JP2021006398A - Film-like firing material with support sheet, roll body, laminate, and method for manufacturing apparatus - Google Patents

Abstract

To provide a film-like firing material with a support sheet capable of stably picking up a semiconductor chip without damaging it, and a roll body including the same, and a laminate including the same, and a method for manufacturing an apparatus.SOLUTION: There is provided a film-like firing material with a support sheet 100 formed by laminating: a second support sheet 2 having a heat-shrinkable base film on a first adhesive layer 4 side of a first support sheet 6 having a first adhesive layer 4 on one surface of a non-heat-shrinkable base film 3; and the film-like firing material 1 in this order.SELECTED DRAWING: Figure 1

Description

The present invention relates to a film-like firing material with a support sheet, a roll body, a laminated body, and a method for manufacturing an apparatus.

In recent years, with the increase in voltage and current of automobiles, air conditioners, personal computers, etc., the demand for power semiconductor devices (power devices) mounted on them has been increasing. Since semiconductor devices for electric power are used under high voltage and high current, heat generation from the semiconductor devices tends to be a problem.
Conventionally, a heat sink may be attached around the semiconductor element to dissipate heat generated from the semiconductor element. However, if the thermal conductivity at the junction between the heat sink and the semiconductor element is not good, efficient heat dissipation will be hindered.

As a bonding material having excellent thermal conductivity, for example, Patent Document 1 describes paste-like metal fine particles in which specific heat-sinterable metal particles, a specific polymer dispersant, and a specific volatile dispersion medium are mixed. The composition is disclosed. It is said that when the composition is sintered, it becomes a solid metal having excellent thermal conductivity.

However, when the baking material is in the form of a paste as in Patent Document 1, it is difficult to make the thickness of the applied paste uniform, and the thickness stability tends to be poor.

Therefore, in order to solve the problem of thickness stability, the present inventors have come up with the idea of providing a baking material, which has been provided as a conventional paste-like composition, as a film. In order to make the firing material into a film, the baking material may be mixed with a binder component to form a film.

Such a film-like firing material can be used, for example, for sintering and joining a chip obtained by dicing a semiconductor wafer into individual pieces and a substrate. Further, if a support sheet is provided on one side (surface) of the film-like firing material, it can be used as a dicing sheet used when the semiconductor wafer is individualized into chips. Further, it can be processed as a film-like firing material having the same shape as the chip by individualizing it together with the semiconductor wafer using a blade or the like.

In the individualized chip with film-shaped firing material before sintering, the chip is pushed up from the back surface of the film-shaped firing material with support sheet by a push-up pin to peel off the support sheet and the chip.

Japanese Unexamined Patent Publication No. 2014-111800

On the other hand, in recent years, the thickness of semiconductor chips has been reduced, and it has become necessary to reduce the thickness of wafers, which was about 350 μm in the past, to 50 to 100 μm or less. However, as the semiconductor wafer becomes thinner, when picking up the individualized diced film-shaped firing material chip before firing, the push-up pin is applied to the film-shaped firing material with a support sheet before sintering. There is a risk of deformation such as damage to the chip or leaving pin marks.

The present invention is intended to solve the above problems, and is a film-shaped firing material and a roll with a support sheet that can pick up a chip with a film-shaped firing material without using a push-up pin when picking up a chip with a film-shaped firing material. It is an object of the present invention to provide a method for manufacturing a body, a laminate, and an apparatus.

