TWI840630B - Adhesive tape for dicing and method for manufacturing semiconductor chip - Google Patents

Abstract

A dicing adhesive tape comprises a substrate and an adhesive layer, wherein the adhesive layer is composed of an adhesive composition, wherein the adhesive composition comprises: a silicone resin mixed with silicone glue (G) and silicone resin (R), an organic polysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule as a crosslinking agent, and a photosensitive platinum (Pt) catalyst, wherein the mixing ratio of the silicone glue (G) to the silicone resin (R) is in the range of 35.0/65.0 to 50.0/50.0, the silicone glue (G) comprises silicone glue (G) composed of an organic polysiloxane containing silicon atom-bonded olefinic groups, and the silicone resin (R) is preferably selected from the group consisting of silicone glue (G) and silicone resin ( _R). ), the content of silicon atom-bonded olefin groups is in the range of 1.8×10 ^-6 mol/g to 1.0×10 ^-5 mol/g.

Description

Adhesive tape for dicing and method for manufacturing semiconductor chip

The present invention relates to a dicing adhesive tape used when dicing a semiconductor material that becomes a semiconductor chip material, and a method for manufacturing a semiconductor chip using the dicing adhesive tape.

Conventionally, as a dicing adhesive tape used for manufacturing semiconductor chips having LEDs (light emitting diodes), there is known an adhesive tape having an adhesive layer composed of an acrylic resin (see Patent Document 1). Also, as a dicing adhesive tape used for manufacturing semiconductor chips having LEDs, there is known an adhesive tape having an adhesive layer composed of a silicone resin (see Patent Document 2 and Patent Document 3). Furthermore, as a method for manufacturing semiconductor chips using a dicing adhesive tape, an adhesive tape is attached to the substrate side of a semiconductor element substrate having a plurality of semiconductor elements formed on the substrate, and the semiconductor element substrate is cut by a dicing machine (see Patent Document 4). [Prior art literature] [Patent literature]

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

[The problem that the invention wants to solve]

On the other hand, in recent years, as a method for producing semiconductor chips that are cut into individual pieces by dicing, a technique has been proposed in which an adhesive tape is attached to a semiconductor material in which a plurality of semiconductor elements are covered with a coating material such as a sealing resin or a fluorescent body, and then cut. This technique corresponds to the so-called wafer-level CSP (chip size package) process. Therefore, when an adhesive tape is attached to a semiconductor material in which a semiconductor element is covered with a coating material, there is a possibility that the adhesive force is insufficient, depending on the composition of the adhesive layer in the adhesive tape or the material of the coating material, and the semiconductor chips that are cut into individual pieces by dicing may scatter. Furthermore, in order to suppress the scattering of semiconductor chips, if the rolling ball viscosity or adhesive force of the adhesive layer is designed to be higher, when the semiconductor chip is peeled off from the adhesive tape, some adhesive will remain attached to the semiconductor chip, which is the so-called adhesive residue.

The purpose of the present invention is to provide an adhesive tape for dicing that has good adhesive strength and tack strength for a semiconductor material having a plurality of semiconductor elements coated with a coating material, and that suppresses the residual adhesive on the semiconductor chip when the semiconductor chip that has been individualized by dicing is peeled off, and a method for manufacturing a semiconductor chip using the same. [Means for solving the problem]

Based on this purpose, the inventors of the present invention have carefully studied the adhesive layer of the adhesive tape for dicing and found that if the adhesive layer is made of a silicone resin comprising at least (1) silicone gum composed of an organic polysiloxane containing an olefin group bonded to a silicon atom, and (2) a specific resin composition containing a crosslinking agent having a hydrogen atom (SiH group) bonded to a silicon atom, and (3) an adhesive composition containing a photosensitive platinum (Pt) catalyst is added, and the silicone gum in the silicone resin is mixed with the silicone resin. By setting the mixing ratio of silicone resin and the content of silicon atom-bonded olefinic groups in the whole silicone resin to a specified range, the conductive material having a plurality of semiconductor elements coated by the coating material has good adhesion, and when the semiconductor chip that has been cut into individual pieces by dicing is peeled off, the residual adhesive on the semiconductor chip is suppressed, thereby completing the present invention. That is, it was found that the following effects can be achieved by making the adhesive layer of the dicing adhesive tape into an adhesive composition composed of a silicone glue and a silicone resin mixed at a specified ratio, and adding a crosslinking agent and a photosensitive platinum (Pt) catalyst to the silicone resin having a specified amount of silicon atom-bonded olefinic groups. First, when a semiconductor material having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips, the adhesive layer is composed of an adhesive composition including a silicone resin formed by mixing silicone glue and silicone resin in an appropriate ratio. Therefore, it is found that the good adhesion and adhesion given by the ratio can suppress the scattering of the individual semiconductor chips during dicing. On the other hand, when the semiconductor chip that has been cut into pieces is peeled off from the dicing adhesive tape, the light-sensitive platinum (Pt) catalyst in the adhesive composition is activated by irradiating the adhesive layer with light such as ultraviolet rays, and the cross-linking reaction (addition reaction) between the silicon atom-bonded olefin group of the silicone adhesive in the silicone resin and the silicon atom-bonded hydrogen atom (SiH group) of the cross-linking agent is promoted, thereby increasing the cross-linking density, and thus the cohesive force of the adhesive composition is increased compared to before light irradiation. As a result, the adhesion of the adhesive layer is moderately reduced, and the destruction mode in the retention test becomes "interface peeling" or "no fall" in the retention test. Thereby, the pick-up property of the semiconductor chip from the dicing adhesive tape becomes good, and it is found that the residual adhesive on the semiconductor chip is suppressed.

The dicing adhesive tape of the present invention is characterized by having a substrate and an adhesive layer laminated on the substrate, and is used when a semiconductor material is divided into a plurality of semiconductor chips, wherein the semiconductor material has a plurality of semiconductor elements coated by a coating material, and the adhesive layer is composed of an adhesive composition, and the adhesive composition includes: a silicone resin mixed with a silicone glue (G) and a silicone resin (R), and a silicone resin as a crosslinker to the silicone resin. The linker comprises an organic polysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) in one molecule, and a photosensitive platinum (Pt) catalyst, wherein the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) in the silicone resin as a whole is in the range of 35.0/65.0 to 50.0/50.0 in terms of mass ratio, the silicone gel (G) comprises: a silicone gel (G _alk ) composed of an organic polysiloxane containing a silicon-bonded alkenyl group, and the content of the silicon-bonded alkenyl group in the silicone resin as a whole is in the range of 1.8×10 ^-6 mol/g to 1.0×10 ^-5 mol/g. Here, the feature is that a plurality of the aforementioned semiconductor elements can be attached to the aforementioned semiconductor material sealed by the aforementioned covering material from the side of the covering material, and the covering material is composed of a silicone resin. In addition, the feature is that the content of the aforementioned silicon atom-bonded olefin groups in the entire silicone resin in the aforementioned adhesive layer is in the range of 3.0×10 ^-6 mol/g or more and 1.0×10 ^-5 mol/g or less. Furthermore, the adhesive layer can be made such that the molar ratio (SiH group/silicon atom bonded olefin group) of the aforementioned crosslinking agent and the aforementioned silicon atom bonded hydrogen atom (SiH group) contained in the adhesive composition to the aforementioned silicon atom bonded olefin group in the aforementioned silicon-oxygen resin contained in the adhesive composition is in the range of 2.0 to 10.0. Furthermore, the adhesive layer can be made such that the content of the aforementioned photosensitive platinum (Pt) catalyst in the adhesive composition is in the range of 0.10 to 3.00 parts by mass based on the solid content, relative to 100 parts by mass of the solid content of the aforementioned silicon-oxygen resin. Furthermore, the adhesive properties according to JIS Z 0237 (2009) can be made to meet all the following conditions (a) to (c): (a) The adhesive force of the BA-SUS test plate before light irradiation is in the range of 2.7N/10mm to 4.1N/10mm; (b) In the ball tack test (tilt angle 30°, temperature 23°C, relative humidity 50%RH), when the ball number before light irradiation is set as BN0 and the ball number after light irradiation is set as BN1, the relationship of BN0＞BN1 is achieved. (c) In the retention test after light irradiation (temperature 40°C, relative humidity 33%RH, placement time 2880 minutes), the damage phenomenon when falling is the interface between the above-mentioned adhesive layer and the BA-SUS test plate peeling off, or there is no falling in the retention test.

Furthermore, when adopting other viewpoints, the manufacturing method of the semiconductor chip to which the present invention is applied is a manufacturing method of the semiconductor chip, which comprises, a bonding step: for a semiconductor element substrate on which a plurality of the aforementioned semiconductor elements are formed on a substrate and sealed by a sealing resin composed of a silicone resin, the above-mentioned dicing adhesive tape is bonded from the side of the sealing resin; a cutting step: for cutting the above-mentioned semiconductor element substrate to which the above-mentioned dicing adhesive tape is attached into a plurality of semiconductor chips; an irradiation step: for irradiating the above-mentioned dicing adhesive tape of the above-mentioned semiconductor element substrate with light; and a peeling step: for peeling the above-mentioned dicing adhesive tape from the above-mentioned plurality of semiconductor chips. [Effect of the invention]

According to the present invention, there can be provided a semiconductor material coated with a coating material having good adhesion and tackiness before light irradiation, and having good pickup properties for semiconductor chips when peeling off individual semiconductor chips by dicing after light irradiation, and at the same time, an adhesive tape for dicing in which residual adhesive on the semiconductor chips is suppressed, and a method for manufacturing semiconductor chips using the same.

Hereinafter, the embodiment of the present invention will be described in detail with reference to the attached drawings. [Composition of Adhesive Tape] Figure 1 is a diagram showing an example of the composition of an adhesive tape 1 for cutting (hereinafter, simply referred to as adhesive tape 1) applicable to the present embodiment. The adhesive tape 1 of the present embodiment is a semiconductor material used as a basis for cutting into semiconductor chips in the manufacturing process of semiconductor chips having semiconductor elements such as LEDs (light emitting diodes) or power semiconductors.

As shown in FIG. 1 , the adhesive tape 1 has a structure in which an adhesive layer 3 is laminated on a substrate 2. Also, although not shown in the figure, the adhesive tape 1 may also have an anchor coating layer between the substrate 2 and the adhesive layer 3 to improve the adhesion between the substrate 2 and the adhesive layer 3 as necessary. In addition, a surface treatment may be applied to the surface of the substrate 2 (the surface opposite to the surface facing the adhesive layer 3). Furthermore, the surface of the adhesive layer 3 (the surface opposite to the surface facing the substrate 2) may also have a peeling liner.

<Substrate> The substrate 2 of this embodiment is made of a material that allows ultraviolet light to penetrate. The material of the substrate 2 is not particularly limited as long as it allows ultraviolet light to penetrate. For example, plastics that allow ultraviolet light to penetrate can be used. Moreover, here, the ability of ultraviolet light to penetrate does not mean that the transmittance of ultraviolet light is 100%. It is sufficient that the light can penetrate at least to the extent that the photosensitive platinum (Pt) catalyst described later contained in the adhesive layer 3 can promote the addition reaction between the silicone resin and the crosslinking agent.

As the material of the substrate 2, specifically, resin films such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxially oriented polypropylene, aliphatic polyimide (transparent polyimide), polycycloolefin, fluorine resin, polyolefin resin, etc. can be used. In addition, depending on the application, the substrate 2 can also use, for example, a composite film formed by laminating polyethylene terephthalate and polyolefin resin films, a composite film formed by laminating these composite films with resin films, a resin film made of multiple layers by co-extrusion, etc. Among them, as the substrate 2, it is preferable to use a material having polyethylene terephthalate as the main component.

<Adhesive layer> The adhesive layer 3 of the present embodiment is composed of an adhesive composition, which contains: a silicone resin mixed with silicone gel (G) and silicone resin (R), a crosslinking agent for the silicone resin having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule, and a photosensitive platinum (Pt) catalyst. The silicone resin is composed of a mixed resin in which "silicone glue (G) composed of an organic polysiloxane containing silicon atoms bonded to alkenyl groups (G _alk )" and "silicone resin (R) composed of an organic polysiloxane" are mixed at a specified ratio. The following describes the components of the adhesive composition constituting the adhesive layer 3 in order.

(Silicone-based resin) The silicone-based resin of the present embodiment is composed of a mixed resin, wherein "silicone gel ( _G ) composed of an organic polysiloxane containing an olefin group bonded to a silicon atom" and "silicone resin (R) composed of an organic polysiloxane" are blended in a range of 35.0/65.0 to 50.0/50.0. That is, the mixed resin is composed of a silicone gel (G) and a silicone resin (R) in a mass ratio ((G)/(R)) in a range of 35.0/65.0 to 50.0/50.0. Furthermore, the silicone resin is configured so that the content of silicon atom-bonded olefin groups in the silicone resin as a whole is in the range of 1.8× ^10-6 mol/g to 1.0× ^10-5 mol/g, preferably in the range of 3.0× ^10-6 mol/g to 1.0× ^10-5 mol/g. Here, "mol/g" means "the mass per 1g of the solid content of the silicone resin as a whole".

If the content of silicon-bonded olefin groups in the entire silicone resin is less than 1.8×10 ^-6 mol/g, when the adhesive tape 1 is irradiated with ultraviolet light or the like, the crosslinking density formed by the crosslinking reaction (addition reaction) between the silicon-bonded olefin groups of the silicone adhesive and the silicon-bonded hydrogen atoms (SiH groups) of the crosslinking agent will not be sufficiently increased, and the adhesive will be difficult to harden and the cohesive force will be difficult to increase. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. After the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become easy to produce residual adhesive. On the other hand, when the content of silicon-atom-bonded alkenyl groups in the entire silicone resin exceeds 1.0×10 ^-5 mol/g, when a release liner treated with fluoroalkyl-modified silicone is provided in the adhesive tape 1, for example, the release force of the release liner on the adhesive layer 3 may increase. In addition, there is a concern that the storage stability of the adhesive tape 1 against light may deteriorate.

