WO2021090863A1

WO2021090863A1 - Laminate body that includes temporary adhesive film; temporary adhesive composition; laminate body manufacturing method; and semiconductor element manufacturing method

Info

Publication number: WO2021090863A1
Application number: PCT/JP2020/041302
Authority: WO
Inventors: 齋江　俊之; 晃山内; 嶋田　和人
Original assignee: 富士フイルム株式会社
Priority date: 2019-11-07
Filing date: 2020-11-05
Publication date: 2021-05-14
Also published as: TW202124145A

Abstract

This laminate body comprises, in order, a substrate, a temporary adhesive film, and a support body, wherein the substrate and the temporary adhesive film are divided into multiple sections by cuts extending from the substrate to the temporary adhesive film, and a first adhesive strength between the substrate and the temporary adhesive film is greater than or equal to a second adhesive strength between the temporary adhesive film and the support body. Also provided are a temporary adhesive composition for such a laminate body, a laminate body manufacturing method, and a semiconductor element manufacturing method.

Description

Laminated body including temporary adhesive film, temporary adhesive composition, manufacturing method of laminated body and manufacturing method of semiconductor element

The present invention relates to a laminate containing a temporary adhesive film, a composition for temporary adhesion, a method for producing a laminate, and a method for producing a semiconductor element.

In the semiconductor element manufacturing process (semiconductor process), a dicing process is performed to convert a base material such as a silicon wafer into chips. In the dicing process, a base material is usually attached to a support (generally also called a dicing tape) via a temporary adhesive film to form a laminate for fixing the base material, and blade dicing, laser dicing, or the like is used. It is carried out by cutting the base material (for example, Patent Document 1).

Further, in a semiconductor process, a technique for temporarily forming a protective film made of resin or the like on the surface of a base material is well known in order to prevent foreign matter from adhering to or scratching the surface of the base material. (For example, Patent Document 2).

Japanese Patent No. 5678682 Japanese Unexamined Patent Publication No. 07-161665

In the semiconductor process, some steps may continue after the dicing process, and it may be preferable to protect the surface of the base material in such steps.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate capable of protecting the chip surface after dicing treatment. Another object of the present invention is to provide a composition for temporary adhesion, a method for producing a laminate, and a method for producing a semiconductor device for such a laminate.

The above problem can be solved by making it possible to use a temporary adhesive film for fixing the base material to the support as a protective film during dicing. Specifically, the above-mentioned problems have been solved by the following means of <1>, preferably by the means of <2> and thereafter.
<1>
A laminate having a base material, a temporary adhesive film, and a support in this order.
The base material and the temporary adhesive film are divided into a plurality of parts by a notch extending from the base material to the temporary adhesive film.
A laminate in which the first adhesive force between the base material and the temporary adhesive film is equal to or greater than the second adhesive force between the temporary adhesive film and the support.
<2>
The difference between the first adhesive force and the second adhesive force is 10 to 100 N / mm ² .
The laminate according to <1>.
<3>
The second adhesive force is 20-100 N / mm ² .
The laminate according to <1> or <2>.
<4>
The thickness of the temporary adhesive film is 10 to 100 μm.
The laminate according to any one of <1> to <3>.
<5>
After the base material is peeled off from the support, the thickness of the temporary adhesive film on the base material is 10 to 100 μm.
The laminate according to any one of <1> to <4>.
<6>
The temporary adhesive film contains a release layer on the surface layer on the support side,
The laminate according to any one of <1> to <5>.
<7>
The support includes a release layer on the surface layer on the temporary adhesive film side.
The laminate according to any one of <1> to <5>.
<8>
The release layer contains a surfactant,
The laminate according to <6> or <7>.
<9>
The thickness of the release layer is 0.1 to 10 μm.
The laminate according to any one of <6> to <8>.
<10>
Temporary adhesive film contains non-curable resin,
The laminate according to any one of <1> to <9>.
<11>
Temporary adhesive film contains water-insoluble resin,
The laminate according to any one of <1> to <10>.
<12>
The laminate according to any one of <1> to <11>, wherein the temporary adhesive film contains a resin having a saturated solubility in 100 g of water at 23 ° C. of 0.9 g or less.
<13>
The temporary adhesive film contains at least one resin selected from the group consisting of polyvinyl acetal, polyalkyl methacrylate and acyl cellulose.
The laminate according to any one of <1> to <12>.
<14>
Temporary adhesive film contains antioxidant,
The laminate according to any one of <1> to <13>.
<15>
The base material contains a semiconductor circuit on the surface layer on the temporary adhesive film side,
The support is a dicing tape,
The laminate according to any one of <1> to <14>.
<16>
A composition for temporary adhesion used for forming a temporary adhesive film in the laminate according to any one of <1> to <15>.
<17>
This includes adhering a temporary adhesive film formed on one surface of the base material and the support to the other surface of the base material and the support, and then forming a notch extending from the base material to the temporary adhesive film. , A method of manufacturing a laminate,
A method for producing a laminate, wherein the first adhesive force between the base material and the temporary adhesive film is equal to or greater than the second adhesive force between the temporary adhesive film and the support.
<18>
Further, it includes a step of forming a temporary adhesive film on one surface of the base material and the support.
In the step of forming the temporary adhesive film, the temporary adhesive composition is applied to the surface of the base material or the support, and then the temporary adhesive composition is dried.
The method for producing a laminate according to <17>.
<19>
The method of applying the temporary bonding composition to the surface of the base material or the support is a spin coating method, a slit coating method or a spiral coating method.
The method for producing a laminate according to <18>.
<20>
A method for manufacturing a semiconductor device, which comprises the method for manufacturing a laminate according to any one of <17> to <19>.

The laminate of the present invention makes it possible to protect the chip surface after dicing.

FIG. 1 is a schematic cross-sectional view showing a laminated body of the present invention. FIG. 2 is a schematic view showing a state when the divided base material piece (chip) is taken out. FIG. 3 is a schematic view showing an example of some steps in the method for producing a laminate of the present invention.

Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.

The numerical range represented by the symbol "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.

In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.

In the present specification, the notation that does not describe substitution and non-substitution with respect to a group (atomic group) means that a group having a substituent (atomic group) is included as well as a group having no substituent (atomic group). is there. For example, when simply described as "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Means.

In the present specification, "exposure" means not only drawing using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of energy rays used for drawing include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, active rays such as extreme ultraviolet rays (EUV light) and X-rays, and particle beams such as electron beams and ion beams. Be done.

As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , Either, and "(meth) acryloyl" means both "acryloyl" and "methacryloyl", or either.

In the present specification, the solid content in the composition means other components other than the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, based on the total mass of the composition. It is represented by the mass percentage of other components excluding the solvent.

In the present specification, unless otherwise specified, the temperature is 23 ° C. and the atmospheric pressure is 101325 Pa (1 atm).

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. For this weight average molecular weight (Mw) and number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the measurement is carried out using THF (tetrahydrofuran) as the eluent. Unless otherwise specified, a UV ray (ultraviolet) wavelength 254 nm detector is used for detection in GPC measurement.

In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is above or below the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.

Hereinafter, embodiments of the laminate of the present invention will be described with reference to the drawings, but the present invention is not limited thereto. In order to make it easier to see, the scale of each component in the drawing is appropriately different from the actual one.

<Laminated body>
FIG. 1 is a schematic cross-sectional view showing a laminated body of the present invention, and FIG. 2 is a schematic view showing a state when one of the divided base material pieces (chips) is taken out.

As shown in FIG. 1, the laminate 1 of the present invention has a base material 10, a temporary adhesive film 12, and a support 14 in this order. Then, in the laminated body 1, the base material 10 and the temporary adhesive film 12 are divided into a plurality of parts by a notch 16 extending from the base material 10 to the temporary adhesive film 12, and between the base material 10 and the temporary adhesive film 12. The first adhesive force is equal to or greater than the second adhesive force between the temporary adhesive film 12 and the support 14.

In the laminated body of the present invention, since the first adhesive force is equal to or greater than the second adhesive force, the temporary adhesive film 12 adheres to the chip C when the chip C is taken out from the support 14 as shown in FIG. It will be in the state of. This makes it possible to use the temporary adhesive film 12 as a protective film that protects the surface of the chip C, and in each step after the dicing process (for example, die bonding, wire bonding, chip coating, etc.), the chip surface can be used. It becomes possible to protect.

Further, for example, as a method of protecting the surface of the base material in each step after the dicing treatment, a method of forming a protective film on the surface of each chip after the dicing treatment can be considered. However, forming a protective film on the surface of individual chips having a small size after the dicing process is complicated as a work, and further increases the number of steps of the semiconductor process, which may cause a problem that the manufacturing efficiency is lowered. .. From this point of view, when the laminate of the present invention is used, it is not necessary to separately provide a step of forming a protective film after the dicing treatment, so that it is possible to obtain an effect that a decrease in production efficiency can be suppressed.

The peeling mode of the laminated body is not particularly limited as long as the temporary adhesive film remains on the surface of the base material to be protected. As a peeling mode, for example, a state in which the support 14 and the temporary adhesive film 12 are peeled off at the adhesive interface S2 (that is, all of the temporary adhesive film 12 remains on the surface of the base material), and further, the inside of the temporary adhesive film 12 (It is a so-called cohesive failure of the temporary adhesive film, and a part of the temporary adhesive film remains on the surface of the base material). In particular, when the first adhesive force is equal to the second adhesive force or when the difference between them is small, the temporary adhesive film 12 is likely to be coagulated and broken, and the temporary adhesive film 12 is likely to be peeled off inside. .. When the temporary adhesive film 12 is peeled off internally, the thickness of the temporary adhesive film is smaller than that in the laminated state, but the problem of the present invention is achieved because the temporary adhesive film is present on the base material. can do. When cohesive failure occurs, the adhesive forces on both sides of the temporary adhesive film are considered to be equal to each other. The temporary adhesive film 12 does not have to be present on the entire adhesive surface of the base material 10. Therefore, it is sufficient that the temporary adhesive film 12 remains at least in the region of the base material 10 that is used as the chip C, and the temporary adhesive film 12 remains in the region that is not used as the chip C, such as the outer edge of the base material 10. It is not necessary, and the temporary adhesive film 12 may be peeled off at the adhesive interface S1 of the base material 10 and the temporary adhesive film 12.