The present invention has the following aspects.
[1] A second having a heat-shrinkable base film on the first pressure-sensitive adhesive layer side of the first support sheet having the first pressure-sensitive adhesive layer on one surface of the non-heat-shrinkable base film. A film-like firing material with a support sheet in which a support sheet and a film-like firing material are laminated in this order.
[2] The film-like firing material is laminated on the second pressure-sensitive adhesive layer side of the second support sheet, wherein the second support sheet is provided with a second pressure-sensitive adhesive layer. Film-like firing material with support sheet.
[3] The film-like firing material with a support sheet according to [2], wherein the second pressure-sensitive adhesive layer is energy ray-curable.
[4] The film-like firing with a support sheet according to [3], wherein the second pressure-sensitive adhesive layer contains a pressure-sensitive adhesive resin, and the pressure-sensitive adhesive resin has an energy ray-polymerizable unsaturated group in its side chain. material.
[5] The film-like firing material with a support sheet according to any one of [1] to [4], wherein the first pressure-sensitive adhesive layer is non-energy ray-curable.
[6] The diameter of the first support sheet is the same as the diameter of the second support sheet, or larger than the diameter of the second support sheet, and the diameter of the second support sheet is in the form of a film. The film-shaped firing material with a support sheet according to any one of [1] to [5], which has the same diameter as the firing material or is larger than the diameter of the film-shaped firing material.
[7] The support sheet according to any one of [1] to [6], wherein the heat-shrinkable base film comprises at least one selected from the group consisting of stretched polyethylene, stretched polypropylene, and stretched polyethylene terephthalate. Attached film-like firing material.
[8] The film-like firing material with a support sheet according to any one of [1] to [7] is laminated on the long release film with the film-shaped firing material inside.
A roll body in which the release film and the film-like firing material with a support sheet are rolled.
[9] The film-like firing material with a support sheet according to any one of [1] to [7] and the wafer are attached, and the first support sheet, the second support sheet, and the film-like form are attached. A laminate in which a firing material and the wafer are laminated in this order.
[10] The laminate according to [9], wherein the diameter of the film-like fired material is the same as the diameter of the wafer or larger than the diameter of the wafer.
[11] A method for manufacturing an apparatus in which the following steps (1) to (5) are sequentially performed:
Step (1): A step of dicing the wafer and the film-like baking material of the laminate according to [9] or [10].
Step (2): A step of heating the diced film-like firing material and shrinking the second support sheet.
Step (3): A step of peeling the diced film-shaped firing material and the second support sheet to obtain a chip with a film-shaped firing material.
Step (4): A step of attaching the film-shaped firing material of the chip with the film-shaped firing material to the surface of the substrate.
Step (5): A step of firing the film-shaped firing material of the chip with the film-shaped firing material and joining the chip and the substrate.

According to the present invention, it is possible to provide a film-shaped firing material with a support sheet that can stably pick up a chip with a film-shaped firing material that has been diced without damaging it.

It is sectional drawing which shows typically the film-like firing material with a support sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the state in which the film-like firing material with a support sheet is attached to the ring frame which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the state in which the film-like firing material with a support sheet is attached to the ring frame which concerns on one Embodiment of this invention. It is a perspective view which shows typically the state which the film-like firing material with a support sheet is attached to the ring frame which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the roll body which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the laminated body which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the manufacturing method of the apparatus which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the manufacturing method of the apparatus which concerns on one Embodiment of this invention.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings as appropriate.
In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

≪Film-like firing material with support sheet≫
The film-like fired material with a support sheet of the present embodiment has a first support sheet having a first pressure-sensitive adhesive layer on one surface of the non-heat-shrinkable base film, on the side of the first pressure-sensitive adhesive layer. A second support sheet having a heat-shrinkable base film and a film-like firing material with a support sheet in which film-like firing materials are laminated in this order.

FIG. 1 is a cross-sectional view schematically showing a film-shaped fired material with a support sheet according to the present embodiment.
The film-like fired material 100 with a support sheet is provided on the side of the first pressure-sensitive adhesive layer 4 of the first support sheet 6 having the first pressure-sensitive adhesive layer 4 on one surface of the non-heat-shrinkable base film 3. A second support sheet 2 having a heat-shrinkable base film and a film-like firing material 1 containing the sinterable metal particles 10 and the binder component 20 are laminated in this order. It is preferable that the second support sheet 2 includes a second pressure-sensitive adhesive layer, and the film-like firing material is laminated on the second pressure-sensitive adhesive layer side of the second support sheet. The film-like fired material may be provided in direct contact with the second pressure-sensitive adhesive layer, or may be provided in direct contact with the heat-shrinkable base film. The film-like firing material with a support sheet of the present embodiment can be used as a dicing sheet used when the semiconductor wafer is individualized into chips. Moreover, it can be processed as a film-like firing material having the same shape as the chip by individualizing it together with the semiconductor wafer using a blade or the like, and a chip with a film-like firing material can be manufactured.

Hereinafter, an embodiment of a film-like fired material with a support sheet will be described. 2 and 3 show schematic cross-sectional views of the film-shaped fired material with a support sheet according to the present embodiment. As shown in FIGS. 2 and 3, the film-shaped firing materials 100a and 100b with a support sheet of the present embodiment have the film-shaped firing material 1 on the inner peripheral portion of the second support sheet 2 having an adhesive portion on the outer peripheral portion. Is temporarily attached so that it can be peeled off. As shown in FIG. 2, the second support sheet 2 is an adhesive sheet having a second pressure-sensitive adhesive layer 8 on the upper surface of the heat-shrinkable base film 7, and is an inner circumference of the second pressure-sensitive adhesive layer 8. The surface of the portion is covered with the film-like firing material 1, and the adhesive portion is exposed on the outer peripheral portion. In this configuration example, the film-like fired material 1 having a diameter smaller than that of the second support sheet 2 is concentrically and concentrically laminated on the second adhesive layer 8 of the second support sheet 2 so as to be peelable. preferable. Further, as shown in FIG. 3, the second support sheet 2 may have a ring-shaped second pressure-sensitive adhesive layer 8 on the outer peripheral portion of the heat-shrinkable base film 7. In the configuration example shown in FIG. 3, a ring-shaped second pressure-sensitive adhesive layer 8 is formed on the outer peripheral portion of the heat-shrinkable base film 7 to form a pressure-sensitive adhesive portion.