The content of silicon-atom-bonded alkenyl groups in the entire silicone resin can be calculated by measuring the ¹ H-NMR (nuclear magnetic resonance) spectrum relative to the non-volatile components of the silicone resin and finding the resonance signal area (integral value) of the alkenyl groups. The details are described below.

Furthermore, the silicone resin of the present embodiment may also include silicone gel (G 0 ) composed of an organic polysiloxane containing no silicon atom-bonded olefinic group, as long as the "mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin _(R )" and the "content of silicon atom-bonded olefinic group" are within the above ranges. That is, the silicone gel (G) may be a single "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G _alk )" or a mixture of two or more thereof, or a mixture of a "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G _alk )" and a "silicone gel composed of an organic polysiloxane not containing an alkenyl group bonded to a silicon atom (G ₀ )" or a mixture of two or more thereof.

The following is a more detailed description of the silicone resins including "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G _alk )", "silicone gel composed of an organic polysiloxane containing no alkenyl group bonded to a silicon atom (G ₀ )", and "silicone resin composed of an organic polysiloxane containing no alkenyl group bonded to a silicon atom (R)". Furthermore, in the following description, silicone gel (G _alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group may be described as silicone gel containing a silicon atom-bonded alkenyl group (G _alk ) or simply as silicone gel (G _alk ). Similarly, silicone gel (G ₀ ) composed of an organic polysiloxane not containing a silicon atom-bonded alkenyl group may be described as silicone gel not containing a silicon atom-bonded alkenyl group (G ₀ ) or simply as silicone gel (G ₀ ). Furthermore, there are cases where a silicone resin (R) composed of an organic polysiloxane is simply described as a silicone resin (R).

(Silicon oxide gel (G _alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group) The silicone oxide gel (G _alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group in this embodiment is not particularly limited as long as it is generally used as an addition reaction type silicone resin, that is, it contains at least 2 silicon atom-bonded alkenyl groups in one molecule on average. Specifically, as the silicone oxide gel (G _alk ), the content of silicon atom-bonded alkenyl groups can be in the range of 1.0×10 ^-6 mol/g or more and 1.0×10 ^-1 mol/g or less. In this embodiment, from the viewpoint of controlling the adhesive properties of the adhesive layer 3 or the ease of obtaining when using commercial products, it is preferred to use a silicon atom-bonded olefinic group content in the range of 1.7× ^10-6 mol/g or more and 1.0× ^10-2 mol/g or less. The silicone gel (G _alk ) is a silicone resin obtained by mixing the silicone gel (G) and the silicone resin (R) described above so that the olefinic group content in the whole silicone resin is in the range of 1.8× ^10-6 mol/g or more and 1.0× ^10-5 mol/g or less. One type may be used alone or two or more types may be used in combination.

As the molecular structure of the organic polysiloxane containing silicon atoms bonded to alkenyl groups constituting silicone gel ( _Galk ), for example, a linear chain structure consisting of a main chain portion composed of repeated two organic siloxane units, a structure in which a part of the molecular structure includes a branched chain structure, a branched chain structure, or a ring structure can be cited. Among them, from the perspective of the mechanical strength and physical properties of the adhesive after irradiation with ultraviolet light, etc., an organic polysiloxane with a linear chain structure is preferred.

Silicone glue (G _alk ) composed of organic polysiloxane containing silicon atoms bonded to alkenyl groups can be either oily or rubbery, with the rubbery form being preferred. In the case of oily form, the viscosity of silicone glue (G _alk ) composed of organic polysiloxane is preferably 1,000 mPa·s or more at 25°C. If the viscosity is less than 1,000 mPa·s, there is a concern that the adhesive before and after irradiation with ultraviolet light or the like may not exhibit the desired adhesive properties, or that the adhesion between the adhesive layer 3 and the substrate 2 may deteriorate. In the case of raw rubber, the viscosity of silicone gel (G _alk ) composed of organic polysiloxane is preferably 100,000 mPa·s or less at 25°C when dissolved in toluene at a concentration of 30 mass%. If the viscosity exceeds 100,000 mPa·s, stirring may become difficult when preparing the adhesive composition. In addition, the viscosity of silicone gel (G _alk ) composed of organic polysiloxane can be measured with a B-type rotational viscometer (using a BM-type rotor, the same below).

Silicone gel ( _Galk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group may be, for example, represented by the following general formula (1) or general formula (2), but is not limited thereto.

Here, in the above general formula (1) and general formula (2), ^R1 is independently a monovalent hydrocarbon group without an aliphatic unsaturated bond, and X is an organic group containing an alkenyl group. a is an integer of 0 to 3, m is an integer greater than 0, and n is an integer greater than 100, but a and m are not both 0, and only when a is 0, m is an integer greater than 2. m+n is a value at which the viscosity of the silicone gel ( _Galk ) composed of the above organic polysiloxane at 25°C becomes greater than 1,000 mPa·s.

R ¹ is preferably a monovalent alkyl group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and having no aliphatic unsaturated bond. Examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl. Methyl or phenyl is particularly preferred.

X is preferably an organic group containing an alkenyl group having 2 to 10 carbon atoms. Examples thereof include vinyl, allyl, hexenyl, octenyl, acrylylpropyl, acrylylmethyl, methacrylpropyl, acryloxypropyl, acryloxymethyl, methacryloxypropyl, methacryloxymethyl, cyclohexenylethyl, and vinyloxypropyl. Among them, lower alkenyl groups such as vinyl and allyl are preferred, and vinyl is particularly preferred from an industrial point of view. The bonding position of the alkenyl group is not particularly limited, and may be at the molecular chain end, the molecular chain side chain, or both the molecular chain end and the molecular chain side chain.

The number of alkenyl groups varies depending on the content of silicone resin (R) composed of organopolysiloxane contained in the silicone adhesive, the type and amount of crosslinking agent, and the balance of other additives, so it is impossible to generalize. For example, it is usually preferably in the range of 0.1 to 3.0 relative to 100 organic groups of organopolysiloxane. And, within the range of this ratio, the molecular weight is adjusted in such a way that the viscosity range mentioned above is achieved, and it is preferably adjusted in such a way that the number of alkenyl groups in one molecule of organopolysiloxane mentioned above is at least 2. If the number of alkenyl groups is less than 0.1 relative to 100 organic groups of the organopolysiloxane, when the adhesive tape 1 is irradiated with ultraviolet light or the like, the crosslinking density obtained by the crosslinking reaction (addition reaction) between the silicon atom-bonded alkenyl groups of the silicone glue ( _Galk ) and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent for the silicone resin will be insufficient, and the adhesive will be difficult to harden and the cohesive force will be difficult to improve. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. After the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become easy to produce residual adhesive. On the other hand, if the number of alkenyl groups exceeds 3.0 relative to 100 organic groups of the organopolysiloxane, when a release liner treated with fluoroalkyl-modified silicone is provided in the adhesive tape 1, there is a concern that the release force of the release liner on the adhesive layer 3 may increase.

Specific examples of such silicone gels containing alkenyl groups bonded to silicon atoms _include dimethyl polysiloxane having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, dimethyl polysiloxane-methyl vinyl silicone copolymer having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, dimethyl polysiloxane-methyl phenyl silicone copolymer having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, methyl phenyl polysiloxane having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, dimethyl polysiloxane-methyl phenyl silicone copolymer having trimethyl silicone groups chain-blocked at both ends of the molecular chain, and dimethyl polysiloxane-methyl phenyl silicone copolymer having trimethyl silicone groups chain-blocked at both ends of the molecular chain. Vinyl siloxane copolymer, dimethylsiloxane/methylvinylsiloxane/methylphenylsiloxane copolymer with trimethylsiloxy groups chain-blocked at both ends of the molecular chain, dimethylsiloxane/methylhexenylsiloxane copolymer with trimethylsiloxy groups chain-blocked at both ends of the molecular chain, dimethylsiloxane/methylhexenylsiloxane copolymer with dimethylvinylsiloxane groups chain-blocked at both ends of the molecular chain, dimethylsiloxane/methylhexenylsiloxane copolymer with dimethylhexenylsiloxane groups chain-blocked at both ends of the molecular chain, etc.

(Silicone gel (G ₀ ) composed of an organic polysiloxane containing no silicon atom-bonded alkenyl group) The silicone gel (G ₀ ) composed of an organic polysiloxane containing no silicon atom-bonded alkenyl group in the present embodiment is not particularly limited as long as it is generally used as a peroxide-curable silicone resin, that is, it does not contain a silicon atom-bonded alkenyl group. Examples of the molecular structure of the organic polysiloxane constituting the silicone gel (G ₀ ) include a straight chain structure in which the main chain portion is composed of repeated two organic polysiloxane units, a structure in which a part of the molecular structure includes a branched chain structure, a branched chain structure, or a ring structure.

The silicone gel (G ₀ ) composed of an organic polysiloxane that does not contain a silicon atom-bonded alkenyl group may be either oily or rubbery, with the rubbery form being preferred. In the case of an oily form, the viscosity of the silicone gel (G ₀ ) composed of an organic polysiloxane is preferably 1,000 mPa·s or more at 25°C. If the viscosity is less than 1,000 mPa·s, there is a concern that the adhesive may not exhibit the desired adhesive properties before and after irradiation with ultraviolet light or the adhesion between the adhesive layer 3 and the substrate 2 may deteriorate. In the case of recycled rubber, the viscosity of silicone rubber (G ₀ ) composed of organic polysiloxane at 30 mass% concentration when dissolved in toluene is preferably 100,000 mPa·s or less at 25°C. If the viscosity exceeds 100,000 mPa·s, stirring may become difficult when preparing the adhesive composition. In addition, the viscosity of silicone rubber (G ₀ ) composed of organic polysiloxane can be measured using a B-type rotational viscometer.

The silicone gel (G ₀ ) composed of an organic polysiloxane having no silicon atom-bonded alkenyl group may be, for example, one represented by the following general formula (3) or general formula (4), but is not limited thereto.

Here, in the general formula (3) and the general formula (4), R ⁴ is independently a monovalent hydrocarbon group having no aliphatic unsaturated bond, t is an integer greater than 100, and the viscosity of the silicone gel (G ₀ ) composed of the two organopolysiloxanes is greater than 1,000 mPa·s at 25°C.

R ⁴ is preferably a monovalent alkyl group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and having no aliphatic unsaturated bond. Examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl. Methyl is particularly preferred.

(Silicone resin (R) composed of organic polysiloxane) The silicone resin (R) composed of organic polysiloxane in this embodiment is an organic polysiloxane having R ² ₃ SiO _0.5 units (M units) and SiO ₂ units (Q units), and is generally a so-called MQ resin used in silicone adhesives. The silicone resin (R) composed of organic polysiloxane basically does not have an alkenyl group in the molecule, and any conventionally known one can be used. R ² is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include those exemplified as R ¹ above. The organopolysiloxane constituting the silicone resin (R) preferably contains R ² ₃ SiO _0.5 units and SiO ₂ units in a molar ratio of R ² ₃ SiO _0.5 units/SiO ₂ units of 0.5 to 1.7. If the molar ratio of R ² ₃ SiO _0.5 units/SiO ₂ units is less than 0.5, the adhesion or adhesive force of the obtained adhesive layer 3 may be reduced. On the other hand, if the molar ratio of R ² ₃ SiO _0.5 units/SiO ₂ units exceeds 1.7, the adhesion or retention of the obtained adhesive layer 3 may be reduced. Furthermore, the organopolysiloxane constituting the silicone resin (R) may also have an OH group. In this case, the OH group content is preferably 4.0 mass % or less relative to the total mass of the organopolysiloxane. If the OH group content exceeds 4.0 mass %, there is a concern that the curability of the adhesive may be reduced.

The above-mentioned organopolysiloxane may be used in combination of two or more kinds. Furthermore, the above-mentioned organopolysiloxane may have R ² SiO _1.5 units (T units) and/or R ² ₂ SiO units (D units) within a range not impairing the properties of the present invention.

Usually, "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G _alk )", "silicone gel composed of an organic polysiloxane containing no alkenyl group bonded to a silicon atom (G ₀ )", and "silicone resin composed of an organic polysiloxane (R)" can be used simply by mixing. Furthermore, when the organopolysiloxane represented by the general formula (2) is contained as a silicone gel (G _alk ) composed of an organopolysiloxane containing an alkenyl group bonded to a silicon atom, or when the organopolysiloxane represented by the general formula (4) is contained as a silicone gel (G ₀ ) composed of an organopolysiloxane containing no alkenyl group bonded to a silicon atom, as long as the characteristics of the present invention are not impaired, a (partial) condensation reaction product obtained by reacting the silicone gel (G _alk ) with the silicone resin (R) or reacting the silicone gel (G ₀ ) with the silicone resin (R) in advance may be used.

(Mixture ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) in the whole silicone resin) In the whole silicone resin contained in the adhesive layer 3 of the present embodiment, the mixture ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) is in the range of 35.0/65.0 to 50.0/50.0 in terms of mass ratio. Here, when two or more silicone glues (G) are used in combination, the total amount of the respective silicone glues (G) is regarded as the mass of the silicone glue (G) in the whole silicone resin. For example, when silicone glue (G _alk ) and silicone glue (G ₀ ) are used together as silicone glue (G), the mass of silicone glue (G) in the entire silicone resin is the sum of the mass of silicone glue (G _alk ) and the mass of silicone glue (G ₀ ). Similarly, when two or more silicone resins (R) are used together, the sum of the respective silicone resins is also regarded as the mass of silicone resin (R) in the entire silicone resin.

If the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) in the silicone resin contained in the adhesive layer 3 of the present embodiment is less than the lower limit of the above range, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the crosslinking density obtained by the crosslinking reaction (addition reaction) between the silicon atom-bonded olefin groups of the silicone gel (G) and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent for the silicone resin is insufficiently provided, and the adhesive becomes difficult to harden and the cohesive force becomes difficult to improve. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. After the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become easy to produce adhesive residue.