In the laminate 1 of the present invention, the base material 10 and the temporary adhesive film 12 are adhered to each other at the adhesive interface S1, and the temporary adhesive film 12 and the support 14 are adhered to each other at the adhesive interface S2. The first adhesive force is the force related to the adhesion between the base material 10 and the temporary adhesive film 12 as described above, and the second adhesive force is related to the adhesion between the temporary adhesive film 12 and the support 14 as described above. It is power. The adhesive force acting between two substances in a bonded state can be measured as an external force per unit area required to separate the two substances (that is, release the bonded state). The method for measuring the adhesive force is not particularly limited as long as such an external force can be measured, but it can be carried out, for example, by the measuring method described in Examples described later. The first adhesive force is preferably larger than the second adhesive force. As a result, peeling is likely to occur more effectively at the adhesive interface between the support and the temporary adhesive film, and the strength of the temporary adhesive film as a protective film is likely to be ensured. Further, the difference between the first adhesive force and the second adhesive force is preferably ^{10 to 100 N / mm 2.} The upper limit of this numerical range ^{is preferably 90 N / mm 2} or less, more preferably 80 N / mm ² or less, and further preferably 50 N / mm ² or less. Further, the lower limit of this numerical range ^{is preferably 11 N / mm 2} or more, more preferably 20 N / mm ² or more, and further preferably 30 N / mm ² or more. The second adhesive force is preferably 20 to 110 N / mm ^2. As a result, peeling is more likely to occur more effectively at the adhesive interface between the support and the temporary adhesive film, and the holding force of the base material during dicing can be sufficiently secured. The upper limit of this numerical range ^{is preferably 100 N / mm 2} or less, more preferably 90 N / mm ² or less, and further preferably 50 N / mm ² or less. The lower limit of the numerical range, is preferably 21N / mm ² or more, more preferably 25 N / mm ² or more, more preferably 30 N / mm ² or more.

Further, the second adhesive force may be reduced after the dicing treatment by altering the support or the like. When the second adhesive force can be adjusted before and after dicing in this way, it becomes easier to achieve both peeling at the adhesive interface between the support and the temporary adhesive film and securing the holding force of the base material during dicing. In the present invention, when the second adhesive force between the support and the temporary adhesive film changes with the deterioration of the support, as in the case of having an adhesive layer made of a curable composition, the base is used in the present invention. The first adhesive force between the material and the temporary adhesive film may be greater than or equal to the second adhesive force after the change and before peeling. In this case, the difference between the adhesive strengths is the value after the change and before the peeling. Second adhesive strength after reduction, it is preferably 1.0 N / mm ² or less, more preferably 0.5 N / mm ² or less, and more preferably 0.3 N / mm ² or less .. Further, the second adhesive force before reduction, is preferably 3.0 N / mm ² or more, more preferably 5.0 N / mm ² or more, it is 10.0 N / mm ² or more More preferred. Further, the above difference between the adhesive forces after the second adhesive force is reduced ^{is preferably 2.0 N / mm 2} or more, more preferably 4.0 N / mm ² or more, and 9. It is more preferably 0 N / mm ^{2 or more.}

<< Base material >>
The base material is a member that is chipped by a dicing process, and is not particularly limited, and various base materials that can be used in the semiconductor process can be used depending on the use of the laminate. As the base material, for example, a transparent substrate used for a liquid crystal display device or the like, and a semiconductor substrate used for a light emitting element, a solid-state image sensor, a semiconductor memory, or the like can be used. Further, the base material may be a metal substrate, a resin substrate, or a prepreg (a sheet formed by impregnating a fiber member with a resin).

The transparent substrate is, for example, a glass substrate such as quartz glass, non-alkali glass, soda glass, borosilicate glass and aluminosilicate glass. Other structures such as a transparent conductive film, a reflective film, and a protective film may be formed on these transparent substrates. Semiconductor substrates include, for example, silicon, sapphire, silicon carbide, gallium nitride, aluminum, amorphous aluminum oxide, polycrystalline aluminum oxide, silicon nitride, silicon nitride, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, etc. It is a substrate made of InP, ZnO, or the like. Other structures such as a PN junction layer, a light emitting layer, a photoelectric conversion layer, a complementary metal oxide semiconductor (CMOS) layer, and an electrode layer may be formed on these semiconductor substrates. The metal substrate is, for example, an aluminum substrate, a copper substrate, a stainless steel substrate, or the like. The resin substrate is, for example, an epoxy substrate, a polycarbonate substrate, a flexible substrate (polyimide substrate, polyethylene naphthalate (PEN) substrate, polyethylene terephthalate (PET) substrate) and the like.

Further, if necessary, the base material may include an undercoat layer in the surface layer portion on the temporary adhesive film side in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface. Further, the base material may include, for example, a semiconductor circuit in the surface layer portion on the temporary adhesive film side. The base material may have a single-layer structure or a laminated structure.

The thickness of the base material (the maximum thickness when a structure or the like is included) is not particularly limited, and is appropriately set according to the application of the laminate. The thickness of the base material is, for example, 0.3 to 2 mm. The upper limit of this numerical range is preferably 1.5 mm or less, more preferably 1 mm or less, and further preferably 0.8 mm or less. Further, the lower limit of this numerical value range is preferably 0.4 mm or more, more preferably 0.5 mm or more, and further preferably 0.6 mm or more.

The shape of the base material is not particularly limited and is appropriately set according to the use of the laminated body. The shape of the base material is, for example, a disk shape (wafer type substrate) and a rectangular shape (panel type substrate). When the base material has a disk shape, the diameter is, for example, 50 to 500 mm. The upper limit of this numerical range is preferably 400 mm or less, more preferably 300 mm or less, and even more preferably 250 mm or less. Further, the lower limit of this numerical value range is preferably 100 mm or more, more preferably 150 mm or more, and further preferably 170 mm or more. On the other hand, when the base material has a rectangular shape, the maximum side length is, for example, 200 to 1000 mm. The upper limit of this numerical range is preferably 900 mm or less, more preferably 800 mm or less, and further preferably 700 mm or less. Further, the lower limit of this numerical value range is preferably 300 mm or more, more preferably 400 mm or more, and further preferably 450 mm or more. The base material may have an orientation flat or a notch.

The role of the surface on the base material protected by the temporary adhesive film is not particularly limited, and is appropriately set as necessary from the viewpoint of preventing the adhesion of foreign substances and the occurrence of scratches. The surface on the substrate thus protected is, for example, the surface of the substrate on which a predetermined structure or semiconductor circuit is formed. In this case, the surface of the base material on which a predetermined structure or semiconductor circuit is formed is attached so as to come into contact with the temporary adhesive film. Further, the surface on the base material thus protected may be, for example, the surface of the base material itself (so-called back surface) opposite to the surface of the base material on which a predetermined structure or semiconductor circuit is formed. In this case, the back surface is attached so as to come into contact with the temporary adhesive film. In the latter case, a protective film may be separately formed before dicing from the viewpoint of protecting the structure and the semiconductor circuit from debris generated during dicing. Further, even if the surface is on the same side, it is sufficient that the region where the structure or the semiconductor circuit is formed, that is, the region used as the chip can be protected. Therefore, for example, a temporary adhesive film is formed in the outer edge region which is not used as the chip. It is not mandatory to be done. However, from the viewpoint of dicing stability, it is preferable that the entire surface of the base material on the temporary adhesive film side adheres to the temporary adhesive film.

<< Temporary adhesive film >>
The temporary adhesive film is mainly composed of resin. The resin is appropriately selected within a range in which the first adhesive force is equal to or greater than the second adhesive force. The temporary adhesive film preferably contains a non-curable resin. As used herein, "non-curable" means at least one of heat (for example, 150 ° C. or higher, preferably 200 ° C. or higher) or light (for example, a wavelength in the range of 180 to 800 nm) exposed in the step after dicing treatment. It means that the hardness (Rockwell hardness) does not increase due to light in the band, preferably light having a wavelength of 200 to 400 nm. This makes it easier to remove the temporary adhesive film. Further, the temporary adhesive film preferably contains a thermoplastic resin (a resin that softens when heated to a glass transition point or a melting point). This makes it easier to remove the temporary adhesive film. It is also preferable that the temporary adhesive film contains a water-insoluble resin. As used herein, the term "water-insoluble" means a property in which the saturated solubility (g) in 100 g of water at 23 ° C. is 1 g or less. As a result, the protective function in the post-process using water is further improved. The saturated solubility of the water-insoluble resin in 100 g of water at 23 ° C. is preferably 0.9 g or less, more preferably 0.5 g or less, and further preferably 0.1 g or less. Further, with respect to the water-insoluble resin, the saturated solubility in water at 23 ° C. is practically 0.001 g or more, and may be 0.01 g or more. It is also preferable that the temporary adhesive film contains a transparent resin. This makes it possible to visually recognize the surface of the base material covered with the temporary adhesive film in the process after the dicing treatment. When the temporary adhesive film contains a transparent resin, the minimum light transmittance of the temporary adhesive film having a thickness of 50 mm in the wavelength range of 400 to 700 nm is preferably 85% or more, more preferably 88% or more. , 90% or more is more preferable. Further, the minimum light transmittance of the temporary adhesive film is practically 99.9% or less, and may be 98% or less. In particular, the temporary adhesive film preferably contains a non-curable and water-insoluble resin or a thermoplastic and water-insoluble resin, and is a non-curable, water-insoluble and transparent resin or a thermoplastic and water-insoluble resin. It is more preferable to contain a transparent resin, and further preferably to contain a thermoplastic, water-insoluble and transparent resin.