The film-shaped fired material 1 is preferably formed on the inner peripheral portion of the second support sheet 2 in substantially the same shape as the work (wafer or the like) to be attached.

Examples of the wafer or chip include a semiconductor wafer or a semiconductor chip, an insulator wafer or an insulator chip, a conductor wafer or a conductor chip, and the like. Examples of the insulator wafer include, but are not limited to, glass wafers and sapphire wafers. In the embodiment, a case where a semiconductor wafer or a semiconductor chip is used as the wafer or the chip will be described.

The outer peripheral portion of the second support sheet 2 has an adhesive portion. In a preferred embodiment, the film-shaped fired material 1 having a diameter smaller than that of the second support sheet 2 is concentrically laminated on the circular second support sheet 2. The adhesive portion on the outer peripheral portion is used for fixing the ring frame 5 as shown in the figure.
The film-like firing material 100a with a support sheet having the above configuration is attached to the ring frame 5 in the second pressure-sensitive adhesive layer 8 exposed on the outer peripheral portion of the second support sheet 2.

Further, an annular double-sided tape or an adhesive layer may be separately provided on the glue margin (exposed second adhesive layer on the outer peripheral portion of the adhesive sheet) for the ring frame. The double-sided tape has a structure of an adhesive layer / core material / adhesive layer, and the adhesive layer in the double-sided tape is not particularly limited, and for example, an adhesive such as rubber, acrylic, silicone, or polyvinyl ether is used. .. The pressure-sensitive adhesive layer is attached to the ring frame at the outer peripheral portion thereof when the substrate with a chip described later is manufactured. As the core material of the double-sided tape, for example, a polyester film, a polypropylene film, a polycarbonate film, a polyimide film, a fluororesin film, a liquid crystal polymer film and the like are preferably used.

FIG. 4 shows a perspective view of the film-shaped fired material 100b with a support sheet shown in FIG. At this time, the second pressure-sensitive adhesive layer 8 may be a single-layer pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive, or is a double-sided pressure-sensitive adhesive tape containing the pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive cut in a ring shape. May be good. The film-like fired material 1 is releasably laminated on the inner peripheral portion of the heat-shrinkable base film 7 surrounded by the adhesive portion. In this configuration example, the film-like fired material 1 having a diameter smaller than that of the second support sheet 2 is concentrically and concentrically laminated on the heat-shrinkable base film 7 of the second support sheet 2. preferable.

The film-shaped fired material with a support sheet of the present embodiment is provided with surface protection on the surface of either or both of the film-shaped fired material and the adhesive portion until it is used, in order to avoid contact with the outside. A release film may be provided for the purpose.

The surface protective film (release film) can be obtained by subjecting the surface of a base film such as polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polypropylene mentioned above to the above-mentioned release treatment using a release agent. You can also do it. Examples of the release agent used in the release treatment include the release agents exemplified above in the description of the base film.

The thickness of the film-like fired material with a support sheet is preferably 1 to 500 μm, more preferably 5 to 300 μm, and even more preferably 10 to 200 μm.

(Film-like firing material)
As shown in FIG. 1, the film-shaped firing material 1 contains the sinterable metal particles 10 and the binder component 20.

The film-like firing material may be composed of one layer (single layer) or may be composed of two or more layers. When the film-like firing material is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
In the present specification, not only in the case of the film-like fired material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers". May be different, and only some of the layers may be the same. ”Furthermore,“ a plurality of layers are different from each other ”means“ the constituent materials of each layer, the compounding ratio of the constituent materials, and the thickness. At least one of them is different from each other. "

The thickness of the film-like firing material before firing is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 150 μm, and even more preferably 30 to 90 μm. Here, the "thickness of the film-shaped firing material" means the thickness of the entire film-shaped firing material, and for example, the thickness of the film-shaped firing material composed of a plurality of layers is all that constitute the film-shaped firing material. Means the total thickness of the layers of.

In the present specification, the "thickness" can be obtained by using a constant pressure thickness measuring device according to JIS K7130 as a value represented by the average of the thickness measured at any five points.