On the other hand, if the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) in the entire silicone resin contained in the adhesive layer 3 of the present embodiment exceeds the upper limit of the above range, when the semiconductor device substrate is cut before the adhesive is irradiated with ultraviolet light or the like and the adhesive has not yet hardened, the vibration of the cutting becomes easy to be transmitted to the adhesive layer 3 and the vibration amplitude becomes larger, for example, there is a concern that the semiconductor device substrate is offset from the reference position. And, accompanying this, there is a concern that the individualized semiconductor chips will be damaged (chipping), or there is a concern that each individual semiconductor chip will have a deviation in size. In addition, there is also a concern that the adhesion of the adhesive layer 3 will be reduced or the adhesion will be reduced. In this case, when the adhesive tape 1 is used for cutting a semiconductor device substrate or a fluorescent substrate described later, there is a concern that the semiconductor chips of the cut pieces may fly away.

In contrast, in the entire silicone resin contained in the adhesive layer 3 of the present embodiment, by making the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) within the above range, the following effects can be achieved. That is, at the stage before irradiation with ultraviolet light or the like, the adhesive layer 3 in a state that has not yet been cured can be given an appropriate adhesive force and adhesion that does not cause the semiconductor chips etc. to fly apart when cut into pieces during dicing. On the other hand, after irradiation with ultraviolet light or the like, the silicone resin of the adhesive layer 3 is constructed in such a manner that the content of the silicon atom-bonded olefinic groups in the silicone resin as a whole is in the range of 1.8×10 ^-6 mol/g or more and 1.0×10 ^-5 mol/g or less, so the cross-linking reaction (addition reaction) between the silicon atom-bonded olefinic groups of the silicone glue (G) and the silicon atom-bonded hydrogen atoms (SiH groups) of the cross-linking agent for the silicone resin will fully proceed. As a result, as the adhesive layer 3 is cured, the cross-linking density becomes higher and the cohesive force is enhanced, so that the desired adhesion reduction or the destruction mode in the retention test can be obtained. As a result, after the adhesive tape 1 is used for dicing a semiconductor element substrate, etc., good pickup performance can be achieved when the obtained semiconductor chip etc. is peeled off from the adhesive tape 1, and at the same time, residual adhesive on the semiconductor chip etc. can be suppressed.

Furthermore, as the silicone resin of the present invention, which is a mixture of silicone glue (G) and silicone resin (R), the commercially available materials listed below may be appropriately combined and mixed. Here, "appropriately combined and mixed" means "appropriately combining and mixing the materials in such a way that the content of silicon atom-bonded alkenyl groups in the entire silicone resin of the adhesive layer 3 is in the range of 1.8×10 ^-6 mol/g or more and 1.0×10 ^-5 mol/g or less, and the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) is in the range of 35.0/65.0 to 50.0/50.0". Examples of commercially available materials that can be suitably combined and mixed for preparation include the following materials (1) to (4).

Examples of silicone resins containing alkenyl groups bonded to silicon atoms include (1) commercially available addition reaction type silicone adhesives in which silicone glue (G _alk ) and silicone resin (R) are mixed at a specified ratio, or (2) commercially available addition reaction type silicone release agents containing silicone glue (G _alk ) as a main component. Examples of silicone resins not containing alkenyl groups bonded to silicon atoms include (3) commercially available peroxide curing type silicone adhesives in which silicone glue (G ₀ ) and silicone resin (R) are mixed at a specified ratio, or (4) commercially available silicone resin (R) alone. In the present invention, when the commercially available materials are appropriately combined and mixed, it is preferred to contain at least the addition reaction type silicone-oxygen release agent of (2), and it is more preferred to further contain the addition reaction type silicone-oxygen adhesive of (1).

As described above, as the silicone resin containing a silicon atom-bonded olefin group, (1) a commercially available addition reaction type silicone adhesive in which silicone glue (G _alk ) and silicone resin (R) are mixed at a specified ratio, or (2) a commercially available addition reaction type silicone release agent having silicone glue (G _alk ) as a main component can be used. Specific commercially available materials are exemplified below.

(1) Addition reaction type silicone adhesive As the above-mentioned commercially available addition reaction type silicone adhesive, there is no particular limitation as long as it is a silicone adhesive generally used for silicone adhesive tapes. Specifically, for example, KR-3700, KR-3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40-3270, X-40-3306 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., TSR1512, TSR1516, XR37-B9204 ( In the models such as SD4580, SD4584, SD4585, SD4560, SD4564, SD4565, SD4570, SD4574, SD4575, SD4600PFC, SD4593, and DC7651ADHESIVE (all trade names) manufactured by Dow Toray Co., Ltd., no platinum (Pt) catalyst and the crosslinking agent described below are added. In addition, although the type with the crosslinking agent added can also be used, the content of silicon atom-bonded hydrogen atoms (SiH groups) in the added crosslinking agent is unknown, and the content can be obtained by analysis such as ¹ H-NMR (nuclear magnetic resonance) spectroscopy measurement described below.

(2) Addition reaction type silicone release agent The commercially available addition reaction type silicone release agent is not particularly limited as long as it is a release treatment agent generally used as a silicone release film for adhesive tapes. Specifically, for example, LTC750A, LTC310, LTC300B (all trade names) manufactured by Dow Toray Industries, Ltd., KS3600, KS778 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., TPR6710, TPR6700 (all trade names) manufactured by Maitu Advanced Materials Co., Ltd., etc. can be used. In this case, either the type without adding a crosslinking agent or the type with adding a crosslinking agent may be used, and the content of silicon atom-bonded hydrogen atoms (SiH groups) in the added crosslinking agent can be determined by analysis such as ¹ H-NMR (nuclear magnetic resonance) spectroscopy measurement.

In the case where the mixing ratio of silicone glue (G) and silicone resin (R) in the above commercially available addition reaction silicone adhesive is unknown, the mixing ratio can be obtained from the peak area ratio of D unit and Q unit (silicone glue: silicone resin = D unit: Q unit) by ²⁹ Si-NMR (nuclear magnetic resonance) spectroscopy measurement. Alternatively, it can be obtained from the ratio of individual peak areas measured by gel permeation chromatography (GPC).

As the silicone resin containing no silicon atom-bonded alkenyl group, for example, a commercially available peroxide-curable silicone adhesive in which silicone glue (G ₀ ) and silicone resin (R) are mixed at a predetermined ratio, or a commercially available silicone resin (R) alone can be used. Specific commercially available materials are exemplified below.

(3) Peroxide-curing silicone adhesive The above-mentioned commercially available peroxide-curing silicone adhesive is not particularly limited as long as it is a silicone adhesive generally used for silicone adhesive tapes. Specific examples include KR-100 and KR-101-10 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., YR3340, YR3286, PSA610-SM, XR37-B6722, and YF3897 (all trade names) manufactured by Maitu Advanced Materials Co., Ltd., and SH4280, SH4282, SE4200, BY24-717, BY24-715, and Q2-7735 (all trade names) manufactured by Dow Toray Industries, Inc.

(4) Silicone resin Specific examples of commercially available silicone resins (R) include YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XC96-723, and 2D SILANOL FLUID (all trade names) manufactured by Maitu High-Tech Materials Co., Ltd.

In the case where the mixing ratio of silicone glue (G) and silicone resin (R) in the above-mentioned commercially available peroxide-curing silicone adhesive is unknown, the mixing ratio can be obtained from the peak area ratio of D unit and Q unit (silicone glue: silicone resin = D unit: Q unit) by ²⁹ Si-NMR (nuclear magnetic resonance) spectroscopy measurement in the same manner as above. Alternatively, it can be obtained from the ratio of individual peak areas measured by gel permeation chromatography (GPC).

The commercially available silicone resins can be used in a state of being appropriately combined and mixed so that the content of silicon atom-bonded alkenyl groups in the silicone resin as a whole of the adhesive layer 3 is in the range of 1.8×10 ^-6 mol/g to 1.0×10 ^-5 mol/g, and the mixing ratio ((G)/(R)) of the silicone glue (G) and the silicone resin (R) is in the range of 35.0/65.0 to 50.0/50.0. As a preferred example of using these commercially available silicone resins, specifically, for example, (a) a silicone resin to which an addition-reaction silicone release agent is added to an addition-reaction silicone adhesive, or (b) a silicone resin to which a peroxide-curing silicone adhesive and/or silicone resin (R) is further added, can be used as the main component of the adhesive composition constituting the adhesive layer 3. Moreover, in the description of this embodiment, "as the main component" means that the solid component of the adhesive composition accounts for 75 parts by mass or more, preferably 90 parts by mass or more, and more preferably 95 parts by mass or more, when the solid component of the adhesive composition is set to 100 parts by mass.

(Crosslinking agent) The crosslinking agent in this embodiment functions as a crosslinking agent for the silicone adhesive by irradiating the adhesive layer 3 with light such as ultraviolet rays. That is, the crosslinking agent in this embodiment is used to crosslink the adhesive layer 3 by irradiating the adhesive layer 3 with light such as ultraviolet rays, so that the photosensitive platinum (Pt) catalyst in the silicone adhesive is activated and undergoes an addition reaction with the silicon atom-bonded olefin group of the silicone glue ( _Galk ) contained in the silicone resin. Since the silicone resin is crosslinked by the crosslinking agent and the adhesive layer 3 is cured and the crosslinking density is increased, the cohesive force of the adhesive layer 3 is increased compared to before the irradiation with light such as ultraviolet rays. As the crosslinking agent, an organic polysiloxane (organic hydropolysiloxane) having at least two, preferably three or more silicon-atom-bonded hydrogen atoms (SiH groups) in one molecule is used. In the following description, the organic polysiloxane having silicon-atom-bonded hydrogen atoms (SiH groups) may be simply described as organic hydropolysiloxane.

The molecular structure of the organohydropolysiloxane used as a crosslinking agent may be, for example, a linear chain, a linear chain partially branched, a branched chain, or a network. The viscosity of the organohydropolysiloxane at 25°C is preferably in the range of 1 mPa·s to 5,000 mPa·s. The above viscosity can be measured using a B-type rotational viscometer.

The organohydropolysiloxane used as the crosslinking agent may be a conventionally known one. For example, the organohydropolysiloxane may be one represented by the following general formula (5) or general formula (6), but the present invention is not limited thereto.

Here, in general formula (5) and general formula (6), ^R3 is a monovalent alkyl group having 1 to 10 carbon atoms, b is 0 or 1, p and q are integers, and the viscosity of the organohydropolysiloxane at 25°C is a value of 1 mPa·s or more and 5,000 mPa·s or less. 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. The organohydropolysiloxane may be a mixture of two or more types.

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

The content of the organohydropolysiloxane used as a crosslinking agent in the adhesive layer 3 of the present embodiment is determined by the balance between the content of silicon-bonded olefinic groups of the silicone gel ( _Galk ) and the content of silicon-bonded hydrogen atoms of the organohydropolysiloxane, and its appropriate range varies and cannot be generalized. Generally, for example, the molar ratio of the content (total amount) of silicon-bonded hydrogen atoms (SiH groups) of the crosslinking agent contained in the adhesive composition to the content (total amount) of silicon-bonded olefinic groups of the silicone resin contained in the adhesive composition constituting the adhesive layer 3 is preferably in the range of 2.0 to 10.0.

When the content of the organohydropolysiloxane is less than the above lower limit, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the crosslinking density obtained by the crosslinking reaction (addition reaction) between the silicon atom-bonded olefin groups of the silicone adhesive and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent becomes insufficient, and the adhesive becomes difficult to harden and the cohesive force becomes difficult to improve. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. After the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become easy to produce adhesive residue.

On the other hand, if the content of the organohydropolysiloxane exceeds the above upper limit, there is a concern that the unreacted organohydropolysiloxane may contaminate the semiconductor chip. In addition, there is a concern that the silicon atom-bonded hydrogen atom (SiH group) in the unreacted organohydropolysiloxane may react with oxygen or moisture in the air to be converted into SiOH, and the adhesive layer 3 may have a greater adhesion to the adherend, thereby deteriorating the pickup properties of the individualized semiconductor chips.

The content of the crosslinking agent in the adhesive layer 3 of the present embodiment is as described above, and the molar ratio of the content (total amount) of the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent in the adhesive layer 3 to the content (total amount) of the silicon atom-bonded olefin group of the silicon-oxygen resin in the adhesive layer 3 is adjusted to be within the above range. The content of the crosslinking agent that satisfies this range varies depending on the number of silicon atom-bonded hydrogen atoms (SiH groups) possessed by the crosslinking agent. For example, the crosslinking agent may be added in a range of 0.20 parts by mass to 20.00 parts by mass based on the solid content, relative to 100 parts by mass of the entire solid content of the silicone-based resin contained in the adhesive composition constituting the adhesive layer 3.

By setting the content of the crosslinking agent in the adhesive layer 3 to the silicone resin within the above range, when the semiconductor chip is peeled off from the dicing adhesive tape, the light such as ultraviolet rays is irradiated to the adhesive layer 3, so that the photosensitive platinum (Pt) catalyst in the silicone adhesive is activated, thereby promoting the crosslinking reaction (addition reaction) between the silicon atom-bonded olefin groups of the silicone glue (G _alk ) in the silicone resin and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent for the silicone resin, thereby increasing the crosslinking density and increasing the cohesive force of the adhesive compared to before the irradiation with the ultraviolet rays. As a result, the adhesive force of the adhesive layer 3 can be appropriately reduced, and good pickup performance can be achieved when the semiconductor chip or the like is peeled off from the adhesive tape 1, and residual adhesive on the semiconductor chip or the like can be suppressed.

As the crosslinking agent, any crosslinking agent generally used as an addition reaction type silicone adhesive, that is, an organopolysiloxane (organohydropolysiloxane) having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule can be used, and there is no particular limitation. Specifically, for example, X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and BY24-741 (trade name) manufactured by Dow Toray Industries, Ltd. can be cited. Moreover, if the content of silicon atom-bonded hydrogen atoms (SiH groups) possessed by such crosslinking agents is unknown, the content can be obtained by analysis such as ¹ H-NMR (nuclear magnetic resonance) spectroscopy measurement described later.