In particular, the temporary adhesive film preferably contains at least one resin selected from the group consisting of polyvinyl acetal, polyalkyl methacrylate and acylcellulose, and at least selected from the group consisting of polyvinyl acetal and polyalkyl methacrylate. It is more preferable to contain one kind of resin, and it is further preferable to contain polyvinyl acetal.

<<< Polyvinyl Acetal >>>
The polyvinyl acetal is preferably a resin obtained by reacting polyvinyl alcohol with an aldehyde to acetalize it, and more preferably a compound containing each repeating unit represented by the following formula (PV-1).

In formula (PV-1), R ¹ represents an alkyl group, R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and x, y and z are each repeating unit. It represents the molar ratio (mol%) in the resin, and x + y + z is 80 to 100 mol%. In addition, an asterisk "*" represents a bond or terminal site between repeating units.

R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 2 or 3 carbon atoms. In particular, ^{it is more preferable that R 1} is a propyl group (-C ₃ H ₇ ), that is, the polyvinyl acetal is polyvinyl butyral.

It is preferred R ² ~ ^{R 5} are hydrogen atoms. On the other hand, when R ² to R ⁵ represent a monovalent substituent, the monovalent substituent is preferably, for example, the following substituent T. Further, when R ² to R ⁵ represent a monovalent substituent, R ² may be the same or different ^{between different repeating units, and R 3} is the same among different repeating units. R ⁴ may be the same or different ^{between different repeating units, and R 5} may be the same or different between different repeating units. Good.

The substituent T is a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRT. ¹ Rt ² , -NHCONRT ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ and -SO ₂ NRt ¹ Rt ² is there. Here, Rt ¹ and Rt ² independently represent a hydrogen atom, a hydrocarbon group, or a heterocyclic group, respectively. When Rt ¹ and Rt ² are hydrocarbon groups, they may be bonded to each other to form a ring.

Regarding the above-mentioned substituent T, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 or 2. The alkyl group may be linear, branched or cyclic, preferably linear or branched. The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and particularly preferably 2 or 3 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched. The alkynyl group preferably has 2 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms. The alkynyl group may be linear or branched. The aryl group preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, and even more preferably 6 to 7 carbon atoms. The heterocyclic group may be monocyclic or polycyclic. The heterocyclic group is preferably a single ring or a polycycle having 2 to 4 rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 5.

The hydrocarbon group and the heterocyclic group as the substituent T may have yet another substituent or may be unsubstituted. As a further substituent here, the above-mentioned substituent T can be mentioned.

Specifically, the substituent T as described above includes, for example, a halogen atom (particularly a fluorine atom, a chlorine atom and a bromine atom), an alkyl group having 1 to 5 carbon atoms (particularly a methyl group, an ethyl group and a propyl group). Alkenyl groups with 2 to 5 carbon atoms (particularly ethenyl groups (vinyl groups) and propenyl groups), alkoxy groups with 1 to 5 carbon atoms (particularly methoxy groups, ethoxy groups and propoxy groups), hydroxyl groups, thiol groups, carbonyl groups, thio These include a carbonyl group, a carboxy group, an amino group, a nitro group and a phenyl group. In particular, the substituent T is preferably a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, a carbonyl group and a carboxy group. These substituents may have yet another substituent or may be unsubstituted.

X + y + z is preferably 85 to 100 mol%. The upper limit of this numerical range is usually 100 mol%, but may be about 98 mol%. The lower limit of this numerical range is more preferably 90 mol% or more, and further preferably 95 mol% or more. That is, the polyvinyl acetal may contain a repeating unit other than the above three repeating units, but the molar ratio of such other repeating units is preferably 0 to 20 mol%, and 0 to 10 mol. It is more preferably%, further preferably 0 to 5 mol%, and particularly preferably 0 mol%. x corresponds to the degree of acetalization in the polyvinyl acetal resin, and is preferably 50 to 90 mol%. The upper limit of this numerical range is preferably 85 mol% or less, more preferably 80 mol% or less, and further preferably 76 mol% or less. Further, the lower limit of this numerical value range is preferably 60 mol% or more, more preferably 65 mol% or more, and further preferably 70 mol% or more. y corresponds to the content of hydroxyl groups in the polyvinyl acetal resin, and is preferably 10 to 50 mol%. The upper limit of this numerical range is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less. Further, the lower limit of this numerical value range is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 24 mol% or more. z corresponds to the content of the acetyl group in the polyvinyl acetal resin, and is preferably 1 to 5 mol%. The upper limit of this numerical range is preferably 4 mol% or less, more preferably 3.5 mol% or less, and further preferably 3 mol% or less. Further, the lower limit of this numerical value range is preferably 1.5 mol% or more, more preferably 1.7 mol% or more, and further preferably 2 mol% or more.

The weight average molecular weight of polyvinyl acetal is preferably 10,000 to 300,000. The upper limit of this numerical range is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 120,000 or less. Further, the lower limit of this numerical range is preferably 20,000 or more, more preferably 50,000 or more, and further preferably 80,000 or more.

In the temporary adhesive film containing polyvinyl acetal as a main component, the content of polyvinyl acetal in the temporary adhesive film is preferably 50 to 100% by mass. The upper limit of this numerical range may be 98% by mass or less, 95% by mass or less, or 93% by mass or less. Further, the lower limit of this numerical range is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more. The polyvinyl acetal in the temporary adhesive film may be composed of one kind alone or a mixture containing two or more kinds of polyvinyl acetals. When the polyvinyl acetals are mixtures, their total amount is preferably in the above range.

<<< Alkyl methacrylate >>>
The polyalkyl methacrylate is more preferably a compound containing each repeating unit represented by the following formula (PM-1).

In formula (PM-1), R ⁷ represents an alkyl group, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a monovalent organic group, and p and q are each repeating unit in the resin. P is 60 to 100 mol%, q is 0 to 40 mol%, and p + q is 80 to 100 mol%. In addition, an asterisk "*" represents a bond or terminal site between repeating units. The repeating unit with q is a repeating unit that does not satisfy the requirements for the repeating unit with p.

For the repeating unit with p, p is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. Further, p may be 98 mol% or less. R ⁷ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms. In particular, R ⁷ is preferably a methyl group. R ⁷ may be different between different repeating units, but is preferably the same. Further, the polyalkyl methacrylate is preferably polymethyl methacrylate (PMMA) in which p is 90 mol% or more and R ^{7 is a methyl group.}

For the repeating unit with q, q is preferably 20 mol% or less, more preferably 10 mol% or less, and further preferably 5 mol% or more. Further, q may be 2 mol% or more.

Further, the repeating unit with q is preferably a repeating unit derived from (meth) acrylate that does not meet the requirements for the repeating unit with p. ^{Such repeating units include the case where R 8} is a hydrogen atom and R ⁸ is a methyl group and R ⁹ is -COOR ¹⁰ (R ¹⁰ is an organic other than an alkyl group) in the repeating unit with q. It may be represented by ().

Further, it is also preferable that the repeating unit with q is a repeating unit represented by the following formula (PM-2).

In the formula (PM-2), ^{R 8} has the same meaning as ^{R 8} in formula ^{(PM-1), R 20} is a monovalent substituent, m represents an integer of 0-4. Here, examples of the substituent include the above-mentioned substituent T, and specific examples thereof include a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, a carbonyl group and a carboxy group. The group of may further have a substituent. m may be 3 or less, or 1 or more.

Further, the hydrogen atom in the polyalkyl methacrylate may be substituted with a substituent. Examples of the substituent include the above-mentioned substituent T, and specific examples thereof include a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, a carbonyl group and a carboxy group.

The weight average molecular weight of the polyalkyl methacrylate is preferably 10,000 to 300,000. The upper limit of this numerical range is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 120,000 or less. Further, the lower limit of this numerical range is preferably 20,000 or more, more preferably 50,000 or more, and further preferably 80,000 or more.

In the temporary adhesive film containing polyalkyl methacrylate as a main component, the content of polyalkyl methacrylate in the temporary adhesive film is preferably 50 to 100% by mass. The upper limit of this numerical range may be 98% by mass or less, 95% by mass or less, or 93% by mass or less. Further, the lower limit of this numerical range is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more. The polyalkyl methacrylate in the temporary adhesive film may be composed of one kind alone or a mixture containing two or more kinds of polyalkyl methacrylate. When the polyalkyl methacrylates are mixtures, their total amount is preferably in the above range.

<<< Acyl Cellulose >>
Acyl cellulose is a compound obtained by acyl esterifying cellulose, and is more preferably a compound represented by the following formula (AC-1).

In the formula (AC-1), R ¹¹ to R ¹⁶ independently represent a hydrogen atom or an acyl group (-COR ¹⁷ : R ¹⁷ is an alkyl group), and ^{at least one of R 11} to R ¹⁶ is an acyl group. It is a group, and n represents the degree of polymerization.

Regarding R ¹¹ to R ¹⁶ , the alkyl group R ¹⁷ in the acyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. It is more preferably an alkyl group of 3. In particular, ^{it is preferable that R 17} is a methyl group, that is, the acyl group is an acetyl group and the acyl cellulose is cellulose acetate. Within the same repeating unit and between different repeating units, the types of acyl groups are usually the same, but may be partially different.

^{For R 11} to R ¹⁶ in the same repeating unit, at least two are preferably acyl groups, at least four are more preferably acyl groups, and all six may be acyl groups. Between different repeating units, the number of acyl groups may be the same or different. The degree of acylation (the ratio of carboxylic acid liberated by saponifying acyl cellulose, which is also called the degree of vinegarization when the acyl cellulose is cellulose acetate), which indicates the degree of acyl esterification, is 35 to 75%. Is preferable. The upper limit of this numerical range is preferably 70% or less, more preferably 65% or less, and even more preferably 60% or less. Further, the lower limit of this numerical range is preferably 40% or more, more preferably 45% or more, and further preferably 50% or more. The degree of substitution representing the degree of substitution of the acyl group is preferably 0.1 to 3. The upper limit of this numerical range is preferably 2.9 or less, more preferably 2.8 or less, and even more preferably 2.7 or less. Further, the lower limit of this numerical range is preferably 0.2 or more, more preferably 0.3 or more, and further preferably 0.4 or more. Here, the degree of substitution means the average number of acetylated (acylated) groups of three hydroxyl groups per glucose unit. Cellulose acetate may have, for example, the above-mentioned substituent T.