(Release film)
The film-like firing material can be provided in a state in which release films are laminated. When used, the release film may be peeled off and the film-like fired material may be placed on an object to be sintered and bonded. The release film also has a function as a protective film for preventing damage and dirt adhesion of the film-like fired material. The release film may be provided on at least one side of the film-like firing material.

Examples of the release film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, and polyurethane. Film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin A transparent film such as a film is used. These crosslinked films are also used. Further, these laminated films may be used. Further, a film colored by these, an opaque film, or the like can be used. Examples of the release agent include silicone-based, fluorine-based, olefin-based, alkyd-based, and long-chain alkyl group-containing carbamate-based release agents.

The thickness of the release film is usually 10 to 500 μm, preferably 15 to 300 μm, and particularly preferably about 20 to 250 μm.

<Sinterable metal particles>
Sinterable metal particles are metal particles capable of forming a sintered body by melting and bonding with each other by heat treatment at a temperature equal to or higher than the melting point of the metal particles as firing of a film-like firing material. By forming the sintered body, it is possible to sinter-bond the film-shaped fired material and the article fired in contact with the film-shaped fired material. Specifically, the chip and the substrate can be sintered and joined via a film-like firing material.

Examples of the metal species of the sinterable metal particles include silver, gold, copper, iron, nickel, aluminum, silicon, palladium, platinum, titanium, barium titanate, oxides or alloys thereof, and silver and silver oxide. Is preferable. Only one type of sinterable metal particles may be blended, or a combination of two or more kinds may be blended.

The sinterable metal particles are preferably silver nanoparticles, which are nano-sized silver particles.

The particle size of the sinterable metal particles contained in the film-like firing material is not particularly limited as long as it can exhibit the above-mentioned sinterability, but may be 100 nm or less, and may be 50 nm or less. It may be 30 nm or less. The particle size of the metal particles contained in the film-shaped firing material is the diameter equivalent to the projected area circle of the particle size of the metal particles observed with an electron microscope. Metal particles belonging to the above particle size range are preferable because they are excellent in sinterability.
The particle size of the sintered metal particles contained in the film-like firing material is the number average of the particle sizes of the metal particles observed with an electron microscope, which are obtained for particles having a projected area circle equivalent diameter of 100 nm or less. , 0.1-95 nm, 0.3-50 nm, 0.5-30 nm. The number of metal particles to be measured is 100 or more randomly selected per film-like firing material.

Sinterable metal particles are pre-dispersed in a high boiling point solvent such as isobornyl cyclohexanol or decyl alcohol in order to make them agglomerate-free before mixing with the binder component and other additive components. You may let me. The boiling point of the high boiling point solvent may be, for example, 200 to 350 ° C. At this time, if a high boiling point solvent is used, it hardly volatilizes at room temperature, so that the concentration of the sinterable metal particles is prevented from increasing, the workability is improved, and the sinterable metal particles are used. Reaggregation is also prevented and the quality is good. Examples of the dispersion method include a kneader, a triple roll, a bead mill, and ultrasonic waves.

In addition to metal particles having a particle diameter of 100 nm or less (sinterable metal particles), non-sinterable metal particles having a particle diameter of more than 100 nm, which does not correspond to the metal particles (sinterable metal particles), may be further blended in the film-like firing material. The particle size of non-sinterable metal particles having a particle size of more than 100 nm is the number of particle sizes obtained for particles having a projected area circle equivalent diameter of more than 100 nm, which is the particle size of metal particles observed with an electron microscope. The average may be more than 150 nm and less than 50,000 nm, may be 150 to 10,000 nm, and may be 180 to 5000 nm.

Examples of the metal species of the non-sinterable metal particles having a particle diameter of more than 100 nm include the same as those exemplified as the metal species of the above-mentioned sintered metal particles, and silver, copper, and oxides thereof are preferable. ..
The metal particles having a particle diameter of 100 nm or less and the non-sinterable metal particles having a particle diameter of more than 100 nm may be the same metal species or different metal species from each other. For example, metal particles having a particle diameter of 100 nm or less may be silver particles, and non-sinterable metal particles having a particle diameter of more than 100 nm may be silver or silver oxide particles. For example, metal particles having a particle diameter of 100 nm or less may be silver or silver oxide particles, and non-sinterable metal particles having a particle diameter of more than 100 nm may be copper or copper oxide particles.

In the film-like fired material, the content of the sintered metal particles with respect to the total mass (100% by mass) of all the metal particles may be 10 to 100% by mass or 20 to 95% by mass. Good.