(Photosensitive platinum (Pt) catalyst) Photosensitive platinum (Pt) catalyst is used to promote the curing of the silicone resin and the crosslinking agent constituting the adhesive layer 3 by irradiation with light such as ultraviolet rays. In order to promote the curing obtained by the addition reaction of the silicon atom-bonded olefin group of the silicone glue ( _Galk ) in the silicone adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent, the wavelength of light that can be used is preferably in the range of 240nm to 400nm. As the photosensitive platinum (Pt) catalyst, a photoactive cyclopentadienyl platinum (IV) compound is preferably used from the viewpoint of good photosensitivity and reaction speed.

The photoactive cyclopentadienyl platinum (IV) compound is not particularly limited, and examples thereof include (cyclopentadienyl) dimethyl trimethyl silyl methyl platinum, (cyclopentadienyl) diethyl trimethyl silyl methyl platinum, (cyclopentadienyl) dipropyl trimethyl silyl methyl platinum, (cyclopentadienyl) diisopropyl trimethyl silyl methyl platinum, (cyclopentadienyl) diallyl trimethyl silyl methyl platinum, (cyclopentadienyl) dibenzyl trimethyl silyl methyl platinum, (cyclopentadienyl) dimethyl triethylsilylmethyl platinum, (cyclopentadienyl)dimethyltripropylsilylmethyl platinum, (cyclopentadienyl)dimethyltriisopropylsilylmethyl platinum, (cyclopentadienyl)dimethyltriphenylsilylmethyl platinum, (cyclopentadienyl)dimethyldimethylphenylsilylmethyl platinum, (cyclopentadienyl)dimethylmethyldiphenylsilylmethyl platinum, (cyclopentadienyl)dimethyldimethyl(trimethylsiloxy)silylmethyl platinum, (cyclopentadienyl)dimethyldimethyl(dimethylvinylsiloxy)silyl Methylplatinum, [(1'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [(2'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [1-methyl-3-(1'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [1-methyl-3-(2'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [(4'-biphenylyl)cyclopentadienyl]trimethylsilylmethylplatinum, [1-(4'-biphenylyl)-3-methylcyclopentadienyl]trimethylsilylmethylplatinum methyl platinum, [(9'-phenanthrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, [1-methyl-3-(9'-phenanthrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, [1-(2'-anthryl)-3-methylcyclopentadienyl]trimethylsilylmethyl platinum, [(2'-anthryl)cyclopentadienyl]trimethylsilylmethyl platinum, [(1'-pyrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, [1-methyl-3-(1'-pyrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, and the like.

The cyclopentadienyl ring in the above compounds may be substituted by methyl, chlorine, fluorine, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, phenyl, fluorophenyl, chlorophenyl, methoxy, naphthyl, biphenyl, anthracenyl, pyrene, 2-benzylanthracene, thiothione, 2-chlorothiothione, 2-isopropylthiothione, anthraquinone, 1-chloroanthraquinone, acetophenone, benzophenone, 9,10-dimethylanthracene, 9,10-dichloroanthracene, and a cyclopentadienyl ring substituted by one or more groups selected from the above. In addition, in the above compounds, the cyclopentadienyl ring may be substituted by η5-fluorenyl.

The cyclopentadienyl ring in the above-mentioned compound is preferably unsubstituted, substituted with one or more aromatic organic groups, substituted with one or more aliphatic organic groups, or substituted with one or more aromatic organic groups and one or more aliphatic organic groups. In addition, the organic group substituted with the cyclopentadienyl ring is preferably naphthyl, biphenyl, anthracenyl, phenanthrenyl, and pyrenyl.

The content of the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the present embodiment is not particularly limited as long as it can promote the addition reaction between the silicon atom-bonded olefin group of the silicone glue ( _Galk ) in the silicone adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent due to the irradiation of light such as ultraviolet rays. The content of the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the present embodiment is preferably in the range of 0.10 mass parts to 3.00 mass parts based on the solid content, for example, relative to 100 mass parts of the total solid content of the silicone resin in the adhesive composition constituting the adhesive layer 3. When the content of the photosensitive platinum (Pt) catalyst is less than 0.10 parts by weight, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the crosslinking reaction (addition reaction) between the silicon atom-bonded olefin group of the silicone adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent cannot be fully performed, and the crosslinking density is insufficiently increased, the adhesive is difficult to harden, and the cohesive force is difficult to increase. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. When the adhesive tape 1 is used for cutting semiconductor device substrates, etc., and the obtained semiconductor chips are peeled off from the adhesive tape 1, there is a concern that the pickup of the individualized semiconductor chips will deteriorate, or there is a concern that the semiconductor chips will become easy to produce adhesive residues. On the other hand, when the content of the photosensitive platinum (Pt) catalyst exceeds 3.00 parts by mass, the above-mentioned crosslinking reaction (addition reaction) will fully proceed. For example, even if the content is 10.0 parts by mass, there will be no special problem as the characteristics of the adhesive tape 1, but from the perspective of economic efficiency, it is not good.

(Other components) The silicone adhesive layer of this embodiment is composed of an adhesive composition, which includes: a silicone resin mixed with silicone glue (G) and silicone resin (R), an organic polysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) in one molecule as a crosslinking agent for the silicone resin, and a photosensitive platinum (Pt) catalyst as the main components, but other components may also be contained within the scope of the effect of the present invention. As other components, cohesion enhancers, reinforcing fillers, peeling control agents, etc. can be cited.

(Cohesion enhancer) The cohesion enhancer is used as needed to enhance the cohesion of the adhesive layer 3. The cohesion enhancer is not particularly limited, and for example, polyfunctional mercaptan can be used. Examples of cohesion enhancers composed of polyfunctional mercaptan include Kalenz (registered trademark) MT-PE1 and Kalenz MT-NR1 manufactured by Showa Denko Co., Ltd.

However, polyfunctional thiol is not compatible with the silicone resin in the adhesive composition constituting the adhesive layer 3. Therefore, in order to use the polyfunctional thiol as a cohesive agent, it is necessary to use a compatibilizer for the silicone resin and the polyfunctional thiol. The compatibilizer is not particularly limited, and examples thereof include KBM-802 and KBM-803 (both trade names) manufactured by Shin-Etsu Chemical Co., Ltd., which are silane coupling agents having a butyl group, and SH6062 (trade name) manufactured by Dow Toray Industries, Ltd. When the cohesive agent is used for the adhesive layer 3, the amount of the cohesive agent added is preferably within a range of 6 parts by mass or less based on the solid content of 100 parts by mass of the total solid content of the silicone resin. When the amount of the cohesion enhancer added exceeds 6 parts by weight based on the solid content of the silicone resin (100 parts by weight), there is a concern that the silicone resin and the multifunctional thiol of the cohesion enhancer will separate even if a compatibilizer is added.

(Reinforcing filler) Reinforcing fillers are used when necessary to increase the strength of the adhesive layer 3. Reinforcing fillers are not particularly limited, and examples thereof include Aerosil (registered trademark) 130, Aerosil 200, Aerosil 300 manufactured by Japan Aerosil Co., Ltd., Reolosil (registered trademark) QS-102, Reolosil QS-30 manufactured by Tokuyama Co., Ltd., Carplex (registered trademark) 80 manufactured by DSL. Japan Co., Ltd., and Hi-Sil (registered trademark) -233-D manufactured by PPG.

(Peeling control agent) Peeling control agents are used as necessary to further reduce the adhesion of the adhesive layer 3 after exposure to ultraviolet light or the like. Peeling control agents are not particularly limited, and examples thereof include light peeling additives such as silicone oil. However, when the amount of peeling control agent added is large, there is a concern that the surface of the adherend may be contaminated by seepage, so it is better to add the amount within the range that the contamination level of the adherend surface can be tolerated.

<Thickness of adhesive layer> The thickness of the adhesive layer 3 is preferably in the range of 10μm to 100μm, and more preferably in the range of 20μm to 40μm. When the thickness of the adhesive layer 3 is less than 10μm, the thickness of the silicone adhesive contained in the adhesive layer 3 becomes thinner, so the adhesive force of the adhesive tape 1 is easily reduced. On the other hand, when the thickness of the adhesive layer 3 is thicker than 100μm, there is a concern that the coagulation and destruction of the adhesive layer 3 becomes easy to occur. Furthermore, after the adhesive tape 1 is used to cut a semiconductor device substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that residual adhesive is likely to be generated on the semiconductor chip. Furthermore, when cutting the semiconductor device substrate, the vibration of the cutting is likely to be transmitted to the adhesive layer 3 and the amplitude becomes larger, and there is a concern that, for example, the semiconductor device substrate is offset from the reference position. And, accompanying this, there is a concern that defects (chipping) may occur on the individualized semiconductor chips, or there is a concern that each individual semiconductor chip may vary in size.

<Anchor coating> As described above, in the adhesive tape 1 of this embodiment, depending on the manufacturing conditions of the adhesive tape 1 or the use conditions of the adhesive tape 1 after manufacturing, an anchor coating may be provided between the substrate 2 and the adhesive layer 3, or a surface treatment such as a corona treatment may be applied depending on the type of the substrate 2. This improves the adhesion between the substrate 2 and the adhesive layer 3.

<Surface treatment> The surface of the substrate 2 (the surface opposite to the adhesive layer 3) may be subjected to a surface treatment such as a release-improving treatment. The treatment agent used for the surface treatment of the substrate 2 is not particularly limited, and non-silicone-based release agents such as long-chain alkyl vinyl monomer polymers, fluorinated alkyl vinyl monomer polymers, polyvinyl alcohol urethane, and amino alkyd resins may be used. Examples of such non-silicone-based release agents include Peeloil (registered trademark) 1050 and Peeloil 1200 manufactured by Lion Special Chemicals Co., Ltd.

<Peel-off pad> In addition, a peel-off pad may be provided on the surface of the adhesive layer 3 (the surface opposite to the substrate 2) as necessary. As the peel-off pad, a film such as paper, polyethylene, polypropylene, polyethylene terephthalate, etc., which has been subjected to a peel-off treatment for improving the release property of the silicone adhesive contained in the adhesive layer 3, may be used. The material used for the peel-off treatment of the peel-off pad is not particularly limited, and materials such as fluoroalkyl modified silicone, long-chain alkyl vinyl monomer polymer, aminoalkyd resin, etc. may be used.

<Thickness of Adhesive Tape> The overall thickness of the adhesive tape 1 having the structure described above is preferably in the range of 20 μm to 200 μm. When the thickness of the adhesive tape 1 is less than 20 μm, it may become difficult to peel off the formed semiconductor chip from the adhesive tape 1 when the adhesive tape 1 is used to cut the semiconductor device substrate. On the other hand, when the thickness of the adhesive tape 1 exceeds 200 μm, it may become difficult for the adhesive tape 1 to follow the unevenness formed on the attachment surface of the semiconductor device substrate when the adhesive tape 1 is attached to the semiconductor device substrate. In this case, the contact area between the adhesive tape 1 and the semiconductor device substrate etc. becomes smaller, and there is a concern that the semiconductor chip etc. may be easily scattered during dicing.

[Manufacturing method of adhesive tape] Next, the manufacturing method of the adhesive tape 1 of this embodiment is described. The manufacturing method of the adhesive tape 1 described below is only an example, and the manufacturing method of the adhesive tape 1 is not limited to this.

When manufacturing the adhesive tape 1, first, the above-mentioned silicone adhesive, crosslinking agent, photosensitive platinum (Pt) catalyst and other components are dissolved in a general organic solvent such as toluene or ethyl acetate to obtain an adhesive solution. Then, the adhesive solution is applied to the surface of the substrate 2, which has been subjected to surface treatment or anchor coating as necessary, in a manner to a predetermined thickness using a comma coater or the like. Next, the adhesive solution is dried by heating the substrate 2 coated with the adhesive solution using a drying oven to form an adhesive layer 3. As heating and drying conditions, the conditions disclosed in, for example, Japanese Patent Application Laid-Open No. 2012-107125 can be referred to. Specifically, for example, an adhesive solution for applying an adhesive layer 3 to a substrate 2 is applied, and the temperature is gradually increased at 40 to 90°C in the front half of the drying furnace for initial drying, and then heated and dried at 120 to 200°C for 1 to 5 minutes in the rear half of the drying furnace, and then rolled up as a raw material roll. Through the above steps, as shown in FIG1 , an adhesive tape 1 having an adhesive layer 3 laminated on a substrate 2 can be obtained.

[How to use the adhesive tape] The adhesive tape 1 of this embodiment is used for cutting the semiconductor material that becomes the basis of the semiconductor chip in the manufacturing step of the semiconductor chip having semiconductor elements such as LED (light emitting diode) or power semiconductor.

Specifically, the adhesive tape 1 is used to obtain a semiconductor chip, which is a semiconductor chip obtained by cutting and individualizing a semiconductor element substrate on which a plurality of semiconductor elements such as LED elements or power semiconductor elements are formed on a substrate made of resin or ceramic. Here, the semiconductor element substrate on which a plurality of semiconductor elements are formed is usually provided with a sealing resin as an example of a covering material in order to protect the semiconductor element from an external environment such as temperature or humidity. The adhesive tape 1 of this embodiment can be particularly preferably used for cutting a semiconductor element substrate provided with a sealing resin.

As a method for obtaining a plurality of semiconductor chips by cutting a semiconductor element substrate provided with a sealing resin, the following method is known in the past. First, an adhesive tape for cutting is attached to 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 chips formed by cutting are peeled off from the adhesive tape to obtain a plurality of semiconductor chips.