Further, the hydrogen atom at the terminal in the formula (AC-1) may be substituted with a substituent (for example, another sugar).

The weight average molecular weight of acylcellulose is preferably 10,000 to 300,000. The upper limit of this numerical range is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 120,000 or less. Further, the lower limit of this numerical range is preferably 20,000 or more, more preferably 50,000 or more, and further preferably 80,000 or more.

In the temporary adhesive film containing acyl cellulose as a main component, the content of acyl cellulose in the temporary adhesive film is preferably 50 to 100% by mass. The upper limit of this numerical range may be 98% by mass or less, 95% by mass or less, or 93% by mass or less. Further, the lower limit of this numerical range is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more. The acyl cellulose in the temporary adhesive film may be composed of one kind alone or a mixture containing two or more kinds of acyl cellulose. When the acylcellulose is a mixture, it is preferable that the total amount thereof is in the above range.

<<< Elastomer >>>
As the resin used for the temporary adhesive film, for example, an elastomer can also be used. Since the temporary adhesive film contains an elastomer, it can follow the fine irregularities of the base material and the support, and can form a film having excellent adhesiveness by an appropriate anchor effect. Further, when the chip is peeled from the support, the chip can be easily peeled from the support without applying stress to the chip, and damage or peeling of the device or the like on the base material can be prevented.

In addition, in this specification, an elastomer means a polymer compound exhibiting elastic deformation. That is, it is a polymer compound having a property of being instantly deformed in response to the external force when an external force is applied and recovering to the original shape in a short time when the external force is removed. For example, an elastomer can be elastically deformed to a length of 200% by applying an external force and pulling both ends when the length of the original shape is 100% at room temperature (23 ° C.), and the external force is applied. It is preferable to have a property of returning to a length of 130% in a short time when the above is removed.

In the present invention, the elastomer has a 5% thermogravimetric reduction temperature raised from 25 ° C. to 20 ° C./min at 375 ° C. or higher, preferably 380 ° C. or higher, further preferably 390 ° C. or higher, and 400 ° C. or higher. Most preferred. The upper limit is not particularly limited, but is preferably 1000 ° C. or lower, more preferably 800 ° C. or lower, for example. According to this aspect, it is easy to form a film such as a sheet having excellent heat resistance. The mass reduction temperature is a value measured by a thermogravimetric analyzer (TGA) under the above-mentioned temperature rising conditions under a nitrogen stream. When the composition of the present invention contains two or more types of elastomers, it means a value in a mixture of two or more types of elastomers.

In the present invention, the glass transition temperature of the elastomer (hereinafter, also referred to as “Tg”) is preferably −50 to 300 ° C., more preferably 0 to 200 ° C. When Tg is in the above range, it has good followability to the surface of the device wafer at the time of bonding, and a film such as a void-free sheet can be formed. When the elastomer has two or more points of Tg, the value of Tg means the lower glass transition temperature.

In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and particularly preferably 50,000 to 100,000. Within this range, since the elastomer exhibits excellent solubility in a solvent, there is an advantage that no residue remains on the chip when the temporary adhesive film is removed.

In the present invention, the elastomer includes an elastomer containing a repeating unit derived from styrene (polystyrene-based elastomer), a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyamide-based elastomer, a polyacrylic elastomer, a silicone-based elastomer, and a polyimide-based elastomer. Etc. can be used. One or more selected from polystyrene-based elastomers, polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic elastomers, silicone-based elastomers, and polyimide-based elastomers is preferable, and from the viewpoint of solubility, heat resistance, and the like. Polystyrene elastomers are particularly preferred.

The polystyrene-based elastomer is not particularly limited and can be appropriately selected according to the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene. Examples thereof include copolymers (SBBS) and their hydrogenators, styrene-ethylene-propylene-styrene block copolymers (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymers.

The content of the repeating unit derived from styrene in the polystyrene-based elastomer is preferably 40% by mass or more, preferably 45% by mass or more, and more preferably 46% by mass or more. The upper limit can be, for example, 90% by mass or less, or 85% by mass or less.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer having one end or both ends being a styrene block, and both ends being a styrene block. It is particularly preferable that it is a block copolymer. If both ends of the polystyrene-based elastomer are styrene blocks (repeating units derived from styrene), the heat resistance is further improved. This is because a repeating unit derived from styrene, which has high heat resistance, is present at the end. In particular, since the styrene block is a reactive polystyrene-based hard block, it tends to be more excellent in heat resistance and chemical resistance, which is preferable. Further, it is considered that the phase separation between the hard block and the soft block is performed at 200 ° C. or higher by using an elastomer which is a block copolymer. The shape of the phase separation is considered to contribute to the suppression of the occurrence of unevenness on the substrate surface of the device wafer. In addition, such elastomers are more preferred from the standpoint of solvent solubility and resistance to resist solvents.

In addition, when polystyrene-based elastomers are hydrogenated, their stability against heat is improved, and deterioration such as decomposition and polymerization is unlikely to occur. Further, it is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.

In the present specification, the "styrene-derived repeating unit" is a styrene-derived structural unit contained in the polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, a carboxy group and the like.

For details on other elastomers (for example, polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic elastomers, silicone-based elastomers, polyimide-based elastomers, etc.), see, for example, JP-A-2018-037558. It has been described and these statements are incorporated herein by reference.

Further, the elastomer is preferably a hydrogenated product. In particular, a polystyrene-based elastomer hydrogenated product is preferable. When the elastomer is a hydrogenated product, it is easy to form a film such as a sheet having excellent heat resistance. Furthermore, it is easy to form a film such as a sheet having excellent peelability and cleaning / removing property after peeling. The above effect is remarkable when a polystyrene-based elastomer hydrogenated product is used. The hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated.

The elastomer preferably contains 10 to 100% by mass of polystyrene-based elastomer, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass. It is more preferable that the mixture is substantially composed of a polystyrene-based elastomer only. Further, among them, it is more preferable that the polystyrene-based elastomer hydrogenated product is contained in the above ratio.

In the temporary adhesive film containing an elastomer as a main component, the content of the elastomer in the temporary adhesive film is preferably 50 to 100% by mass. The upper limit of this numerical range may be 98% by mass or less, 95% by mass or less, or 93% by mass or less. Further, the lower limit of this numerical range is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more. The elastomer may contain a plurality of the types listed above. When the resin in the temporary adhesive film contains a plurality of elastomers, the total amount thereof is preferably in the above range.

<<< Other Thermoplastic Resins >>>
In the present invention, a thermoplastic resin other than the above-mentioned polyvinyl acetal, polymethyl methacrylate, cellulose acetate and elastomer (hereinafter, also simply referred to as “other thermoplastic resin”) can also be used. Other thermoplastic resins may be used alone or in combination of two or more. Specific examples of other thermoplastic resins include acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinylpyrrolidone resin, cycloolefin resin, thermoplastic siloxane resin, unsaturated polyester resin, thermoplastic polyimide resin, and polyvinyl chloride. Examples thereof include resins, polyvinyl acetate resins, polycarbonate resins, polyphenylene ether resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, polyether sulfone resins, polyarylate resins, and cellulose resins.

For example, acrylic resins as other thermoplastic resins include 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, and n-octyl. (Meta) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-nonyl (meth) acrylate, isoamyl (meth) acrylate , N-decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and 2-methylbutyl ( Meta) acrylate and the like. In addition to the above, examples thereof include Mitsubishi Rayon Co., Ltd., Acrypet MF 001, 3M Japan Ltd., LC-5320 F1035, and the like.

Further, the acrylic resin may be a compound obtained by copolymerizing a (meth) acrylate monomer and another monomer without departing from the spirit of the present invention. When the (meth) acrylate monomer is copolymerized with another monomer, the amount of the other monomer is preferably 10 mol% or less of the total monomer.

The content of the resin in the temporary adhesive film is preferably 8% by mass or more. In particular, the upper limit of this numerical range is preferably 30% by mass or less, more preferably 26% by mass or less, and further preferably 22% by mass or less. Further, the lower limit of this numerical value range is preferably 10% by mass or more, more preferably 11% by mass or more, and further preferably 12% by mass or more. The resin in the temporary adhesive film may be composed of one kind alone or a mixed resin containing two or more kinds of resins. When the resin is a mixed resin, it is preferable that the total amount thereof is in the above range.

The thickness of the temporary adhesive film in the laminated body is preferably 10 to 100 μm. When the thickness of the temporary adhesive film is within the above range, the thickness of the temporary adhesive film is within an appropriate range on the chip peeled from the support, and the function of the temporary adhesive film as a protective film is more effectively exhibited. To. The upper limit of this numerical range is preferably 90 μm or less, more preferably 85 μm or less, and further preferably 80 μm or less. Further, the lower limit of this numerical value range is preferably 15 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more.

Further, after the base material piece (chip) is peeled off from the support, the thickness of the temporary adhesive film on the chip is preferably 10 to 100 μm. When the thickness of the temporary adhesive film on the chip is within the above range after the base material is peeled off from the support, the function of the temporary adhesive film as a protective film is more effectively exhibited. The upper limit of this numerical range is preferably 90 μm or less, more preferably 85 μm or less, and further preferably 80 μm or less. Further, the lower limit of this numerical value range is preferably 15 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more.

<<< Plasticizer >>>
The temporary adhesive film may contain a plasticizer, if necessary. As the plasticizer, phthalates, fatty acid esters, aromatic polyvalent carboxylic acid esters, polyesters and the like can be used.