The surface of the sinterable metal particles and / or the non-sinterable metal particles may be coated with an organic substance. By having the coating of the organic substance, the compatibility with the binder component is improved, the agglomeration of the particles can be prevented, and the particles can be uniformly dispersed.
When the surface of the sinterable metal particles and / or the non-sinterable metal particles is coated with an organic substance, the masses of the sinterable metal particles and the non-sinterable metal particles are the values including the coating. To do.

<Binder component>
By blending the binder component, the firing material can be molded into a film shape, and the film-shaped firing material before firing can be imparted with adhesiveness. The binder component may be thermally decomposable, which is thermally decomposed by being heat-treated as the firing of the film-shaped firing material.
The binder component is not particularly limited, but a resin can be mentioned as a preferable example of the binder component. Examples of the resin include acrylic resins, polycarbonate resins, polylactic acids, polymers of cellulose derivatives, and the like, and acrylic resins are preferable. Acrylic resins include homopolymers of (meth) acrylate compounds, two or more copolymers of (meth) acrylate compounds, and copolymers of (meth) acrylate compounds and other copolymerizable monomers. included.

In addition, in this specification, a "derivative" means a compound in which one or more hydrogen atoms of the original compound are substituted with a group (substituent) other than the hydrogen atom.

In the resin constituting the binder component, the content of the structural unit derived from the (meth) acrylate compound is preferably 50 to 100% by mass, preferably 80 to 100% by mass, based on the total mass (100% by mass) of the structural unit. It is more preferably by mass%, and even more preferably 90 to 100% by mass.
The term "origin" as used herein means that the monomer has undergone a structural change necessary for polymerization.

Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl. (Meta) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meta) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Alkyl (meth) acrylates such as acrylates and isostearyl (meth) acrylates;
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates;
Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate. ) Acrylate;
Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene Polyalkylene glycol (meth) acrylates such as glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, Bornyl (meth) acrylate, Isobornyl ( Cycloalkyl (meth) acrylates such as meta) acrylates and tricyclodecanyl (meth) acrylates;
Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like can be mentioned. Alkyl (meth) acrylate or alkoxyalkyl (meth) acrylate is preferable, and particularly preferable (meth) acrylate compound is butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-. Ethylhexyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate can be mentioned.

As used herein, the term "(meth) acrylate" is a concept that includes both "acrylate" and "methacrylate".
As the acrylic resin, methacrylate is preferable. Since the binder component contains a structural unit derived from methacrylate, it can be fired at a relatively low temperature, and the conditions for obtaining sufficient adhesive strength after sintering can be easily satisfied.

In the resin constituting the binder component, the content of the composition unit derived from methacrylate is preferably 50 to 100% by mass, preferably 80 to 100% by mass, based on the total mass (100% by mass) of the composition unit. More preferably, it is more preferably 90 to 100% by mass.

The other copolymerizable monomer is not particularly limited as long as it is a compound copolymerizable with the above (meth) acrylate compound, but for example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, vinyl phthalic acid and the like. Unsaturated carboxylic acids; vinyl group-containing radically polymerizable compounds such as vinylbenzylmethyl ether, vinylglycidyl ether, styrene, α-methylstyrene, butadiene, and isoprene can be mentioned.

The mass average molecular weight (Mw) of the resin constituting the binder component is preferably 1,000 to 1,000,000, and more preferably 10,000 to 800,000. When the mass average molecular weight of the resin is within the above range, it becomes easy to develop sufficient film strength as a film and impart flexibility.
In the present specification, the "mass average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the resin constituting the binder component can be obtained by calculation using the Fox formula shown below, which is preferably -60 to 50 ° C, preferably -30 to 10 ° C. More preferably, it is more preferably −20 ° C. or higher and lower than 0 ° C. When the Tg of the resin obtained from the Fox formula is not more than the above upper limit value, the adhesive strength between the film-like firing material and the adherend (for example, chip, substrate, etc.) before firing is improved. In addition, the flexibility of the film-like firing material is increased. On the other hand, when the Tg of the resin obtained from the Fox formula is at least the above lower limit value, the film shape can be maintained, and the film-like fired material can be more easily separated from the support sheet or the like.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... + (Wm / Tgm) (In the formula, Tg is the glass transition temperature of the resin constituting the binder component, and Tg1, Tg2, ... Tgm are the binders. It is the glass transition temperature of the homopolymer of each monomer which is a raw material of the resin constituting the component, and W1, W2, ... Wm is the mass fraction of each monomer. However, W1 + W2 + ... + Wm = 1. .)
For the glass transition temperature of the homopolymer of each monomer in the Fox formula, the values described in the Polymer Data Handbook or the Adhesive Handbook can be used.

