results of the ball adhesion test and the retention test changed, the cohesion increased and the adhesion was low. Therefore, in the cutting test, the fixing force of the cutting test piece was low, and many chips were scattered. In addition, no residue of adhesive was found in the test of residue of silicone adhesive and the test of residue of epoxy resin. In addition, in the dicing test, no adhesive residue was found on the unscattered wafers.

In addition, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) is less than the adhesive layer of the second aspect. For the adhesive tape 1 of Comparative Example 5 of the lower limit value, before and after UV irradiation, although the results of the ball adhesion test and the retention test changed slightly and the cohesive force was improved, it was still not sufficient. In the cutting test, we learned that the cutting test The pick-up of the wafer is slightly poor. In addition, in the silicone resin adhesive residue test and the epoxy resin adhesive residue test, the adhesive residue is slightly present. In the dicing test, the pickable wafer, no adhesive residue was found .

In addition, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) exceeds the adhesive layer of the second aspect in three aspects In the adhesive tape 1 of Comparative Example 6 of the upper limit value, before and after UV irradiation, although the results of the ball adhesion test and the retention test change, the cohesive force is improved and the adhesive force is low, so the cutting test is fixed by the cutting test piece The force is low, and many wafers are found to be scattered. In addition, no residue of adhesive was found in the test of residue of silicone adhesive and the test of residue of epoxy resin. In addition, in the dicing test, no adhesive residue was found on the unscattered wafers.

In addition, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) exceeds the adhesive layer of the second aspect in three aspects The upper limit value of the polysiloxane (G) and the polysiloxane resin (R) in the total mass of the polysiloxane (G1) with an alkenyl group content ratio is less than the second form of the adhesive layer 3 In the adhesive tape 1 of Comparative Example 7 of the lower limit value, the adhesive strength is high due to the hardening of the peroxide-curable silicone adhesive, and the results of the ball adhesion test and the retention test before and after UV irradiation There are few changes in the aspect, and the further improvement of cohesion is slightly insufficient. To this end, in the silicone resin adhesive residue test and epoxy resin adhesive residue test, found many adhesive residues. In addition, during the dicing test, the wafer of the dicing test piece was also poorly picked up, and adhesive residue was found on the wafer surface.

In addition, the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) exceeds the upper limit of the third aspect of the adhesive layer 3 In the adhesive tape 1 of Comparative Example 8, before and after UV irradiation, although the results of the ball adhesion test and the retention test changed, the cohesive force was improved and the adhesive force was low. Therefore, the cutting test has a low fixing force for the cutting test piece. It was found that many wafers were scattered. In addition, no residue of adhesive was found in the test of residue of silicone adhesive and the test of residue of epoxy resin. In addition, in the dicing test, no adhesive residue was found on the unscattered wafers.

1: adhesive tape 2: substrate 3: Adhesive layer 100: semiconductor element substrate 101: substrate 102: Semiconductor components 103: Sealing resin 200: semiconductor chip

[Fig. 1] A diagram showing an example of a configuration to which the adhesive tape for cutting according to this embodiment is applied. [Fig. 2] (a) to (e) are diagrams illustrating a method of manufacturing a semiconductor wafer using the adhesive tape of this embodiment. [Fig. 3] A schematic diagram showing the relationship between the crosslinking density of the addition reaction type polysiloxane-based adhesive in the adhesive layer and the result (fall time) of the adhesive tape retention test.

1: adhesive tape

2: substrate

3: Adhesive layer

Claims (6)

An adhesive tape for dicing, which is provided with a base material and a polysiloxane adhesive layer laminated on the base material, and is used to divide a semiconductor material having a plurality of semiconductor elements covered by a covering material into a plurality of semiconductor chips On occasion, The aforementioned polysiloxane-based adhesive layer uses an addition-reactive polysiloxane-based adhesive as a main agent, including a photosensitive platinum (Pt) catalyst and a crosslinking agent for the addition-reactive polysiloxane-based adhesive, The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the polysiloxane adhesive layer to the total mass (Rw) of the polysiloxane resin (R) is 35 In the range of /65 to 50/50, the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (G) is 35% by mass or more And the range below 50% by mass, The standard meets all of the following conditions (a) to (c) under the adhesive properties of JIS Z 0237 (2009): (a) The adhesion to the BA-SUS test plate before light irradiation is 2.4N/10mm or more and 5.5N/10mm or less; (b) The value of the number of balls in the tilted ball viscosity test (inclination angle 30°, temperature 23°C, relative humidity 50% RH) before the light irradiation is BN0, after light irradiation When the value of the number of balls is BN1, the relationship is BN0>BN1; (c) Retention test after light irradiation (temperature 40°C, relative humidity 33%RH, storage time 5000 minutes), the failure phenomenon when falling is the interface between the aforementioned polysiloxane adhesive layer and the BA-SUS test board Failure, or do not fall during the retention test. An adhesive tape for dicing as claimed in item 1 of the patent application, wherein a plurality of the semiconductor materials sealed with the coating material made of polysiloxane resin are bonded and used from the coating material side. An adhesive tape for dicing, which is provided with a base material and a polysiloxane adhesive layer laminated on the base material, and is used to divide a semiconductor material having a plurality of semiconductor elements covered by a covering material into a plurality of semiconductor chips On occasion, The aforementioned polysiloxane-based adhesive layer is mainly composed of a mixture of an addition-reactive polysiloxane-based adhesive and a peroxide-curable polysiloxane-based adhesive, including a photosensitive platinum (Pt) catalyst and the addition Crosslinking agent for reactive polysiloxane adhesives, The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the aforementioned polysiloxane adhesive layer to the total mass (Rw) of the polysiloxane resin (R) is 40 In the range of /60 to 56/44, the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (G) is 14% by mass or more And the range below 42% by mass, The standard meets all of the following conditions (a) to (c) under the adhesive properties of JIS Z 0237 (2009): (a) The adhesion to the BA-SUS test plate before light irradiation is 2.4N/10mm or more and 5.5N/10mm or less; (b) The value of the number of balls in the tilted ball viscosity test (inclination angle 30°, temperature 23°C, relative humidity 50% RH) before the light irradiation is BN0, after light irradiation When the value of the number of balls is BN1, the relationship is BN0>BN1; (c) Retention test after light irradiation (temperature 40°C, relative humidity 33%RH, storage time 5000 minutes), the failure phenomenon when falling is the interface between the aforementioned polysiloxane adhesive layer and the BA-SUS test board Failure, or do not fall during the retention test. An adhesive tape for dicing as claimed in item 3 of the patent application, wherein the semiconductor material sealed by the coating material made of polysiloxane resin is used by sticking the semiconductor material from the side of the coating material. An adhesive tape for cutting as claimed in item 3 or 4 of the patent application, wherein the polysiloxane adhesive layer further contains an initiator made of peroxide. A method for manufacturing a semiconductor wafer, including: A pasting process for forming a plurality of the aforementioned semiconductor elements sealed with a sealing resin made of polysiloxane resin on the substrate by cutting the adhesive tape for dicing according to any one of claims 1 to 5 Of the semiconductor element substrate, from the side of the sealing resin; A cutting process, which is to cut the semiconductor element substrate to which the adhesive tape for dicing is stuck into a plurality of semiconductor chips; An irradiation procedure, which is to irradiate light to the dicing adhesive tape of the semiconductor element substrate; and The peeling procedure is a method of peeling the dicing adhesive tape from the plurality of semiconductor wafers.

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