However, when the semiconductor device substrate is cut by attaching a dicing adhesive tape from the substrate side of the semiconductor device substrate, there is a problem that a cut surface (substrate side of the semiconductor chip) may be missing, i.e., sunken, or the cut surface may become rough. Therefore, in recent years, in order to solve such a problem, a method has been proposed in which a dicing adhesive tape is attached not only to the substrate side but also to the side where the semiconductor device is formed, i.e., from the sealing resin side where the semiconductor device is sealed, and then the semiconductor device substrate is cut.

Here, as a sealing resin for semiconductor elements such as LEDs and power semiconductors, epoxy resins with excellent electrical properties or heat resistance have been used in the past. However, epoxy resins have the problem of easy discoloration when used for high-output LEDs or power semiconductors, when used for short-wavelength LEDs, or depending on the use environment of the semiconductor chip.

In contrast, silicone resins are less likely to discolor due to heat or light than epoxy resins, so in recent years silicone resins are often used as sealing resins for semiconductor components such as LEDs and power semiconductors. More specifically, silicone resins containing either or both methyl and phenyl groups as functional groups, i.e., silicone resins containing methyl groups, silicone resins containing phenyl groups, and silicone resins containing both methyl groups and phenyl groups, are often used.

By using silicone resin as a sealing resin for semiconductor components, discoloration of the sealing resin caused by heat or light can be suppressed. In addition, silicone resin can adjust the light transmittance to be as high as 88% or more (wavelength 400~800nm), and the refractive index can be adjusted to a range of 1.41 or more and 1.57 or less. Therefore, when the semiconductor component is an LED, by using a silicone resin with a higher refractive index as a sealing resin, the radiated light from the LED can be efficiently taken out to the outside of the package. Among the above-mentioned silicone resins, by using a silicone resin containing phenyl, the refractive index of the sealing material can be further increased compared to the case of using a silicone resin containing methyl, thereby seeking a higher efficiency of the radiated light.

As silicone resins containing methyl groups, there are no particular limitations. Examples include KER-2300, KER-2460, KER-2500N, KER-2600, KER-2700, KER-2900, and X-32-2528 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., and IVS4312, IVS4312, and XE14-C20 manufactured by Maitu Advanced Materials Co., Ltd. 42, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG0810, IVSG5778, XE13-C2479, IVSM4500 (all trade names), OE-6351, OE-6336, OE-6301 (all trade names) manufactured by Dow Toray Co., Ltd., etc. Silicone resins containing methyl and phenyl groups are not particularly limited, and examples thereof include KER-6075, KER-6150, KER-6020 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., etc. Examples of silicone resins containing phenyl groups are not particularly limited, and include KER-6110, KER-6000, KER-6200, ASP-1111, ASP-1060, ASP-1120, and ASP-1050P (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., XE14-C2508 (trade name) manufactured by Maitu Advanced Materials Co., Ltd., and OE-6520, OE-6550, OE-6631, OE-6636, OE-6635, and OE-6630 (all trade names) manufactured by Dow Toray Industries, Inc.

On the other hand, as a dicing adhesive tape used in the past for cutting semiconductor elements, an adhesive tape whose adhesive layer is composed of an acrylic resin-based adhesive is used. However, when such a conventional adhesive tape is attached 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, if the adhesion between the sealing resin and the adhesive tape is insufficient, there is a concern that the semiconductor chip may fly during cutting.

In particular, the silicone resin has a high release property compared to epoxy resins used as sealing resins in the past. Therefore, when a semiconductor device substrate using silicone resin as a sealing resin is attached with an adhesive tape whose adhesive layer is composed of an acrylic resin-based adhesive, the adhesion between the silicone resin of the sealing resin and the adhesive tape is likely to decrease. As a result, problems such as semiconductor chip scattering are more likely to occur when the semiconductor device substrate is cut.

In contrast, the adhesive tape 1 of the present embodiment is as described above, because the adhesive layer 3 is composed of an adhesive composition, and the adhesive composition includes a silicone resin formed by mixing silicone glue (G) and silicone resin (R) at an appropriate ratio, when cutting a semiconductor device substrate, even if it is attached from the sealing resin side composed of silicone resin, the adhesion and adhesion of the semiconductor device substrate to the sealing resin can still be well maintained. Moreover, compared with the conventional adhesive tape, when cutting a semiconductor device substrate, the generation of semiconductor chip scattering can still be suppressed. On the other hand, the adhesive composition constituting the adhesive layer 3 contains the above-mentioned silicone resin, photosensitive platinum (Pt) catalyst and crosslinking agent together. When irradiated with light such as ultraviolet rays, the photosensitive platinum (Pt) catalyst in the silicone resin is activated, and the crosslinking reaction (addition reaction) between the silicon atom-bonded olefin group of the silicone gel ( _Galk ) in the silicone resin and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent to the silicone resin is promoted, thereby increasing the crosslinking density. Therefore, the cohesive force of the adhesive becomes greater than that before irradiation with light such as ultraviolet rays. As a result, the adhesive force of the adhesive layer 3 is moderately reduced, and the failure mode in the holding force test is "interface peeling" or "no fall" in the holding force test. This makes it possible to achieve good pickup when peeling the semiconductor chip from the adhesive tape 1, and to suppress residual adhesive on the semiconductor chip.

The following describes in detail the method for using the adhesive tape 1 of the present embodiment and the method for manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment. FIG. 2(a) to (e) are diagrams showing the method for manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment. Moreover, the method described below is an example of the method for using the adhesive tape 1 and the method for manufacturing a semiconductor chip having an LED element as a semiconductor element, but is not limited to the following method.

In this embodiment, a plurality of semiconductor elements 102 are mounted on a substrate 101 made of, for example, a resin material or ceramic to produce a semiconductor element substrate 100. The semiconductor element 102 is, for example, an LED element, which is not shown in the figure, but is composed of a plurality of semiconductor layers such as a light-emitting layer that emits light when an electric current is applied, and an electrode is formed on the upper part. Next, a sealing resin 103 made of a silicon-based resin is used to seal the plurality of semiconductor elements formed on the substrate 101 of the semiconductor element substrate 100 (sealing step). In this example, the plurality of semiconductor elements 102 are sealed as a whole by the sealing resin 103, but individual semiconductor elements 102 may also be sealed individually by the sealing resin 103.

Next, as shown in FIG. 2(a), the adhesive layer 3 of the adhesive tape 1 is bonded to the semiconductor element substrate 100 in a manner facing the sealing resin 103 of the semiconductor element substrate 100 (bonding step). Next, as shown in FIG. 2(b) and (c), in a state where the adhesive tape 1 and the semiconductor element substrate 100 are bonded, the semiconductor element substrate 100 is cut along the predetermined cutting line X by a cutting machine or the like (cutting step). In this example, the semiconductor element substrate 100 to which the adhesive tape 1 is bonded is cut from the side of the substrate 101. In addition, as shown in FIG. 2(c), in this example, the semiconductor element substrate 100 is completely cut in the thickness direction, i.e., the so-called full cutting is performed.

Next, as shown in FIG. 2( d ), the adhesive tape 1 attached to the semiconductor device substrate 100 is irradiated with light such as ultraviolet rays from the substrate 2 side (irradiation step). As described above, the substrate 2 is made of a material through which light such as ultraviolet rays can penetrate. Therefore, by irradiating the adhesive tape 1 with light such as ultraviolet rays from the substrate 2 side, the light such as ultraviolet rays can penetrate the substrate 2 and irradiate 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 photosensitive platinum (Pt) catalyst is activated by irradiating the adhesive layer 3 with light such as ultraviolet rays, thereby promoting the addition reaction between the silicone resin containing silicon atoms bonded to alkenyl groups and the crosslinking agent in the adhesive layer 3. As a result, compared with before irradiation with light such as ultraviolet rays, the crosslinking density of the adhesive layer 3, that is, the cohesive force, increases, and the adhesive force of the adhesive layer 3 decreases.

Next, the semiconductor chip 200 formed by cutting the semiconductor device substrate 100 is peeled off (picked up) from the adhesive tape 1, as shown in FIG. 2(e), and the individualized semiconductor chips 200 can be obtained (peeling step).

As described above, the adhesive layer 3 of the adhesive tape 1 of the present embodiment is composed of a silicone resin formed by mixing silicone glue (G) and silicone resin (R) in an appropriate ratio. Thus, when the adhesive tape 1 is used for cutting, the adhesive force and adhesion of the adhesive tape 1 to the semiconductor element substrate 100 can be well maintained. In particular, in recent years, as the sealing resin 103 for sealing the semiconductor element 102, many silicone resins with high release properties are used. In contrast, the adhesive tape 1 of the present embodiment has the above-mentioned structure, and still has good adhesion and adhesion even to the sealing resin 103 composed of silicone resin. As a result, the adhesive tape 1 of this embodiment can still suppress the scattering of the semiconductor chip 200 when used for cutting the semiconductor device substrate 100.

Furthermore, the adhesive composition of the adhesive tape 1 of the present embodiment, which includes the silicone resin constituting the adhesive layer 3, has good adhesion to the sealing resin 103 as described above, and has a high release property. That is, the adhesive tape 1 of the present embodiment includes, for example: a photosensitive platinum (Pt) catalyst that promotes the addition reaction of the silicone resin containing silicon atom-bonded alkenyl groups in the adhesive layer 3 and the crosslinking agent by irradiation with light such as ultraviolet rays. Furthermore, by irradiating the adhesive layer 3 with ultraviolet light or the like through the substrate 2 after the cutting step and before the peeling step, the photosensitive platinum (Pt) catalyst is activated, and the addition reaction between the silicone resin containing silicon atoms bonded to alkenes in the adhesive layer 3 and the crosslinking agent is promoted. Compared with before irradiation with ultraviolet light or the like, the crosslinking density in the adhesive layer 3 can be increased, that is, the cohesive force is increased, and the adhesive force of the adhesive layer 3 is reduced. Thus, in the peeling step, when the semiconductor chip 200 obtained by cutting the semiconductor device substrate 100 is peeled off (picked up) from the adhesive tape 1, the adhesion of the adhesive on the semiconductor chip 200, i.e., the occurrence of so-called residual adhesive, can be suppressed. In addition, good pickup performance when the semiconductor chip 200 is peeled off from the adhesive tape 1 can be achieved.

Furthermore, the above has described a method for obtaining individualized semiconductor chips by cutting a semiconductor element substrate having a plurality of semiconductor elements formed on the substrate by attaching an adhesive tape 1 from the sealing resin side. However, the use of the adhesive tape 1 of this embodiment is not limited to this. The adhesive tape 1 of this embodiment can also be used to obtain, for example, in the manufacture of chip-sized packaged LEDs, a semiconductor material coated with a fluorescent body as an example of a coating material by cutting a plurality of LED elements to obtain individualized chip-sized packaged LEDs. Furthermore, a fluorescent body refers to a component in which a fluorescent material is dispersed in a resin material or ceramics.

In recent years, with the miniaturization of chip-size packaged LEDs, the chip-size packaged LEDs that have been cut into individual pieces tend to scatter easily during cutting. In contrast, by using the adhesive tape 1 of the present embodiment having the above-mentioned structure, it is possible to maintain good adhesion between the phosphor and the adhesive layer 3, and to suppress the scattering of the chip-size packaged LEDs that have been cut into individual pieces. In addition, after cutting, by irradiating the adhesive layer 3 with light such as ultraviolet rays to reduce the adhesive force, it becomes easy to peel off the chip-size packaged LEDs that have been cut into individual pieces from the adhesive tape 1, and the generation of residual adhesive on the peeled chip-size packaged LEDs can be suppressed. [Example]

Next, the present invention will be described in more detail using embodiments and comparative examples. However, the present invention is not limited to the following embodiments.

In order to adjust the various adhesive compositions used in the embodiments and comparative examples, the following silicone resins (a) to (h) are used as the main components of the adhesive compositions, and the following organopolysiloxanes (organohydropolysiloxanes) (m) and (n) having silicon atom-bonded hydrogen atoms (SiH) are used as crosslinking agents.

Silicone resins (a) to (c) are mixtures of silicone gel (G _alk ) containing silicon atom-bonded alkenyl groups and silicone resin (R), and the mixing ratio and silicon atom-bonded alkenyl content are different from each other. The silicone gel (G _alk ) uses a dimethylsiloxane-methylvinylsiloxane copolymer with a weight average molecular weight (Mw) of about 500,000 and dimethylvinylsiloxy groups at both ends of the molecular chain, and the silicone resin (R) uses an organic polysiloxane (MQ resin) with a weight average molecular weight (Mw) of about 5,000 and R ² ₃ SiO _0.5 units (M units) and SiO ₂ units (Q units).

In addition, both silicone resins (d) and (e) are single products of silicone gel (G _alk ) containing silicon-bonded alkenyl groups, and the contents of silicon-bonded alkenyl groups are different from each other. The silicone gel (G _alk ) of silicone resin (d) is a dimethylsiloxane-methylhexenylsiloxane copolymer with a weight average molecular weight (Mw) of about 300,000 and dimethylhexenylsiloxy groups at both ends of the molecular chain blocked, and the silicone gel (G _alk ) of silicone resin (e) is a dimethylsiloxane polymer with a weight average molecular weight (Mw) of about 200,000 and dimethylvinylsiloxane groups at both ends of the molecular chain blocked.

Furthermore, the silicone resins (f) and (g) are both mixtures of silicone gel (G ₀ ) and silicone resin (R) that do not contain a silicon atom-bonded olefin group, and the mixing ratios thereof are different from each other. The silicone gel (G ₀ ) uses a dimethylsiloxane polymer having a weight average molecular weight (Mw) of about 500,000, and the silicone resin (R) uses an organic polysiloxane (MQ resin) having a weight average molecular weight (Mw) of about 5,000 and having R ² ₃ SiO _0.5 units (M units) and SiO ₂ units (Q units).

Furthermore, the silicone resin (h) is a single silicone resin (R), and the silicone resin (R) is an organic polysiloxane (MQ resin) having a weight average molecular weight (Mw) of about 5,000 and having R ² ₃ SiO _0.5 units (M units) and SiO ₂ units (Q units).