The binder component may be thermally decomposable, which is thermally decomposed by heat treatment as the firing of the film-shaped firing material. The fact that the binder component was thermally decomposed can be confirmed by the mass reduction of the binder component due to firing. The component blended as the binder component may be substantially thermally decomposed by firing, but the total mass of the component blended as the binder component may not be thermally decomposed by firing.
The binder component may have a mass of 10% by mass or less after firing with respect to the total mass (100% by mass) of the binder component before firing, and may be 5% by mass or less. It may be mass% or less.

In addition to the above-mentioned sinterable metal particles, non-sinterable metal particles and binder components, the film-like fired material includes sinterable metal particles and non-sinterable metal particles as long as the effects of the present invention are not impaired. It may contain metal particles and other additives that do not correspond to the binder component.

Other additives that may be contained in the film-like baking material include solvents, dispersants, plasticizers, tackifiers, storage stabilizers, defoamers, pyrolysis accelerators, antioxidants and the like. .. Only one kind of additive may be contained, or two or more kinds of additives may be contained. These additives are not particularly limited, and those usually used in this field can be appropriately selected.

Since the binder component is preferably thermally decomposed by being heat-treated as the firing of the film-like firing material, the content of the thermosetting resin such as epoxy resin is 10% by mass or less with respect to 100% by mass of the binder component. It is more preferable that the content is 5% by mass or less, and it is further preferable that the thermosetting resin is substantially not contained.
From the same viewpoint, in the resin constituting the binder component, the content of the acrylate-derived structural unit among "acrylate" and "methacrylate" is 10 with respect to the total mass (100% by mass) of the structural unit. It is preferably 5% by mass or less, more preferably 5% by mass or less, and further preferably substantially free of acrylate-derived structural units.

<Composition>
The film-like firing material may be composed of sinterable metal particles, a binder component, and other additives, and the sum of these contents (% by mass) may be 100% by mass. When the film-like calcined material contains non-sinterable metal particles, the film-like calcined material comprises sinterable metal particles, non-sinterable metal particles, a binder component, and other additives. The sum of these contents (% by mass) may be 100% by mass.

In the film-like fired material, the content of the sintered metal particles is preferably 15 to 98% by mass with respect to the total mass (100% by mass) of all the components other than the solvent (hereinafter referred to as "solid content"). It is more preferably 15 to 90% by mass, further preferably 20 to 80% by mass. When the content of the sinterable metal particles is not more than the above upper limit value, the content of the binder component can be sufficiently secured, so that the film shape can be easily maintained. On the other hand, when the content of the sintered metal particles is equal to or higher than the above lower limit, the sintered metal particles or the sintered metal particles and the non-sinterable metal particles are fused to each other during firing and fired. It is also possible to obtain the effect of developing high bonding adhesive strength (shearing adhesive force) later.

When the film-like fired material contains non-sinterable metal particles, the total content of the sintered metal particles and the non-sinterable metal particles with respect to the total mass (100% by mass) of the solid content in the film-like fired material. Is preferably 50 to 98% by mass, more preferably 70 to 95% by mass, and even more preferably 80 to 95% by mass.

The content of the binder component with respect to the total mass (100% by mass) of the solid content in the film-like fired material is preferably 2 to 50% by mass, more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass. When the content of the binder component is not more than the above upper limit value, the content of the sinterable metal particles can be sufficiently secured, so that the bonding adhesive force between the film-like fired material and the adherend is further improved. On the other hand, when the content of the binder component is at least the above lower limit value, it becomes easy to maintain the film shape.

In the film-like fired material, the mass ratio of the sinterable metal particles to the binder component (sinterable metal particles: binder component) is preferably 50: 1 to 1: 5, and more preferably 20: 1 to 1: 2. 10: 1 to 1: 1 is more preferable. When the film-like fired material contains non-sinterable metal particles, the mass ratio of the sinterable metal particles and the non-sinterable metal particles to the binder component ((sinterable metal particles + non-sinterable metal particles + non-sinterable) (Metal particles): Binder component) is preferably 50: 1 to 1: 1, more preferably 20: 1 to 2: 1, and even more preferably 9: 1 to 4: 1.

The film-like firing material may contain a high boiling point solvent used for mixing sinterable metal particles, non-sinterable metal particles, a binder component and other additive components. The content of the high boiling point solvent with respect to the total mass (100% by mass) of the film-like baking material is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[Manufacturing method of film-like firing material]
The film-like firing material can be formed by using a firing material composition containing the constituent material. For example, a firing material composition containing each component and a solvent for forming a film-shaped firing material is applied or printed on a surface to be formed of the film-shaped firing material, and the solvent is volatilized as necessary. A film-like firing material can be formed at the site to be used.
An example of the surface to be formed of the film-like fired material is the surface of a release film.