Examples of phthalates include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical Industry Co., Ltd.), PL-200, DOIP (above, manufactured by CGG Ester Co., Ltd.), Examples include Sun Associate DUP (manufactured by New Japan Chemical Co., Ltd.).

Examples of fatty acid esters include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaceto 800B, Panaceto 875, Panaceto 810 (all manufactured by NOF CORPORATION), and DBA. , DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (all manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

Examples of the aromatic polyvalent carboxylic acid ester include TOTM, monosizer W-705 (above, manufactured by Daihachi Chemical Industry Co., Ltd.), UL-80, UL-100 (above, manufactured by ADEKA Corporation), and the like.

Examples of polyester include Polysizer TD-1720, Polysizer S-2002, Polysizer S-2010 (all manufactured by DIC Corporation), BAA-15 (manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

Among the above plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL, and Polysizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable. Only one type of plasticizer may be used, or two or more types may be combined.

In particular, since the thermoplasticity of cellulose acetate is relatively small, it is useful to add a plasticizer to cellulose acetate. Preferred plasticizers for cellulose acetate are, for example, triethyl citrate, acetyl triethyl citrate, dibutyl phthalate (DBP), diaryl phthalate, diethyl phthalate (DEP), dimethyl phthalate (DMP), di-2 phthalate. -Methoxyethyl, dibutyl tartrate, ethyl o-benzoylbenzoate, ethylphthalyl ethylglycolate (EPEG), methylphthalyl ethylglycolate (MPEG), N-ethyltoluenesulfonamide, triacetin, p-toluenesulfonic acid O-cresyl, Triethyl phosphate (TEP), triphenyl phosphate (TPP), tripropionin and the like.

From the viewpoint of preventing sublimation during heating, the temperature at which the mass of the plasticizer decreases by 1% by mass when the mass change is measured under a nitrogen flow and a constant rate of temperature of 20 ° C./min. It is preferably 250 ° C. or higher, more preferably 270 ° C. or higher, and particularly preferably 300 ° C. or higher. The upper limit is not particularly specified, but can be, for example, 500 ° C. or lower.

The amount of the plasticizer added is preferably 0.01% by mass to 5.0% by mass, more preferably 0.1% by mass to 2.0% by mass in the temporary adhesive film.

<<< Antioxidant >>>
The temporary adhesive film may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant and the like can be used.

Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox1035 (all manufactured by BASF Japan Ltd.), Sumilizer MDP- Examples include S and Sumilizer GA-80 (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl, Sumilizer TPM, Sumilizer TPS, Sumilizer TP-D (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of phosphorus-based antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and poly (dipropylene glycol). Examples thereof include phenylphosphite, diphenylisodecylphosphite, 2-ethylhexyldiphenylphosphite, triphenylphosphite, Irgafos168, Irgafos38 (all manufactured by BASF Japan Co., Ltd.) and the like.

Examples of the quinone-based antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.

Examples of amine-based antioxidants include dimethylaniline and phenothiazine.

As the antioxidant, Irganox1010, Irganox1330, 3,3'-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox1010 and Irganox1330 are more preferable, and Irganox1010 is particularly preferable.

Further, among the above-mentioned antioxidants, it is preferable to use a phenol-based antioxidant in combination with a sulfur-based antioxidant or a phosphorus-based antioxidant, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination. Is most preferable. In particular, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. With such a combination, it is expected that the deterioration of the temporary adhesive composition due to the oxidation reaction can be efficiently suppressed. When a phenolic antioxidant and a sulfur-based antioxidant are used in combination, the mass ratio of the two is preferably phenol-based antioxidant: sulfur-based antioxidant = 95: 5 to 5:95, and 25: 75 to 75. : 25 is more preferable.

As the combination of antioxidants, Irganox1010 and Sumilizer TP-D, Irganox1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, and Irganox1010 and SumilizerTP-D, Irganox1010 and SumilizerTP-D, Ir. More preferred, Irganox 1010 and Sumilizer TP-D are particularly preferred.

From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more.

When the temporary adhesive film contains an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass, preferably 0.005 to 10.0% by mass in the temporary adhesive film. Is more preferable. Only one type of antioxidant may be used, or two or more types may be used. When there are two or more kinds of antioxidants, it is preferable that the total amount thereof is in the above range.

<<< Other Additives >>>
The composition for temporary adhesion used in the present invention is, as long as the effect of the present invention is not impaired, in addition to the above-mentioned additives, various additives such as a curing agent, a curing catalyst, a filler, and adhesion promotion are required. Agents, ultraviolet absorbers, anti-aggregation agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the total solid content of the temporary adhesive composition.

The temporary adhesive film may have a single-layer structure or a multi-layer structure. In the case of a multi-layer structure, the temporary adhesive film can include one or more resin layers made of each of the above resins. Further, the temporary adhesive film may include a release layer described later in the surface layer portion on the support side.

<< Support >>
The support is a member for fixing the laminated body to the dicing frame during the dicing process, and is generally also called a dicing tape. The support may have a single-layer structure or a multi-layer structure. That is, the support can consist of a single-layer or multi-layer support film as a base. In addition, the support can include an adhesive layer formed on the support film. Further, the support can include a release layer described later in the surface layer portion on the temporary adhesive film side. The support preferably has elasticity so that it can be expanded (expanded) and easily taken out after dicing. Further, the support preferably has light transmission property when an adhesive layer made of an ultraviolet curable resin composition is used as described later.

The material of the support film constituting the support is not particularly limited, and may be appropriately selected from known polymer materials for resin films. The polymer materials constituting the support film include, for example, polyethylene, polypropylene, ethylene / propylene copolymers and polyolefins such as polybutene, ethylene / vinyl acetate copolymers, ethylene / (meth) acrylate copolymers, and the like. Ethylene copolymers such as ionomers, including copolymers of ethylene / (meth) acrylic acid esters, and copolymers of ethylene / (meth) acrylic acid metal salts, polyesters such as polyethylene terephthalate and polybutylene terephthalate, Acrylics such as polymethylmethacrylate, polyvinyl chlorides, polycarbonates, polyacetals, polyamides, polyimides, polyurethanes, polystyrenes, natural rubbers, synthetic rubbers and the like are preferred. Further, the support film may be composed of a mixed resin in which two or more kinds selected from these groups are mixed, or may have a structure in which two or more kinds of resins are multi-layered. When the support includes an adhesive layer, the material of the support can be arbitrarily selected in consideration of the adhesiveness with the adhesive layer.

The thickness of the support film is not particularly limited, and is preferably 50 to 300 μm, for example. The upper limit of this numerical range is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 160 μm or less. Further, the lower limit of this numerical value range is preferably 60 μm or more, more preferably 70 μm or more, and further preferably 90 μm or more.

The adhesive layer that can form the support has sufficient adhesiveness to suppress the scattering of the base material such as a semiconductor device during dicing. The material of the adhesive layer is not particularly limited, and conventionally known adhesive materials such as acrylic resin, urethane resin, and silicone resin can be included. The adhesive layer is preferably made of a curable composition that is cured by applying heat or energy rays. As a result, the adhesive layer can be appropriately cured by applying heat or energy rays, and the adhesive force to the temporary adhesive film can be reduced. As a result, peeling is likely to occur more effectively at the adhesive interface between the support and the temporary adhesive film, and the strength of the temporary adhesive film as a protective film is likely to be secured. In particular, the curable composition is preferably a composition that is cured by irradiation with energy rays, and more preferably a composition that is cured by irradiation with ultraviolet rays. The curable composition contains, for example, a monomer or oligomer having a polymerizable functional group, and a polymerization initiator. The adhesiveness of the adhesive layer can be appropriately controlled by controlling the crosslink density of the adhesive material. The cross-linking density of the adhesive material is controlled by, for example, a method of cross-linking with an appropriate cross-linking agent such as a polyfunctional isocyanate compound, an epoxy compound, a melamine compound, a metal salt compound, a metal chelate compound, an amino resin compound and a peroxide. , And a compound having two or more carbon-carbon double bonds can be mixed and subjected to an appropriate method such as a method of cross-linking by irradiation with energy rays or the like.

The curable composition may optionally contain one or more other additives such as polymerization inhibitors, antioxidants, leveling agents, thickeners, thickeners, surfactants and fillers. You may. Further, the ultraviolet curable composition may contain a solvent from the viewpoint of improving the applicability of the composition.

Details of the dicing tape containing the adhesive layer made of the curable composition are described in, for example, Japanese Patent Application Laid-Open No. 2010-251722, and the contents thereof are incorporated in the present specification.

The thickness of the adhesive layer is not particularly limited, and is preferably 5 to 100 μm, for example. The upper limit of this numerical range is preferably 80 μm or less, more preferably 70 μm or less, and further preferably 60 μm or less. Further, the lower limit of this numerical value range is preferably 10 μm or more, and may be 15 μm or more or 20 μm or more.

The thickness of the entire support is preferably 60 to 300 μm. The upper limit of this numerical range is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 160 μm or less. Further, the lower limit of this numerical value range is preferably 70 μm or more, more preferably 80 μm or more, and further preferably 100 μm or more.

The following commercially available dicing tape can also be used as the support. HAE-1503, HAE-1603, UC-334EP-85, UC-353EP-110A, UC3026M-110, UC3044M-110B (all manufactured by Furukawa Electric Co., Ltd.), UHP-1005AT, UHP-1025M3, USP-1520MG, UDT -1915MC (above, manufactured by DENKA), D-series (above, manufactured by Lintec).