・Silicone resin (a) A mixture of silicone gel (G _alk ) and silicone resin (R): (G _alk )/(R) = 40.0 mass%/60.0 mass% Alkenyl (vinyl) content: 2.0×10 ^-6 mol/g

・Silicone resin (b) A mixture of silicone gel (G _alk ) and silicone resin (R): (G _alk )/(R) = 35.0 mass%/65.0 mass% Alkenyl (vinyl) content: 1.8×10 ^-6 mol/g

・Silicone resin (c) A mixture of silicone gel (G _alk ) and silicone resin (R) (G _alk )/(R) = 50.0 mass%/50.0 mass% Alkenyl (vinyl) content: 2.5×10 ^-6 mol/g

・Silicone resin (d) Silicone gel (G _alk ) single olefin (hexenyl) content: 2.0×10 ^-4 mol/g

・Silicone resin (e) Silicone gel (G _alk ) single vinyl content: 2.7×10 ^-3 mol/g

・Silicone resin (f) A mixture of silicone gel (G ₀ ) and silicone resin (R) (G ₀ )/(R)=40.0 mass%/60.0 mass% Does not contain olefinic

・Silicone resin (g) A mixture of silicone gel (G ₀ ) and silicone resin (R) (G ₀ )/(R)=60.0 mass%/40.0 mass% Does not contain olefinic

・Silicone resin (h) Silicone resin (R) single substance Does not contain olefin

・Crosslinking agent (m) Organic hydropolysiloxane SiH group content: 2.0×10 ^-2 mol/g

・Crosslinking agent (n) Organic hydropolysiloxane SiH group content: 2.4×10 ^-3 mol/g

Furthermore, the alkenyl content of the silicone resin and the SiH group content of the crosslinking agent used above are quantitatively determined by measuring 500MHz ^1H -NMR (nuclear magnetic resonance) spectrum. Specifically, the non-volatile components of the silicone resin are fully dissolved in heavy chloroform containing dimethyl sulfoxide as an internal standard sample, and the ^1H -NMR (nuclear magnetic resonance) spectrum is measured using the NMR device "JNM·ECA500" (product name) manufactured by JEOL Ltd. Next, the resonance signal area (integrated value) of dimethyl sulfoxide as an internal standard sample and the resonance signal area (integrated value) of the alkenyl group in the measured spectrum are determined, and the alkenyl content per 1g (solid content) of the silicone resin is calculated from the ratio. The SiH group content of the crosslinking agent is similarly calculated by measuring the ¹ H-NMR spectrum, finding the resonance signal area (integral value) of dimethyl sulfoxide, an internal standard sample, and the resonance signal area (integral value) of the SiH group in the measured spectrum, and calculating the SiH group content per 1g (solid content) of the crosslinking agent from the ratio. In addition, when the crosslinking agent is added to the silicone resin from the beginning, the contents of the alkenyl group and the SiH group can be calculated simultaneously from the ¹ H-NMR spectrum.

1. Preparation of Adhesive Tape (Example 1) <Preparation of Silicone Resin Solution> Silicone resin (S1) in which silicone resin (a) and silicone resin (d) are mixed in a mass ratio (a)/(d) of 96.85/3.15 is diluted and stirred in toluene to prepare a silicone resin (S1) solution (solid content concentration 30 mass %). The silicone resin (S1) is a silicone gel (G) and a silicone resin (R) in a mixing ratio ((G)/(R)) of 41.9/58.1, and the olefin content is 8.2×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (a)" and "silicone glue (G _alk ) of silicone resin (d)". In addition, the total mass of silicone resin (R) is the amount of silicone resin (R) of silicone resin (a).

<Preparation of crosslinking agent solution> Next, crosslinking agent (C1) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 8.82/91.18 was diluted and stirred in toluene to prepare a crosslinking agent (C1) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C1) was 4.0×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass (100 parts by mass in terms of solid content) of the above-mentioned silicone resin (S1) solution was mixed with 3.50 parts by mass (0.70 parts by mass in terms of solid content, SiH group/olefin molar ratio = 3.4) of the crosslinking agent (C1) solution using a disper and stirred and mixed uniformly. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene to a solution of 5.13 parts by mass (0.77 parts by mass in terms of solid content) and mixed uniformly with toluene to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 20 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 58 μm after drying is obtained.

(Example 2) <Preparation of Silicone Resin Solution> Silicone resin (S2) in which silicone resin (b), silicone resin (d) and silicone resin (h) were mixed in a mass ratio (b)/(d)/(h) of 97.30/0.95/1.75 was diluted and stirred in toluene to prepare a silicone resin (S2) solution (solid content concentration 30 mass %). The silicone resin (S2) was a silicone gel (G) and a silicone resin (R) in a mixing ratio ((G)/(R)) of 35.0/65.0, and the alkenyl content was 3.6×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (b)" and "silicone glue (G _alk ) of silicone resin (d)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (b)" and "silicone resin (R) of silicone resin (h)".

<Preparation of crosslinking agent solution> Next, crosslinking agent (C2) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 2.83/97.17 was diluted and stirred in toluene to prepare a crosslinking agent (C2) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C2) was 2.9×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass (100 parts by mass in terms of solid content) of the above-mentioned silicone resin (S2) solution was mixed with 3.30 parts by mass (0.66 parts by mass in terms of solid content, SiH group/olefin molar ratio = 5.3) of the crosslinking agent (C2) solution using a disperser and stirred and mixed uniformly. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene to a solution of 5.20 parts by mass (0.78 parts by mass in terms of solid content) and mixed uniformly with toluene to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 12 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 10 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 22 μm after drying is obtained.

(Example 3) <Preparation of Silicone Resin Solution> Silicone resin (S3) in which silicone resin (c), silicone resin (d) and silicone resin (h) are mixed in a mass ratio (c)/(d)/(h) of 92.66/3.63/3.71 is diluted and stirred in toluene to prepare a silicone resin (S3) solution (solid content concentration 30 mass %). The silicone resin (S3) is a silicone gel (G) and a silicone resin (R) in a mixing ratio ((G)/(R)) of 50.0/50.0, and the alkenyl content is 9.6×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (c)" and "silicone glue (G _alk ) of silicone resin (d)". In addition, the total mass of silicone resin (R) is the total mass of silicone resin (R) of silicone resin (c) and silicone resin (R) of silicone resin (h).

<Preparation of crosslinking agent solution> Next, a crosslinking agent (C3) was prepared by diluting and stirring a crosslinking agent (m) and a crosslinking agent (n) in a mass ratio (m)/(n) of 10.43/89.57 in toluene to prepare a crosslinking agent (C3) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C3) was 4.2×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass (100 parts by mass in terms of solid content) of the above-mentioned silicone resin (S3) solution and 3.45 parts by mass (0.69 parts by mass in terms of solid content, SiH group/olefin molar ratio = 3.0) of the crosslinking agent (C3) solution were mixed and stirred uniformly using a disperser. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene to a solution of 4.93 parts by mass (0.74 parts by mass in terms of solid content) with a solid content concentration of 15% by mass using a disperser, and the mixture was uniformly stirred and mixed to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 50 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 40 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 90 μm after drying is obtained.

(Example 4) <Preparation of Silicone Resin Solution> Silicone resin (S4) mixed with silicone resin (a) and silicone resin (d) in a mass ratio (a)/(d) of 98.08/1.92 was diluted and stirred in toluene to prepare a silicone resin (S4) solution (solid content concentration 30 mass %). The silicone resin (S4) has a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 41.2/58.8, and an olefin content of 5.8×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (a)" and "silicone glue (G _alk ) of silicone resin (d)". In addition, the total mass of silicone resin (R) is the amount of silicone resin (R) of silicone resin (a).

<Preparation of crosslinking agent solution> Next, crosslinking agent (C4) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 10.43/89.57 was diluted and stirred in toluene to prepare a crosslinking agent (C4) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C4) was 4.2×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S4) solution (100 parts by mass in terms of solid content) was mixed with 1.80 parts by mass of the crosslinking agent (C4) solution (0.36 parts by mass in terms of solid content, SiH group/alkenyl molar ratio = 2.6) using a disperser and stirred and mixed uniformly. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Co., Ltd. was diluted with toluene to a solution of 5.20 parts by mass (0.78 parts by mass in terms of solid content) and mixed uniformly with toluene to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 20 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 58 μm after drying is obtained.

(Example 5) The following operation was used to prepare a crosslinking agent (C5) solution. In the preparation of the adhesive solution, except that the crosslinking agent was changed from the crosslinking agent (C4) solution to the crosslinking agent (C5) solution and the amount of the crosslinking agent (C5) solution was changed to 8.30 parts by mass (1.66 parts by mass in terms of solid content, SiH group/alkenyl molar ratio = 8.0), the other operations were the same as those in Example 4 to obtain an adhesive tape 1 having a total thickness of 58 μm after drying.

<Preparation of crosslinking agent solution> A crosslinking agent (C5) mixed with a crosslinking agent (m) and a crosslinking agent (n) at a mass ratio (m)/(n) of 2.28/97.72 was diluted and stirred in toluene to prepare a crosslinking agent (C5) solution (solid content 20 mass %). The SiH group content of the crosslinking agent (C5) was 2.8×10 ^-3 mol/g.

(Example 6) The following operation is used to prepare a crosslinking agent (C6) solution. In the preparation of the adhesive solution, except that the crosslinking agent is changed from the crosslinking agent (C4) solution to the crosslinking agent (C6) solution, the amount of the crosslinking agent (C6) solution is changed to 3.45 parts by mass (0.69 parts by mass in terms of solid content, SiH group/olefin molar ratio = 4.0), and the amount of the photosensitive platinum (Pt) catalyst solution is changed to 1.93 parts by mass (0.29 parts by mass in terms of solid content), the other operations are the same as those of Example 4 to obtain an adhesive tape 1 having a total thickness of 58 μm after drying.

<Preparation of crosslinking agent solution> A crosslinking agent (C6) mixed with a crosslinking agent (m) and a crosslinking agent (n) at a mass ratio (m)/(n) of 5.50/94.50 was diluted and stirred in toluene to prepare a crosslinking agent (C6) solution (solid content concentration 20 mass %). The SiH group content of the crosslinking agent (C6) was 3.4×10 ^-3 mol/g.

(Example 7) Except that the amount of the photosensitive platinum (Pt) catalyst solution mixed in the adhesive solution was changed to 19.60 parts by mass (2.94 parts by mass in terms of solid content), the other operations were the same as those in Example 6 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

(Example 8) The following operation is used to prepare a silicone resin (S5) solution. In the preparation of the adhesive solution, except that the amount of the crosslinking agent (C6) solution is changed to 2.85 mass parts (0.57 mass parts in terms of solid content, SiH group/olefin molar ratio = 3.7), the amount of the photosensitive platinum (Pt) catalyst solution is changed to 4.40 mass parts (0.66 mass parts in terms of solid content), and the thickness of the adhesive layer 3 after drying is changed to 30μm, the other operations are the same as those of Example 6 to obtain an adhesive tape 1 with a total thickness of 68μm after drying.

<Preparation of Silicone Resin Solution> Silicone resin (S5) mixed with silicone resin (a), silicone resin (d) and silicone resin (f) at a mass ratio (a)/(d)/(f) of 81.99/1.61/16.40 was diluted and stirred in toluene to prepare a silicone resin (S5) solution (solid content concentration 30 mass %). The silicone resin (S5) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 49.2/50.8, and an olefin content of 5.3×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (a)", "silicone glue (G _alk ) of silicone resin (d)", and "silicone glue (G ₀ ) of silicone resin (f)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (a)" and "silicone resin (R) of silicone resin (f)".

(Example 9) <Preparation of silicone resin solution> A silicone resin (S6) in which silicone resin (a), silicone resin (d), silicone resin (f) and silicone resin (h) are mixed in a mass ratio of (a)/(d)/(f)/(h) of 66.49/0.26/26.60/6.65 is diluted and stirred in toluene to prepare a silicone resin (S6) solution (solid content concentration 30 mass %). The silicone resin (S6) has a mixing ratio ((G)/(R)) of 37.5/62.5 of silicone gel (G) and silicone resin (R), and an olefin content of 1.9×10 ^-6 mol /g. Here, the total mass of silicone gel (G) is the total mass of "silicone gel (G _alk ) of silicone resin (a)", "silicone gel (G _alk ) of silicone resin (d)", and "silicone gel (G ₀ ) of silicone resin (f)". The total mass of the silicone resin (R) is the total mass of the silicone resin (R) of the silicone resin (a), the silicone resin (R) of the silicone resin (f), and the silicone resin (R) of the silicone resin (h).

<Preparation of crosslinking agent solution> Next, crosslinking agent (C7) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 1.15/98.85 was diluted and stirred in toluene to prepare a crosslinking agent (C7) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C7) was 2.6×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S6) solution (100 parts by mass in terms of solid content) and 2.20 parts by mass of the crosslinking agent (C7) solution (0.44 parts by mass in terms of solid content, SiH group/olefin molar ratio = 6.2) were mixed and stirred uniformly using a disperser. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Co., Ltd. was diluted with toluene to a solution of 3.53 parts by mass (0.53 parts by mass in terms of solid content) with a solid content concentration of 15% by mass using a disperser, and the mixture was stirred and mixed uniformly to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 30 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 68 μm after drying is obtained.

(Example 10) <Preparation of Silicone Resin Solution> Silicone resin (S7) in which silicone resin (c), silicone resin (d) and silicone resin (f) are mixed in a mass ratio (c)/(d)/(f) of 71.18/0.35/28.47 is diluted and stirred in toluene to prepare a silicone resin (S7) solution (solid content concentration 30 mass %). The silicone resin (S7) is a silicone gel (G) and a silicone resin (R) in a mixing ratio ((G)/(R)) of 47.3/52.7, and the alkenyl content is 2.5×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (c)" and "silicone glue (G _alk ) of silicone resin (d)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (c)" and "silicone resin (R) of silicone resin (f)".