When coating the calcined material composition, the solvent preferably has a boiling point of less than 200 ° C., for example, n-hexane (boiling point: 68 ° C.), ethyl acetate (boiling point: 77 ° C.), 2-butanone (boiling point: 80 ° C.). ℃), n-heptane (boiling point: 98 ℃), methylcyclohexane (boiling point: 101 ℃), toluene (boiling point: 111 ℃), acetylacetone (boiling point: 138 ℃), n-xylene (boiling point: 139 ℃) and dimethylformamide. (Boiling point: 153 ° C.) and the like. These may be used alone or in combination.

The coating of the fired material composition may be carried out by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a comma coater (registered trademark), a roll coater, a roll knife coater, a curtain coater, and a die coater. , A method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

When printing the calcined material composition, the solvent may be any solvent that can be volatilized and dried after printing, and the boiling point is preferably 65 to 350 ° C. Examples of such a solvent include the above-exemplified solvents having a boiling point of less than 200 ° C., isophorone (boiling point: 215 ° C.), butyl carbitol (boiling point: 230 ° C.), 1-decanol (boiling point: 233 ° C.), and butyl carbi. Examples thereof include tall acetate (boiling point: 247 ° C.) and isobornylcyclohexanol (boiling point: 318 ° C.).
If the boiling point exceeds 350 ° C, the solvent is less likely to volatilize during volatilization and drying after printing, making it difficult to secure the desired shape, or the solvent remains in the film during firing, resulting in bond adhesion. May deteriorate. If the boiling point is lower than 65 ° C., it may volatilize during printing and the thickness stability may be impaired. If a solvent having a boiling point of 200 to 350 ° C. is used, it is possible to suppress an increase in viscosity due to volatilization of the solvent during printing, and printability can be obtained.

Printing of the fired material composition can be performed by a known printing method, for example, letterpress printing such as flexo printing, concave printing such as gravure printing, flat plate printing such as offset printing, silk screen printing, rotary screen printing and the like. Examples include screen printing and printing with various printers such as inkjet printers.

The shape of the film-shaped fired material may be appropriately set according to the shape of the object to be sintered and joined, and is preferably circular or rectangular. The circular shape corresponds to the shape of the semiconductor wafer. The rectangle is a shape corresponding to the shape of the chip. The corresponding shape may be the same shape as or substantially the same shape as the shape to be sintered and joined.
When the film-shaped firing material is circular, the area of the circle may be 3.5～1,600Cm ^2, may be 85~1,400cm ^2. When the film-shaped firing material is rectangular, rectangular area may be a 0.01～25Cm ^2, may be 0.25~9cm ^2. In particular, if the firing material composition is printed, it is easy to form a film-shaped firing material having a desired shape.

The drying conditions of the calcined material composition are not particularly limited, but when the calcined material composition contains a solvent, it is preferably heat-dried, in this case, for example, at 70 to 250 ° C., for example, 80 to 180 ° C. It is preferable to dry under the condition of 10 seconds to 10 minutes.

(First support sheet)
<Non-heat shrinkable base film>
In the film-like fired material with a support sheet of the present embodiment, the first support sheet 6 has a non-heat shrinkable base film 3.
The non-heat shrinkable base film is usually a film having a heat shrinkage rate of less than 10%. Here, the heat shrinkage rate is calculated based on the dimensions before and after heating the film to 110 ° C., and is calculated based on the following mathematical formula from the dimensions before heat shrinkage and the dimensions after heat shrinkage.

The non-heat shrinkable base film 3 is not particularly limited as long as it is a film having a heat shrinkage rate of less than 10%, and is, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / propylene. Copolymer, polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) A film made of ethyl acrylate copolymer, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, polyurethane film, ionomer or the like is used. In addition, in this specification, "(meth) acrylic" is used in the meaning including both acrylic and methacrylic.
When higher heat resistance is required for the first support sheet 6, the non-heat shrinkable base film 3 includes polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polypropylene, and poly. Examples thereof include a polyolefin film such as methylpentene. Further, these crosslinked films and modified films by radiation / discharge can also be used. The non-heat shrinkable base film may be a laminate of the above films.

In addition, these films may be used by laminating or combining two or more types. Further, colored films, printed films, and the like can also be used. Further, the film may be a sheet obtained by extrusion-forming a thermoplastic resin or may be stretched, and a film obtained by thinning and curing a curable resin by a predetermined means to form a sheet is used. You may be broken.