<< Peeling layer >>
In the laminated body of the present invention, it is preferable that the temporary adhesive film contains a release layer in the surface layer portion on the support side, or the support includes a release layer in the surface layer portion on the temporary adhesive film side. In the present specification, if the release layer is on the temporary adhesive film side before the temporary adhesive film is adhered to the support, the release layer is a part of the temporary adhesive film, and if the release layer is on the support side, the release layer is used. Is part of the support. The release layer has a function of promoting separation between the support and the temporary adhesive film. The thickness of the release layer in the laminate is preferably 10 to 100 μm. When the thickness of the release layer is within the above range, the adhesive force required for the dicing process is secured, and the release of the chip from the support is more effectively promoted. The upper limit of this numerical range is preferably 90 μm or less, more preferably 85 μm or less, and further preferably 80 μm or less. Further, the lower limit of this numerical value range is preferably 15 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more.

The release layer preferably contains a surfactant, preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant, and is a fluorine-based surfactant and a silicone-based surfactant. It preferably consists of at least one type.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass. Here, the fluorine content is the ratio of the mass of all fluorine atoms to the molecular weight. Regarding the fluorine content, the upper limit is more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The lower limit is more preferably 5% by mass or more, and particularly preferably 7% by mass or more. A surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving property, and also has good peelability of the temporary adhesive layer.

The fluorine-based surfactant is not particularly limited, but a fluorine-based surfactant that does not contain perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) is preferable. Examples of the fluorine-based surfactant that can be used in the present invention include commercially available products, Megafuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Co., Ltd.), Florard FC-135, FC- 170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG7105, AG7000, AG950, AG7600, Surfron S-112, S-113, S -131, S-141, S-145, S-381, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC -106 (manufactured by AGC Seimi Chemical Co., Ltd.), Ftop EF301, EF303, EF351, EF352, EF801, EF802 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Fluorent 250 (manufactured by Neos Co., Ltd.) Can be mentioned. In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like can be mentioned.

Examples of the silicone-based surfactant include compounds containing Si—O bonds, such as silicone oil, silane coupling agent, silicone resin, silicone rubber, and cyclic siloxane, and silicone oil is preferable.

Further, it is preferable that the silicone-based surfactant does not contain a reactive group such as a polymerizable group.

The silicone-based surfactant is preferably a polyether-modified silicone. The ratio of the polyether-modified silicone represented by the formula (A) is 80% or more.

Formula (A) {(MO + EO) / AO} x 100
In the above formula (A), MO is the mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is the mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. Yes, AO refers to the mol% of alkylene oxide contained in the polyether structure in the polyether-modified silicone.

The ratio represented by the above formula (A) is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, still more preferably 99% or more. , 100% is even more preferable.

The weight average molecular weight of the polyether-modified silicone is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 40,000.

The polyether-modified silicone is obtained when the polyether-modified silicone is heated from 20 ° C. to 280 ° C. at a heating rate of 20 ° C./min under a nitrogen flow of 60 mL / min and held at a temperature of 280 ° C. for 30 minutes. The mass reduction rate is preferably 50% by mass or less. By using such a compound, the surface texture after processing of the substrate accompanied by heating is further improved. The mass reduction rate of the polyether-modified silicone is preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, still more preferably 30% by mass or less. The lower limit of the mass reduction rate of the polyether-modified silicone may be 0% by mass, but 15% by mass or more, further 20% by mass or more is a sufficiently practical level.

The light refractive index of the polyether-modified silicone is preferably 1.440 or less. The lower limit is not particularly defined, but even if it is 1.400 or more, it is a sufficiently practical level.

The content of the polyoxyalkylene group in the molecule of the polyether-modified silicone is not particularly limited, but it is desirable that the content of the polyoxyalkylene group exceeds 1% by mass in the total molecular weight.

The content of the polyoxyalkylene group is defined by "{(the formula amount of the polyoxyalkylene group in one molecule) / the molecular weight of one molecule} x 100".

Examples of the silane coupling agent include a fluorine atom-containing silane coupling agent, and triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane is preferable.

Further, examples of the silane coupling agent include JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and JP-A. 63-034540, 07-230165, 08-062834, 09-054432, 09-005988, 2001-330953, respectively. Surfactants are also mentioned and these descriptions are incorporated herein.

As the silicone-based surfactant used in the present invention, a commercially available product can also be used.

For example, "ADVALON FA33", "FLUID L03", "FLUID L033", "FLUID L051", "FLUID L053", "FLUID L060", "FLUID L066", "IM22", "WACKER-Belsil DMC 6038" , Asahi Kasei Wacker Silicone Co., Ltd., "KF-352A", "KF-353", "KF-615A", "KP-112", "KP-341", "X-22-4515", "KF" -354L "," KF-355A "," KF-6004 "," KF-6011 "," KF-6011P "," KF-6012 "," KF-6013 "," KF-6015 "," KF-6016 " , "KF-6017", "KF-6017P", "KF-6020", "KF-6028", "KF-6028P", "KF-6038", "KF-6043", "KF-6048", "KF-6123", "KF-6204", "KF-640", "KF-642", "KF-643", "KF-644", "KF-945", "KP-110", "KP" -355 "," KP-369 "," KS-604 "," Polon SR-Conc "," X-22-4272 "," X-22-4952 "(all manufactured by Shin-Etsu Chemical Co., Ltd.), "8526 ADDITIVE", "FZ-2203", "FZ-5609", "L-7001", "SF 8410", "2501 COSMETIC WAX", "5200 FORMURATION AID", "57 ADDITIVE", "8019 ADDITIVE", "8029 ADDITIVE", "8054 ADDITIVE", "BY16-036", "BY16-201", "ES-5612 FORMURATION AID", "FZ-2104", "FZ-2108", "FZ-2123", "FZ" -2162 "," FZ-2164 "," FZ-2191 "," FZ-2207 "," FZ-2208 "," FZ-2222 "," FZ-7001 "," FZ-77 "," L-7002 " , "L-7604", "SF8427", "SF8428", "SH 28 PAINR ADDITIVE", "SH3479", "SH3773M", "SH8400", "SH8700" (all manufactured by Toray Dow Corning Co., Ltd.) , "BYK-378", "BYK-302", "BYK-307", " BYK-331 "," BYK-345 "," BYK-B "," BYK-347 "," BYK-348 "," BYK-349 "," BYK-377 "(all manufactured by Big Chemie Japan Co., Ltd.) ), "Silwet L-7001", "Silwet L-7002", "Silwet L-720", "Silwet L-7200", "Silwet L-7210", "Silwet L-7220", "Silwet L-7230" , "Silwet L-7605", "TSF4445", "TSF4446", "TSF4452", "Silwet Hydrostable 68", "Silwet L-722", "Silwet L-7280", "Silwet L-7500", "Silwet L-7500" -7550 ”,“ Silwet L-7600 ”,“ Silwet L-7602 ”,“ Silwet L-7604 ”,“ Silwet L-7607 ”,“ Silwet L-7608 ”,“ Silwet L-7622 ”,“ Silwet L- 7650 ”,“ Silwet L-7657 ”,“ Silwet L-77 ”,“ Silwet L-8500 ”,“ Silwet L-8610 ”,“ TSF4440 ”,“ TSF4441 ”,“ TSF4450 ”,“ TSF4460 ”(above, momentary)・ Performance Materials Japan GK) is an example.

The silicone-based surfactants include the trade names "BYK-300", "BYK-306", "BYK-310", "BYK-315", "BYK-313", "BYK-320", and "BYK". -322 "," BYK-323 "," BYK-325 "," BYK-330 "," BYK-333 "," BYK-337 "," BYK-341 "," BYK-344 "," BYK-370 " , "BYK-375", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (Manufactured by Co., Ltd.), product names "AC FS 180", "AC FS 360", "AC S 20" (above, manufactured by Algin Chemie), product names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow" KL-401, "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "Polyflow KL-700" (all manufactured by Kyoeisha Chemical Co., Ltd.), product name "KP-301" , "KP-306", "KP-109", "KP-310", "KP-310B", "KP-323", "KP-326", "KP-341", "KP-104", " KP-110 "," KP-112 "," KP-360A "," KP-361 "," KP-354 "," KP-357 "," KP-358 "," KP-359 "," KP- 362 ”,“ KP-365 ”,“ KP-366 ”,“ KP-368 ”,“ KP-330 ”,“ KP-650 ”,“ KP-651 ”,“ KP-390 ”,“ KP-391 ” , "KP-392" (all manufactured by Shin-Etsu Chemical Co., Ltd.), product names "LP-7001", "LP-7002", "8032 ADDITIVE", "FZ-2110", "FZ-2105", " 67 ADDITIVE, 8618 ADDITIVE, 3 ADDITIVE, 56 ADDITIVE (above, manufactured by Toray Dow Corning Co., Ltd.), "TEGO WET 270" (manufactured by Ebonic Degusa Japan Co., Ltd.), "NBX" -15 "(manufactured by Neos Co., Ltd.) and the like can also be used.

The release layer can be formed, for example, by applying the above-mentioned surfactant as it is to a temporary adhesive film or a support to form a film. Further, if necessary, a composition in which the above-mentioned surfactant is dissolved in a solvent may be applied to the temporary adhesive film or the support.

<Composition for temporary adhesion>
The temporary adhesive composition is a composition used for forming a temporary adhesive film. The composition for temporary adhesion contains the above-mentioned material component of the temporary adhesive film as a solid content, and can contain a solvent if necessary. For example, the temporary adhesive film is formed by applying a solvent-containing temporary adhesive composition to the surface of a support or a base material and drying the composition. Alternatively, the temporary adhesive film is formed by attaching a temporary adhesive film formed in a sheet shape to the surface of the support or the base material. The solvent used in the temporary bonding composition is preferably an organic solvent.

Organic solvents include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyoxyacetate (eg alkyl). Methyl oxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg) : Methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) , 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, 2-methoxy) Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate ( For example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid. Esters such as methyl, ethyl 2-oxobutate, 1-methoxy-2-propyl acetate;
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone;
Toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, t-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1 -Phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-simene, indan, 1 , 2,3,4-Tetrahydronaphthalene, 3-ethyltoluene, m-simene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-simene, 1,4-diisopropylbenzene, 4- t-butyltoluene, 1,4-di-t-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-t-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-t-butyl-m-xylene, 3,5-di-t-butyltoluene, 1 , 2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene and other aromatic hydrocarbons;
Hydrocarbons such as limonene, p-menthane, nonane, decane, dodecane, and decalin are preferably mentioned.