<Preparation of crosslinking agent solution> Next, crosslinking agent (C8) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 1.44/98.56 was diluted and stirred in toluene to prepare a crosslinking agent (C8) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C8) was 2.7×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass (100 parts by mass in terms of solid content) of the above-mentioned silicone resin (S7) solution was mixed with 2.35 parts by mass (0.47 parts by mass in terms of solid content, SiH group/alkenyl molar ratio = 5.1) of the crosslinking agent (C8) solution using a disperser and stirred and mixed uniformly. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Co., Ltd. was diluted with toluene to a solution of 3.80 parts by mass (0.57 parts by mass in terms of solid content) with a solid content concentration of 15% by mass using a disperser, and the mixture was stirred and mixed uniformly to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 30 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 68 μm after drying is obtained.

(Comparative Example 1) The following operation was used to prepare a silicone resin (S8) solution. In the preparation of the adhesive solution, the silicone resin was changed from the silicone resin (S4) solution to the silicone resin (S8) solution, no crosslinking agent was added, and the thickness of the adhesive layer 3 after drying was 35 μm. The other operations were the same as those of Example 4 to obtain an adhesive tape 1 with a total thickness of 73 μm after drying.

<Preparation of Silicone Resin Solution> Silicone resin (S8) mixed with silicone resin (a) and silicone resin (e) at a mass ratio (a)/(e) of 99.75/0.25 was diluted and stirred in toluene to prepare a silicone resin (S8) solution (solid content concentration 30 mass %). The silicone resin (S8) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 40.1/59.9, and an olefin content of 8.7×10 ^-6 mol /g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (a)" and "silicone glue (G _alk ) of silicone resin (e)". In addition, the total mass of silicone resin (R) is the amount of silicone resin (R) of silicone resin (a).

(Comparative Example 2) Except that in the preparation of the adhesive solution, 1.93 parts by mass of the photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" solution manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was replaced with 5.88 parts by mass (1.47 parts by mass in terms of solid content) of the platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Industries, Ltd., and the thickness of the adhesive layer 3 after drying was made 20 μm, the other operations were the same as those of Example 6 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

(Comparative Example 3) <Preparation of Silicone Resin Solution> Silicone resin (S9) in which silicone resin (d) and silicone resin (f) and silicone resin (h) were mixed in a mass ratio (d)/(f)/(h) of 0.18/90.75/9.07 was diluted and stirred in toluene to prepare a silicone resin (S9) solution (solid content concentration 30 mass %). The silicone resin (S9) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 36.5/63.5, and an olefin content of 3.6×10 ^-7 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (d)" and "silicone glue (G ₀ ) of silicone resin (f)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (f)" and "silicone resin (R) of silicone resin (h)".

<Preparation of crosslinking agent solution> Next, crosslinking agent (C9) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 0.58/99.42 was diluted and stirred in toluene to prepare a crosslinking agent solution (solid content concentration 20 mass %). The SiH group content of the crosslinking agent (C9) was 2.5×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S9) solution (100 parts by mass in terms of solid content) and 3.00 parts by mass of the crosslinking agent (C9) solution (0.60 parts by mass in terms of solid content, SiH group/alkenyl molar ratio = 42.4) were mixed and stirred uniformly using a disperser. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Co., Ltd. was diluted with toluene to a solution of 4.87 parts by mass (0.73 parts by mass in terms of solid content) with a solid content concentration of 15% by mass using a disperser, and the mixture was uniformly stirred and mixed to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 30 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 68 μm after drying is obtained.

(Comparative Example 4) <Preparation of Silicone Resin Solution> Silicone resin (S10) mixed with silicone resin (d) and silicone resin (g) at a mass ratio (d)/(g) of 5.56/94.44 was diluted and stirred in toluene to prepare a silicone resin (S10) solution (solid content concentration 30 mass %). The silicone resin (S10) had a mixing ratio ((G)/(R)) of 62.2/37.8 between silicone gel (G) and silicone resin (R), and an olefin content of 1.1×10 ^-5 mol/g. Here, the total mass of silicone glue (G) is the sum of "silicone glue (G _alk ) of silicone resin (d)" and "silicone glue (G ₀ ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the amount of silicone resin (R) of silicone resin (g).

<Preparation of crosslinking agent solution> Next, crosslinking agent (C10) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 14.88/85.12 was diluted and stirred in toluene to prepare a crosslinking agent (C10) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C10) was 5.0×10 ^-3 mol/g.

<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S10) solution (100 parts by mass in terms of solid content) and 3.65 parts by mass of the crosslinking agent (C10) solution (0.73 parts by mass in terms of solid content, SiH group/olefin molar ratio = 3.3) were mixed and stirred uniformly using a disperser. Next, a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene to a solution of 5.07 parts by mass (0.76 parts by mass in terms of solid content) with a solid content concentration of 15% by mass using a disperser, and the mixture was uniformly stirred and mixed to prepare a coating adhesive solution.

Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film having a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of a drying furnace, and is dried by heating for 3 minutes in a zone where the maximum temperature of the heat treatment set in the rear half of the drying furnace is 120°C, thereby forming an adhesive layer 3 having a thickness of 40 μm after drying. Next, a release pad subjected to a release treatment with fluoroalkyl modified silicone is attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 78 μm after drying is obtained.

(Comparative Example 5) The following operation is used to prepare a silicone resin (S11) solution. In the preparation of the adhesive solution, except that the amount of the photosensitive platinum (Pt) catalyst solution is changed to 5.07 parts by mass (0.76 parts by mass in terms of solid content) and the thickness of the adhesive layer 3 after drying is changed to 20 μm, the other operations are the same as those of Example 2 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

<Preparation of Silicone Resin Solution> Silicone resin (S11) mixed with silicone resin (b), silicone resin (d) and silicone resin (h) at a mass ratio (b)/(d)/(h) of 91.76/0.90/7.34 was diluted and stirred in toluene to prepare a silicone resin (S11) solution (solid content concentration 30 mass %). The silicone resin (S11) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 33.0/67.0, and an olefin content of 3.4×10 ^-6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G _alk ) of silicone resin (b)" and "silicone glue (G _alk ) of silicone resin (d)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (b)" and "silicone resin (R) of silicone resin (h)".

The structures of the adhesive tapes 1 and the compositions of the adhesive layer 3 prepared in Examples 1 to 10 and Comparative Examples 1 to 5 are shown in Tables 1 to 3.

2. Evaluation method Next, the evaluation method of the adhesive tape 1 is described. (1) Adhesion test (before UV irradiation) The adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 5 were subjected to a BA-SUS adhesion test (peel-off adhesion test) according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)). Specifically, the adhesive tape 1 from which the peel-off liner had been peeled off was attached to a stainless steel plate (SUS304) having a surface roughness (Ra) of 50±25nm and subjected to a buffing annealing (BA) treatment, and was pressed at a speed of 5mm/s by moving a roller having a mass of 2000g back and forth once. Then, after leaving it for 20 to 40 minutes, use a pull-up tester to tear off the stainless steel plate in the 180° direction at a speed of 5mm/s, and measure the adhesion relative to the polished SUS plate. Moreover, the adhesion test is performed on the adhesive tape 1 before irradiation with ultraviolet rays (UV). In addition, as a result of the adhesion test, considering that the fixing force of the adhesive tape 1 when used for cutting semiconductor materials is preferably 2.4N/10mm or more, and from the perspective of the pick-up of semiconductor chips that are individualized by cutting, it is preferably 5.5N/10mm or less. It is preferably 2.7N/10mm or more and 4.1N/10mm or less.

(2) Rolling ball adhesion test (2-1) Measurement of initial (before UV irradiation) rolling ball adhesion For the adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 5 before UV irradiation, a rolling ball adhesion test was performed according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)).

(2-2) Measurement of roller ball adhesion after UV irradiation The substrate side of each adhesive tape prepared in Examples 1 to 10 and Comparative Examples 1 to 5 was irradiated with UV and placed at a temperature of 23°C and a humidity of 50±5%RH for 20 to 40 minutes. The peeling pad of each adhesive tape 1 was peeled off and a roller ball adhesion test was performed in the same manner as the initial roller ball adhesion according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)). The UV irradiation was performed using a high-pressure mercury lamp and adjusted so that the ultraviolet light with a wavelength of 365nm became an accumulated light amount of 1200mJ/ ^cm2 . Furthermore, the rolling ball viscosity was measured in the same manner when the integrated light amount was set to 3000mJ/ ^cm2 , but no difference was found when the integrated light amount was set to 1200mJ/ ^cm2 , so the integrated light amount was set to 1200mJ/ ^cm2 for evaluation.

As a result of the rolling ball viscosity test, when considering the pick-up properties of semiconductor chips that have been cut into pieces by dicing, the rolling ball viscosity (roller ball No.) after UV irradiation is preferably lower than the initial rolling ball viscosity (roller ball No.). That is, when the value of the ball number before UV irradiation is set as BN0 and the value of the ball number after UV irradiation is set as BN1, the relationship of BN0>BN1 is preferred. This relationship means that the cross-linking reaction of the adhesive layer 3 is promoted by UV irradiation, and the cohesive force is increased compared to before UV irradiation.

(3) Holding force test (3-1) Measurement of initial (before UV irradiation) holding force The holding force test was conducted on the adhesive tapes 1 produced in Examples 1 to 10 and Comparative Examples 1 to 5 before UV irradiation according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)). Specifically, the peeling pad of each adhesive tape 1 was peeled off, and the adhesive layer 3 was attached to a stainless steel plate (SUS304) polished with water-resistant abrasive paper. The adhesive tape 1 was loaded with a specified weight and kept at a temperature of 40°C and a humidity of 33% RH. The time (falling time (min)) from the time the adhesive tape 1 peeled off the stainless steel plate and fell off was measured. Furthermore, the failure mode of the adhesive tape 1 when peeled off from the stainless steel plate was observed (the failure mode between the adhesive layer 3 and the stainless steel plate was interface peeling or cohesion failure). Moreover, the measurement of the drop time of the holding force test was carried out until 2880 minutes. In addition, the drop time (minutes) and the failure mode of the adhesive tape 1 are shown as the results of the holding force test shown in Tables 4 to 6 described later.

(3-2) Measurement of holding power after UV irradiation The adhesive tape 1 was irradiated with UV and left to stand under the same conditions as the measurement of rolling ball viscosity after UV irradiation described above, and then the holding power test was performed in the same manner as the initial holding power test.

(3-3) Relationship between holding force and failure mode Here, the relationship between the holding force and failure mode of the adhesive tape 1 is described. Figure 3 is a schematic diagram showing the relationship between the crosslinking density of the silicone resin in the adhesive layer 3 and the result of the holding force test of the adhesive tape 1 (falling time). As shown in FIG. 3 , in the adhesive tape 1 , as the cross-linking density of the silicone resin in the adhesive layer 3 increases, the damage mode of the adhesive tape 1 to the stainless steel plate from the retention test shows a change from [aggregation damage of the adhesive layer 3 (falling)] → [retention (no falling)] → [peeling of the interface between the adhesive layer 3 and the stainless steel plate (falling)].

Furthermore, as shown in FIG3 , in the region where the failure mode of the adhesive tape 1 is coagulation failure, the holding force (drop time) of the adhesive tape 1 increases as the crosslinking density of the silicone resin in the adhesive layer 3 increases. On the other hand, as shown in FIG3 , in the region where the failure mode of the adhesive tape 1 is interface peeling, the holding force (drop time) of the adhesive tape 1 decreases as the crosslinking density of the silicone resin in the adhesive layer 3 increases. This is speculated to be because as the cross-linking density of the silicone resin increases, the cohesive force of the adhesive layer 3 increases, thereby reducing the adhesive force of the adhesive tape 1, resulting in the adhesive tape being easily peeled off from the stainless steel plate and falling off.

As the result of the holding force test, it is preferred that the damage mode after UV irradiation is at least holding or interface peeling, it is more preferred that the damage mode after UV irradiation is interface peeling, and it is more preferred that the damage mode both in the initial stage (before UV irradiation) and after UV irradiation is interface peeling. In addition, in the case where the damage mode both in the initial stage (before UV irradiation) and after UV irradiation is interface peeling, the falling time is preferably as long as possible or does not fall off in the initial stage (before UV irradiation) from the perspective of the fixing force when the adhesive tape 1 is used to cut semiconductor materials, and after UV irradiation, it is preferred that it is shorter than the initial stage (before UV irradiation) from the perspective of the pick-up of semiconductor chips that are cut into pieces. In this case, after the adhesive tape 1 is used for dicing a semiconductor device substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, the adhesive tape 1 is irradiated with UV, so that it becomes difficult for residual adhesive to be generated on the semiconductor chip.

(4) Silicone resin residue test The adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 5 was subjected to a silicone resin residue test. First, agent A and agent B of a methyl silicone resin for LED devices (KER-2500N (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a mixing ratio of 1:1 to prepare a mixed solution. The mixed solution was applied to a stainless steel plate and heated at 100°C for 1 hour and then at 150°C for 2 hours to cure, thereby preparing a silicone test piece A. Similarly, agent A and agent B of a phenyl-containing silicone resin for LED devices (KER-6110 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a mixing ratio of 3:7 to prepare a mixed solution. The mixed solution was applied to a stainless steel plate and heated at 100°C for 2 hours and then at 150°C for 5 hours to cure, thereby preparing a silicone test piece B.

Next, peel off the peeling pad of the adhesive tape 1, and attach the adhesive layer 3 to the silicone test pieces A and B respectively, and press the adhesive with a roller of 2000g back and forth once at a speed of 5mm/s. Then, similar to the conditions for measuring the rolling ball adhesion after UV irradiation, UV is irradiated from the substrate 2 side of the adhesive tape 1, and then placed in an environment of temperature 40℃ and humidity 90%RH for 120 hours. After that, return to room temperature, peel off the adhesive tape 1 at a speed of 800mm/s~1200mm/s in a direction of 90° relative to the silicone test pieces A and B, and visually confirm the residual adhesive on the silicone test pieces A and B.

(5) Epoxy resin residue test The adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 5 was subjected to an epoxy resin residue test. An epoxy test sheet consisting of an epoxy resin sheet (NL-EG-23 (trade name) manufactured by Nikko Chemical Co., Ltd.) in which a glass cloth substrate is impregnated with epoxy resin was attached to the adhesive layer 3 of the adhesive tape 1 from which the peeling liner had been peeled off, and a roller with a mass of 2000 g was pressed back and forth once at a speed of 5 mm/s. Next, the adhesive tape 1 was irradiated with UV from the substrate 2 side under the same conditions as those in the measurement of the rolling ball adhesion after UV irradiation, and then placed in an environment of 40°C and 90%RH for 120 hours. After that, it was returned to room temperature, and the adhesive tape 1 was torn off at a speed of 800mm/s~1200mm/s at a direction of 90° relative to the epoxy test piece, and the residual adhesive on the epoxy test piece was visually confirmed.

The silicone resin residual test and the epoxy resin residual test are evaluated based on the following judgment criteria. In addition, the evaluation of A or B is considered to be qualified. A: No residual adhesive is found within 100% of the test piece per unit area B: Residual adhesive is found within less than 2% of the test piece per unit area C: Residual adhesive is found within 2% or more but less than 5% of the test piece per unit area D: Residual adhesive is found within more than 5% of the test piece per unit area, or, Residual adhesive is found at the edge of the test piece

(6) Cutting Test The cutting test was conducted on the adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 5. Specifically, a molding epoxy resin (CEL-400ZHF40-W75G (trade name) manufactured by Hitachi Chemical Co., Ltd.) was first placed in a mold and heated and hardened under the conditions of a sealing pressure of 50 kgf/cm ² (491 N/cm ² ), a sealing material thickness of 0.3 mm, and a heating temperature of 150° C. for 300 seconds to prepare a circular plate-shaped (diameter 200 mm (8 inches)) cutting test piece. Next, the adhesive layer 3 of the adhesive tape 1 from which the peeling pad has been peeled off is attached to the cutting ring, and after the portion that overflows from the ring is cut off, a fluorine-based peeling film (SS1A (trade name) manufactured by Nippa Co., Ltd., thickness 75μm) is attached. Next, a roller with a mass of 2000g is moved back and forth to press the adhesive tape 1 and the ring portion. Next, the fluorine-based peeling film is peeled off, and the cutting test piece is attached to the adhesive layer 3 in the center of the ring and pressed.

Furthermore, using a dicing device (A-WD-100A (trade name)) manufactured by Tokyo Seimitsu Co., Ltd., and using a dicing blade manufactured by DISCO Co., Ltd., the dicing test piece and the adhesive tape 1 are cut into 10mm×10mm chips. At this time, the number of chips that are scattered is calculated and measured to evaluate the fixing force in the dicing test. Then, the adhesive tape 1 attached to the chip that is individualized into 10mm×10mm is irradiated with UV under the same conditions as the measurement of the rolling ball viscosity after UV irradiation. Thereafter, the individualized chip is picked up from the adhesive tape 1, and the presence or absence of residual adhesive on the chip is visually confirmed to evaluate the residual adhesive in the dicing test. In addition, when picking up the chip, the number of chips that failed to be picked up is calculated and measured to evaluate the pick-up performance in the dicing test.

The fixing force in the dicing test is evaluated based on the following judgment criteria. However, the evaluation of A or B is considered to be qualified. A: The number of scattered chips is 0 out of 100, and no chip defects are found B: The number of scattered chips is 1 out of 100, and no chip defects are found C: The number of scattered chips is 2 out of 100, and no chip defects are found D: The number of scattered chips is 3 or more out of 100, or chip defects are found

The adhesive residue in the dicing test is evaluated based on the following judgment criteria. In this case, the evaluation of A is considered qualified. A: No adhesive residue is found on the chip D: Adhesive residue is found on the chip, or adhesive strands are seen on the side of the chip

The pick-up performance in the dicing test is evaluated based on the following judgment criteria. A or B is considered acceptable. A: The number of chips that failed to be picked up is 0 out of 100 B: The number of chips that failed to be picked up is 1 out of 100 C: The number of chips that failed to be picked up is 2 out of 100 D: The number of chips that failed to be picked up is 3 or more out of 100

3. Test results The evaluation results of the adhesive tape 1 of Examples 1 to 10 and Comparative Examples 1 to 5 are shown in Tables 4 to 6.

As shown in Tables 4 and 5, the adhesive tape 1 of Examples 1 to 10, which is confirmed to have an adhesive layer that meets the requirements of the present invention, can obtain good results in any of the adhesion test, rolling ball viscosity test, holding force test, silicone resin residue test, epoxy resin residue test, and cutting test (fixing force, residue, and pickup).

Among them, compared with the adhesive tapes 1 of Examples 9 and 10 in which the contents of silicon atom-bonded olefinic groups in the entire silicone resin are 1.9× ^10-6 mol/g and 2.5× ^10-6 mol/g, respectively, the adhesive tapes 1 of Examples 1 to 8 in which the contents of silicon atom-bonded olefinic groups in the entire silicone resin are in the range of 3.0× ^10-6 mol/g to 1.0× ^10-5 mol/g have generally good evaluation results in the silicone resin residue test and the epoxy resin residue test.

Thus, it was confirmed that the adhesive tape 1 of Examples 1 to 10 is useful as an adhesive tape for dicing semiconductor materials, and more specifically, is useful as an adhesive tape for dicing semiconductor device substrates that is adhered from the sealing resin side and used for dicing.

In contrast, as shown in Table 6, the adhesive tapes 1 of Comparative Examples 1 to 5, which were confirmed to have adhesive layer 3 that did not meet the requirements of the present invention, showed results worse than those of Examples 1 to 10 in any of the test results of the silicone resin residue test, the epoxy resin residue test, and the cutting test (fixing force, residue, and pickup).

Specifically, in the adhesive tape 1 of Comparative Example 1 in which the adhesive layer 3 does not contain a crosslinking agent, since the silicone resin does not crosslink even when UV irradiation is applied, no change is observed in the results of the rolling ball adhesion test and the holding force test before and after UV irradiation, and no increase in the cohesive force of the adhesive layer 3 caused by UV irradiation is found. Therefore, in the silicone resin residue test and the epoxy resin residue test used to confirm practicality, many residues were found. In addition, in the dicing test, the wafer pickup of the diced test piece was also poor, and residues were also found on the wafer.

In the adhesive tape 1 of Comparative Example 2 in which the adhesive layer 3 does not contain a photosensitive platinum (Pt) catalyst but contains a conventional platinum (Pt) catalyst, in the stage before UV irradiation, that is, in the heating and drying step for applying the adhesive layer 3 on the substrate 2, the silicon atoms of the silicone resin in the adhesive layer 3 have already undergone an addition reaction with the alkenyl groups and the SiH groups of the crosslinking agent by the platinum (Pt) catalyst, and have been crosslinked and hardened to become too hard. Therefore, in the cutting test, the fixing force of the cutting test piece was slightly lower, and a lot of chips were found to fly during cutting. Since the adhesive layer 3 does not contain a photosensitive platinum (Pt) catalyst, the cohesion does not increase even when UV irradiation is applied. No changes were found in the results of the rolling ball adhesion test and the retention test before and after UV irradiation. However, since the cohesion of the adhesive layer 3 is high, no residue was found in the silicone resin residue test and the epoxy resin residue test. In addition, no residue was found in the dicing test for the wafer that did not fly.

Furthermore, the adhesive tape 1 of Comparative Example 3, in which the content of silicon-atom-bonded olefin groups in the silicone resin in the adhesive layer 3 was less than the lower limit of the requirements of the present invention, showed no change in the results of the rolling ball adhesion test and the holding force test before and after UV irradiation. The cohesion increase effect of the adhesive layer 3 formed by UV irradiation was not sufficient, and the cohesion itself was also small. Therefore, a lot of adhesive residues were found in the silicone resin residue test and the epoxy resin residue test. Moreover, even in the dicing test, the wafer pickup of the diced test piece was poor, and adhesive residues were found on the wafer.

Furthermore, in the adhesive tape 1 of Comparative Example 4, in which the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) in the silicone resin in the adhesive layer 3 exceeded the upper limit of the requirements of the present invention, the ratio of silicone glue (G) in the adhesive layer 3 was large, and in the dicing test, the vibration of dicing was easily transmitted to the adhesive layer 3 and the vibration amplitude became large, so defects were found on the individualized semiconductor chips. In addition, since the adhesive force was also low, the fixing force of the dicing test piece was low, and many chips were found to fly during dicing. In addition, since the content of silicon atom-bonded olefin groups in the silicone resin in the adhesive layer 3 exceeded the upper limit of the present embodiment, when the adhesive tape 1 was subjected to the test, the peeling pad was difficult to peel off from the adhesive layer 3 and the workability was poor compared to other adhesive tapes 1. Moreover, since the cohesive force increasing effect of the adhesive layer 3 formed by UV irradiation was sufficient, no residue was found in the silicone resin residue test and the epoxy resin residue test. In addition, in the dicing test, no residue was found for the wafer that did not fly.

Furthermore, in the adhesive tape 1 of Comparative Example 5, in which the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) is less than the lower limit of the requirements of the present invention, the ratio of silicone resin (R) without silicon atom-bonded olefin groups in the adhesive layer 3 is high, so the cohesion increase effect of the adhesive layer 3 formed by UV irradiation is not sufficient. In the silicone resin residue test and the epoxy resin residue test, slightly more residues were found, which are believed to be caused by the uncrosslinked components of the silicone resin (R). In addition, in the dicing test, the chip pickup of the diced test piece was also poor, and many residues were found on the chip.

1: Adhesive tape 2: Base material 3: Adhesive layer 100: Semiconductor component substrate 101: Substrate 102: Semiconductor component 103: Sealing resin 200: Semiconductor chip

[Figure 1] is a diagram showing an example of the structure of the dicing adhesive tape applicable to the present embodiment. [Figure 2] (a) to (e) are diagrams showing a method for manufacturing a semiconductor chip using the adhesive tape of the present embodiment. [Figure 3] is a schematic diagram showing the relationship between the crosslinking density of the silicone resin in the adhesive layer and the result of the holding force test of the adhesive tape 1 (falling time).

1: Adhesive tape

2: Base material

3: Adhesive layer

Claims (7)

A dicing adhesive tape comprises a substrate and an adhesive layer laminated on the substrate, and is used when a semiconductor material is divided into a plurality of semiconductor chips, wherein the semiconductor material has a plurality of semiconductor elements coated by a coating material, and the adhesive layer is composed of an adhesive composition, wherein the adhesive composition comprises: a silicone resin mixed with a silicone glue (G) and a silicone resin (R), a crosslinking agent for the silicone resin, and A photosensitive platinum (Pt) catalyst, the crosslinking agent is an organic polysiloxane having at least two silicon-atom-bonded hydrogen atoms (SiH groups) in one molecule, the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) in the silicone resin as a whole is in the range of 35.0/65.0 to 50.0/50.0 in terms of mass ratio, the silicone gel (G) comprises: a silicone gel (G _alk ) composed of an organic polysiloxane containing a silicon-atom-bonded alkenyl group, and the content of the silicon-atom-bonded alkenyl group in the silicone resin as a whole is in the range of 1.8×10 ^-6 mol/g to 1.0×10 ^-5 mol/g. As in claim 1, the dicing adhesive tape, wherein the plurality of the aforementioned semiconductor elements are attached to the aforementioned semiconductor material sealed by the aforementioned covering material from the side of the covering material, and the covering material is composed of silicone resin. The dicing adhesive tape of claim 1 or 2, wherein in the adhesive layer, the content of the silicon atom-bonded olefin groups in the entire silicone resin is in the range of 3.0×10 ^-6 mol/g to 1.0×10 ^-5 mol/g. As in claim 1 or 2, the adhesive tape for dicing, wherein in the adhesive layer, the molar ratio (SiH group/silicon atom bonded olefin group) of the content (total amount) of the aforementioned silicon atom bonded hydrogen atoms (SiH groups) contained in the aforementioned crosslinking agent to the content (total amount) of the aforementioned silicon atom bonded olefin groups in the aforementioned silicone resin contained in the aforementioned adhesive composition is in the range of 2.0 to 10.0. As in claim 1 or 2, the adhesive tape for cutting, wherein in the adhesive layer, the content of the aforementioned photosensitive platinum (Pt) catalyst in the aforementioned adhesive composition is in the range of 0.10 mass parts to 3.00 mass parts in terms of solid content relative to 100 mass parts of the total solid content of the aforementioned silicone resin. For the adhesive tape for cutting as claimed in claim 1 or 2, the adhesive properties according to JIS Z 0237 (2009) satisfy all of the following conditions (a) to (c): (a) the adhesive force to the BA-SUS test plate before light irradiation is within the range of 2.7 N/10 mm to 4.1 N/10 mm; (b) the ball number (ball tack test) in the ball tack test (tilt angle 30°, temperature 23°C, relative humidity 50% RH) is within the range of 2.7 N/10 mm to 4.1 N/10 mm; (c) In the retention test after light irradiation (temperature 40°C, relative humidity 33%RH, placement time 2880 minutes), the damage phenomenon when falling is the interface between the above-mentioned adhesive layer and the BA-SUS test plate peeling off, or the test plate does not fall in the retention test. A method for manufacturing a semiconductor chip comprises: an attaching step: attaching a dicing adhesive tape as described in any one of claims 1 to 6 from the side of a sealing resin formed by a silicone resin to a semiconductor element substrate on which a plurality of the aforementioned semiconductor elements are formed on the substrate; a cutting step: cutting the aforementioned semiconductor element substrate to which the aforementioned dicing adhesive tape is attached into a plurality of semiconductor chips; an irradiation step: irradiating the aforementioned dicing adhesive tape of the aforementioned semiconductor element substrate with light; and a peeling step: peeling the aforementioned dicing adhesive tape from the aforementioned plurality of semiconductor chips.

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