Among these, mesitylene, t-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate , Diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred.

It is also preferable to mix two or more of these solvents from the viewpoint of improving the properties of the coated surface. In this case, particularly preferably, mesityrene, t-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate. , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. It is a mixed solution composed of two or more kinds.

From the viewpoint of coatability, the content of the solvent in the temporary adhesive composition is preferably such that the total solid content concentration of the composition is 5 to 80% by mass, more preferably 10 to 50% by mass. It is particularly preferably 12 to 40% by mass. The solvent may be only one type or two or more types. When there are two or more kinds of solvents, it is preferable that the total amount thereof is in the above range.

The content of the solvent in the temporary adhesive film obtained by drying is preferably 1% by mass or less, and more preferably 0.1% by mass or less.

<Manufacturing method of laminated body>
Hereinafter, the method for producing the laminate of the present invention will be described with reference to FIG. FIG. 3 is a schematic view showing an example of some steps in the method for producing a laminate of the present invention. The method for producing a laminated body of the present invention is a method for producing the above-mentioned laminated body with a notch by dicing treatment. That is, in the method for producing a laminated body of the present invention, a temporary adhesive film 12 (step A in FIG. 3) formed on the surface of one of the base material 10 and the support 14 (support 14 in FIG. 3) is used as a base material. Adhesion to the surface of 10 and the other of the support 14 (base material 10 in FIG. 3) (step B in FIG. 3), and then forming a notch 16 extending from the base material 10 to the temporary adhesive film 12 (step B in FIG. 3). It is characterized by including the step C) of FIG. Then, in the method for producing a laminated body of the present invention, the first adhesive force between the base material 10 and the temporary adhesive film 12 is equal to or greater than the second adhesive force between the temporary adhesive film 12 and the support 14. By the method for producing a laminated body of the present invention as described above, a laminated body capable of protecting the chip surface after dicing treatment can be obtained.

In step A, the temporary adhesive film is formed by using the above-mentioned temporary adhesive composition. The method for forming the temporary adhesive film is not particularly limited, and as such a method, for example, a method of applying the temporary adhesive composition to one surface of the base material and the support and drying the composition, and a method of preliminarily drying the film. There is a method of attaching the temporary adhesive composition in the form of the above to one surface of the base material and the support. When the release layer is provided, it may be formed on the surface of the support or the surface of the temporary adhesive film before the support and the temporary adhesive film are adhered to each other.

Examples of the method for applying the composition for temporary bonding include a spin coating method, a slit coating method, a spiral coating method, a spray coating method, a screen printing method, an inkjet method, a casting coating method, a roll coating method and a dropping method (drop casting). Can be mentioned. Among them, the application method is preferably a spin coating method, a slit coating method or a spiral coating method. The drying conditions of the applied temporary bonding composition can be adjusted as appropriate, for example, by heating at 80 to 270 ° C. (preferably 150 to 210 ° C.) for 0.5 to 5 minutes (preferably 1 to 4 minutes). Can be done.

In step B, as a method of adhering the temporary adhesive film 12 to the base material 10 or the support 14, for example, a method using a crimping device is preferable. Further, in the bonding using the crimping device, it is preferable to individually or simultaneously apply heat and pressure to the base material, the temporary adhesive film and the support, and it is more preferable to perform both of them at the same time. The heating temperature is, for example, 50 to 300 ° C., although it depends on the components contained in the temporary bonding composition. The upper limit of this numerical range is preferably 250 ° C. or lower, and more preferably 200 ° C. or lower. Further, the lower limit of this numerical value range is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher. The heating time is, for example, 30 seconds to 30 minutes. The upper limit of this numerical range is preferably 15 minutes or less, and more preferably 5 minutes or less. The lower limit of this numerical range is preferably 45 seconds or longer, and more preferably 1 minute or longer. The pressure is, for example, 0.05 to 3 N / mm ² . The upper limit of the numerical range, it is more preferable is preferably 2.5 N / mm ² or less, 2N / mm ² or less. The lower limit of this numerical range ^{is preferably 0.08 N / mm 2} or more, and more preferably 0.1 N / mm ² or more. The pressure application time is, for example, 30 seconds to 30 minutes. The upper limit of this numerical range is preferably 20 minutes or less, and more preferably 10 minutes or less. The lower limit of this numerical range is preferably 45 seconds or longer, and more preferably 1 minute or longer.

<< Dicing >>
The dicing method including forming the notch 16 is not particularly limited, and blade dicing, laser dicing, plasma dicing and the like are appropriately selected. The mode of cutting is not particularly limited, and may be half-cut or full-cut, and any of the full-cut, single-cut, step-cut, bevel-cut, and the like may be used.

The depth of cut is appropriately adjusted according to the thickness of the temporary adhesive film and the base material, and is preferably 50% or more of the total thickness of the temporary adhesive film and the base material, for example. When the notch does not reach the adhesive interface between the temporary adhesive film and the support, the support may be expanded to promote chip formation. The depth of cut is more preferably 70% or more of the total thickness, and further preferably 80% or more of the total thickness. Further, the depth of cut may be 100% of the total thickness (that is, the cut reaches the bonding interface between the temporary adhesive film and the support), and may be 90% or less of the total thickness. The depth of cut may reach the inside of the support within a range that does not interfere with the dicing process, but it is preferable that the depth of the cut does not reach the inside of the support from the viewpoint of stability of the dicing process. The width of the notch can be adjusted as appropriate, for example, 0.01 to 1 mm. The upper limit of this numerical range is preferably 0.5 mm or less, and more preferably 0.3 mm or less. The lower limit of this numerical range is preferably 0.03 mm or more, and more preferably 0.05 mm or more.

The shape of the chip is usually rectangular except for the outer edge region of the base material, but it may be another polygonal shape. The size of the chip (length of the maximum side) is not particularly limited, but is, for example, 0.8 to 3 mm. The upper limit of this numerical range may be 2.5 mm or less, or 2 mm or less. Further, the lower limit of this numerical range may be 0.9 mm or more, or 1 mm or more.

The temporary adhesive film on the chip after dicing may be physically peeled off manually or by using a machine, but it is preferably performed using an organic solvent. As the organic solvent, an organic solvent of the same type as the organic solvent used in the temporary bonding composition can be used. As a method of applying the solvent to the temporary adhesive film on the chip, a known method such as a dip method or a spray method can be appropriately adopted. The temperature of the solvent for removing the temporary adhesive film is, for example, 10 to 50 ° C. The upper limit of this numerical range is preferably 45 ° C. or lower, and more preferably 40 ° C. or lower. Further, the lower limit of this numerical value range is preferably 15 ° C. or higher, and more preferably 20 ° C. or higher. Further, ultrasonic cleaning may be performed by irradiating ultrasonic waves (about 20 to 50 kHz) together with the application of the organic solvent.

<Manufacturing method of semiconductor elements>
The method for manufacturing a semiconductor device of the present invention is characterized by including the above-mentioned method for manufacturing a laminate. That is, in the method for manufacturing a semiconductor element of the present invention, a laminated body with a notch is manufactured by the above-mentioned manufacturing method for a laminated body, a chip is taken out from the laminated body, and the semiconductor element is packaged by packaging the chip or the like. It is a method of manufacturing.

The semiconductor element manufactured by the manufacturing method of the present invention is, for example, an LSI device, but the semiconductor element of the present invention is not limited to this, and the present invention can be applied to various semiconductor elements.

The present invention can be applied to logic integrated circuits such as ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), and ASSP (Application Specific Standard Product), for example. Further, the present invention can be applied to, for example, a microprocessor such as a CPU (Central Processing Unit) and a GPU (Graphics Processing Unit). Further, the present invention provides, for example, DRAM (Dynamic Random Access Memory), HMC (Hybrid Memory Cube), MRAM (Magnetoresistive Random Access Memory), PCM (Phase-Change Memory), ReRAM (Resistance Random Access Memory), FeRAM (Ferroelectric). It can also be applied to memories such as RandomAccessMemory) and flash memory. The present invention also applies to analog integrated circuits such as LEDs (Light Emitting Diodes), power devices, DC (Direct Current) -DC (Direct Current) converters, and insulated gate bipolar transistors (Insulated Gate Bipolar Transistors: IGBTs). Applicable. The present invention is also applicable to MEMS (Micro Electro Mechanical Systems) such as acceleration sensors, pressure sensors, oscillators, and gyro sensors. Further, the present invention relates to, for example, GPS (Global Positioning System), FM (Frequency Modulation), NFC (Near field communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network). For wireless elements such as wireless elements, discrete elements, CMOS (Complementary Metal Oxide Semiconductor), CMOS image sensors, camera modules, Passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, IPD (Integrated Passive Devices), etc. Applicable.

The final product on which the semiconductor element of the present invention is mounted as described above is not particularly limited, and is, for example, a smart TV, a mobile communication terminal, a mobile phone, a smartphone, a tablet terminal, a desktop PC, a notebook PC, or a network device. (Router, switching), wired infrastructure equipment, digital camera, game machine, controller, data center, server, mining PC, HPC, graphic card, network server, storage, chipset, in-vehicle equipment (electronic control equipment, driving support system) ), Car navigation system, PND, lighting (general lighting, in-vehicle lighting, LED lighting, OLED lighting), TV, display, display panel (liquid crystal panel, organic EL panel, electronic paper), music playback terminal, industrial equipment, industrial use Robots, inspection equipment, medical equipment, white goods, space / aircraft equipment, wearable devices, etc.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Formation of laminate>
The materials listed in Table 1 were used to form laminates as described below. First, a coating solution (solid content concentration: 14% by mass) in which a resin (mixed resin if necessary) is dissolved in propylene glycol monomethyl ether is applied onto a support, dried, and temporarily adhered onto the support. A film (thickness listed in the table) was formed. The size of the support was set to a sufficient size so that it could be attached to the dicing frame. Further, in some examples, a release agent was applied on the support and dried before forming the temporary adhesive film to form a release layer (thickness: 50 μm) on the surface of the support. Next, the base material was sufficiently pressed against the temporary adhesive film (for example, with ^{a force of about 0.5 to 1 N / mm 2} ) to adhere the base material to the temporary adhesive film. As a result, a laminated body before the incision was formed was obtained.

Using a dicing device (DAD324, manufactured by Disco Corporation), dicing was performed by forming a single cut with a depth of 0.75 mm in the vertical and horizontal directions at a pitch of 3 mm on the above-mentioned laminated body before cutting. As a result, a laminated body with a notch divided into 3 mm squares was obtained.

In Table 1, the numerical values in the columns of "Resin 1" and "Resin 2" are the mixing ratio (mass%) of each resin in the mixed resin. Further, Example 3 is an example in which the adhesive layer of the dicing tape is cured by irradiating ^{ultraviolet rays (200 mJ / cm 2} , 30 seconds) from the dicing tape side after dicing and before taking out the chips.

The specifications of each material described in the above table are as follows.
<< Support >>
・ S-1: UC-334EP-85 (manufactured by Furukawa Electric Co., Ltd.)
・ S-2: UC3026M-110 (manufactured by Furukawa Electric Co., Ltd.)
・ S-3: UC3044M-110B (manufactured by Furukawa Electric Co., Ltd.)
・ S-4: UC-353EP-110A (manufactured by Furukawa Electric Co., Ltd.)

<< Release agent >>
・ R-1: Mega Fvck F-553 (manufactured by DIC Corporation)
・ R-2: KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
・ R-3: Optool DSX (manufactured by Daikin Industries, Ltd.)

<< Resin >>
-P-1: Polyvinyl acetal acetal (acetalization degree 66 mol%, hydroxyl group content 31 mol%, acetyl group content 3 mol%. Mw 40,000. BL-7, manufactured by Sekisui Chemical Co., Ltd.)
P-2: Polyvinyl butyral (acetalization degree 74 mol%, hydroxyl group content 25 mol%, acetyl group content 1 mol%. Mw108,000. KS-6Z, manufactured by Sekisui Chemical Co., Ltd.)
P-3: Polyvinyl butyral (acetalization degree 71 mol%, hydroxyl group content 27 mol%, acetyl group content 1 mol%. Mw108,000. B75-H, manufactured by Kuraray Co., Ltd.)
-P-4: Polymethyl methacrylate (Mw80,000. Telpet 80NH, manufactured by Asahi Kasei Corporation)
-P-5: Cellulose acetate (55% vinegarization, L-20, manufactured by Daicel)
P-6: Polyvinyl butyral (acetalization degree 74 mol%, hydroxyl group content 25 mol%, acetyl group content 1 mol%. Mw 130,000)
P-7: Polyvinyl butyral (acetalization degree 71 mol%, hydroxyl group content 27 mol%, acetyl group content 2 mol%. Mw 100,000. BX-1, manufactured by Sekisui Chemical Co., Ltd.)
-P-8: Cellulose acetate (61% vinegarization, LT-35, manufactured by Daicel)
-P-9: Cellulose acetate butyrate (Mw70,000. CAB-381-20, manufactured by Tomoe Engineering Co., Ltd.)
-P-10: Polymethyl methacrylate (Mw 90,000. Bimodal 80NEN, manufactured by Asahi Kasei Corporation)
-P-11: Styrene-butadiene-styrene copolymer (Mw20,000. TR2000, manufactured by JSR Corporation)

<< Base material >>
-M-1: Silicon substrate (disk-shaped, thickness 0.7 mm, maximum diameter 200 mm)
-M-2: Copper substrate (disk-shaped, thickness 0.8 mm, maximum diameter 200 mm)
-M-3: Glass substrate (disk-shaped, thickness 1.1 mm, maximum diameter 200 mm)

<Measurement of adhesive strength>
The adhesive force between the base material and the temporary adhesive film (first adhesive force) and the adhesive force between the support and the temporary adhesive film (second adhesive force) were separately measured by the following methods. First, a temporary adhesive film was formed on the base material, and then the upper temporary adhesive film was pulled up at a speed of 50 mm / min in the direction perpendicular to the lower base material. Then, the first adhesive force was obtained by measuring the external force required for the pulling up. Further, the base material was replaced with a support, and a second adhesive force was obtained by the same method. The pulling force was measured using a force gauge (ZTS-100N, manufactured by Imada Co., Ltd.).

<Measurement of saturation solubility>
The saturated solubility of the resin (saturated solubility (g) in 100 g of water at 23 ° C.) was separately measured by the following method. First, a saturated aqueous solution was prepared by adding a small amount of resin to water at 23 ° C. and stirring the mixture several times. A certain amount of the saturated aqueous solution was taken, the water content and the dissolved mass were calculated from the mass before and after the water was evaporated, and the saturated solubility of the resin in water was obtained based on these values. In the column of "saturated solubility" in the table, in the example using the mixed resin, the saturated solubility of each resin is shown.

<Evaluation>
The above-mentioned laminated body with a notch was expanded, and a 3 mm square chip was taken out from this laminated body. Then, the effect was evaluated according to the following criteria by observing the peeled surface of the chip with the naked eye. If necessary, the peeled surface may be observed using a loupe or an optical microscope.
-A: It was peeled off at the adhesive interface between the support and the temporary adhesive film.
-B: It was peeled off inside the temporary adhesive film.
-C: It was peeled off at the adhesive interface between the base material and the temporary adhesive film.

<Evaluation result>
The evaluation results of each Example and Comparative Example are shown in Table 2 above. From this result, by using the laminate of the present invention, the temporary adhesive film remains on the base material side when the chip is peeled off from the support, so that the surface of the chip after the dicing treatment can be maintained while suppressing a decrease in manufacturing efficiency. It turns out that it is possible to protect.

Further, the silicon substrate of Example 1 was replaced with a silicon substrate having a semiconductor circuit formed on the surface, and a chip was produced by the same procedure as in Example 1. At this time, the surface of the silicon substrate on which the semiconductor circuit was formed was adhered to the temporary adhesive film as a surface to be protected. Then, a predetermined semiconductor process was applied to the chip with the temporary adhesive film. Then, the temporary adhesive film adhering to the chip was removed, and the chip was packaged as a semiconductor element. This semiconductor device had no problem in performance.

1 Laminated body 10 Base material 12 Temporary adhesive film 14 Support 16 Notch C chip S1 Adhesive interface between base material and temporary adhesive film S2 Adhesive interface between temporary adhesive film and support

Claims

A laminate having a base material, a temporary adhesive film, and a support in this order.
The base material and the temporary adhesive film are divided into a plurality of parts by a notch extending from the base material to the temporary adhesive film.
A laminate in which the first adhesive force between the base material and the temporary adhesive film is equal to or greater than the second adhesive force between the temporary adhesive film and the support.
The difference between the first adhesive force and the second adhesive force is 10 to 100 N / mm 2 .
The laminate according to claim 1.
The second adhesive force is 20 to 100 N / mm 2 .
The laminate according to claim 1 or 2.
The temporary adhesive film has a thickness of 10 to 100 μm.
The laminate according to any one of claims 1 to 3.
After the base material is peeled off from the support, the thickness of the temporary adhesive film on the base material is 10 to 100 μm.
The laminate according to any one of claims 1 to 4.
The temporary adhesive film contains a release layer on the surface layer portion on the support side.
The laminate according to any one of claims 1 to 5.
The support includes a release layer on the surface layer portion on the temporary adhesive film side.
The laminate according to any one of claims 1 to 5.
The release layer contains a surfactant.
The laminate according to claim 6 or 7.
The thickness of the release layer is 0.1 to 10 μm.
The laminate according to any one of claims 6 to 8.
The temporary adhesive film contains a non-curable resin.
The laminate according to any one of claims 1 to 9.
The temporary adhesive film contains a water-insoluble resin,
The laminate according to any one of claims 1 to 10.
The laminate according to any one of claims 1 to 11, wherein the temporary adhesive film contains a resin having a saturated solubility in 100 g of water at 23 ° C. of 0.9 g or less.
The temporary adhesive film contains at least one resin selected from the group consisting of polyvinyl acetal, polyalkyl methacrylate and acyl cellulose.
The laminate according to any one of claims 1 to 12.
The temporary adhesive film contains an antioxidant.
The laminate according to any one of claims 1 to 13.
The base material contains a semiconductor circuit on the surface layer portion on the temporary adhesive film side.
The support is a dicing tape,
The laminate according to any one of claims 1 to 14.
A composition for temporary adhesion used for forming the temporary adhesive film in the laminate according to any one of claims 1 to 15.
A temporary adhesive film formed on one surface of the base material and the support is adhered to the other surface of the base material and the support, and then a notch extending from the base material to the temporary adhesive film is formed. A method for manufacturing a laminated body, which includes the above-mentioned method.
A method for producing a laminate, wherein the first adhesive force between the base material and the temporary adhesive film is equal to or greater than the second adhesive force between the temporary adhesive film and the support.
Further, the step of forming the temporary adhesive film on the one surface of the base material and the support is included.
The step of forming the temporary adhesive film comprises applying the temporary adhesive composition to the surface of the base material or the support, and then drying the temporary adhesive composition.
The method for producing a laminate according to claim 17.
The method of applying the temporary bonding composition to the surface of the base material or the support is a spin coating method, a slit coating method or a spiral coating method.
The method for producing a laminate according to claim 18.
A method for manufacturing a semiconductor device, which comprises the method for manufacturing a laminate according to any one of claims 17 to 19.