The thickness of the non-heat shrinkable base film is not particularly limited, and is preferably 30 to 300 μm, more preferably 50 to 200 μm. By setting the thickness of the non-heat-shrinkable base film within the above range, tearing of the non-heat-shrinkable base film is unlikely to occur even if cutting is performed by dicing. Further, since the film-like fired material with a support sheet is imparted with sufficient flexibility, it exhibits good adhesiveness to a work (for example, a semiconductor wafer).

The non-heat shrinkable base film can also be obtained by applying a release agent to the surface and performing a release treatment. Alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, wax-based, etc. are used as the release agent used in the peeling treatment, but alkyd-based, silicone-based, and fluorine-based release agents are particularly heat-resistant. It is preferable because it has.

In order to peel off the surface of the non-heat shrinkable base film using the above release agent, the release agent is used as it is without solvent, or after being diluted or emulsionized, a gravure coater, a Mayer bar coater, or an air knife coater. , A non-heat shrinkable base film coated with a release agent by applying with a roll coater, etc., is subjected to normal temperature or heating, or cured by an electron beam, wet lamination, dry lamination, heat melting lamination, etc. A laminate may be formed by melt extrusion lamination, coextrusion processing, or the like.

(First adhesive layer)
The first pressure-sensitive adhesive layer 4 is in the form of a sheet or a film, and can contain a pressure-sensitive adhesive. The first pressure-sensitive adhesive layer may be energy ray-curable or non-energy ray-curable, but non-energy ray-curable is preferable.

In the present specification, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. To do.

As shown in FIG. 2, the first support sheet 6 has a first pressure-sensitive adhesive layer 4 on the entire upper surface of the non-heat-shrinkable base film 3. In the support sheet having the configuration of FIG. 2, in order to strengthen the adhesion between the non-heat shrinkable base film 3 and the first pressure-sensitive adhesive layer 4, the first pressure-sensitive adhesive layer 4 of the non-heat-shrinkable base film 3 is used. If desired, the surface to be provided may be roughened by sandblasting or solvent treatment, or oxidized by corona discharge treatment, electron beam irradiation, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromium acid treatment, hot air treatment, etc. It can be processed. In addition, primer treatment can be applied.

The thickness of the first pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, and particularly preferably 3 to 50 μm.

The first pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. When the first pressure-sensitive adhesive layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

<Adhesive composition>
The first pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target portion by applying the pressure-sensitive adhesive composition to the surface to be formed of the first pressure-sensitive adhesive layer and drying it if necessary. A more specific method for forming the first pressure-sensitive adhesive layer will be described in detail later together with a method for forming the other layers. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the first pressure-sensitive adhesive layer.

The pressure-sensitive adhesive composition may be applied by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. , A method using various coaters such as a Meyer bar coater and a kiss coater.

The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferably heat-dried. The solvent-containing pressure-sensitive adhesive composition is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes, for example.

When the first pressure-sensitive adhesive layer 4 is non-energy ray-curable, the non-energy ray-curable pressure-sensitive adhesive composition includes, for example, a pressure-sensitive adhesive composition (I-) containing a pressure-sensitive adhesive resin (I-1a). 4) and the like.

In the present specification, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, and for example, not only the resin itself having adhesiveness but also the resin itself has adhesiveness. Also included are resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water.

The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having a structural unit derived from at least an alkyl (meth) acrylate.
The structural unit of the acrylic resin may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the adhesive resin constituting the first pressure-sensitive adhesive layer, the content of the structural unit derived from the (meth) acrylate compound shall be 50 to 100% by mass with respect to the total mass (100% by mass) of the structural unit. Is more preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is further preferable.
The term "origin" as used herein means that the monomer has undergone a structural change necessary for polymerization.

Specific examples of the (meth) acrylate compound include those exemplified in the above binder component.

The adhesive strength of the adhesive resin strengthens the adhesion between the non-heat-shrinkable base film 3 and the first pressure-sensitive adhesive layer 4, and makes it possible to stably pick up the diced chips with a film-like firing material. The adhesive strength to the SUS plate at 23 ° C. is preferably 5 N / 25 mm or more.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group may be a starting point of cross-linking by reacting with a cross-linking agent described later, or the functional group may react with an unsaturated group in an unsaturated group-containing compound described later. Then, there is one that enables the introduction of an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohols (ie, unsaturated alcohols having no (meth) acryloyl skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (that is, monocarboxylic acids having ethylenically unsaturated bonds); fumaric acid, itaconic acid, and maleic acid. , Citraconic acid and other ethylenically unsaturated dicarboxylic acids (ie, dicarboxylic acids with ethylenically unsaturated bonds); the anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate. Examples include esters.

The functional group-containing monomer constituting the acrylic polymer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, based on the total amount of the structural units. It is particularly preferably 3 to 30% by mass.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-4) is preferably 5 to 99% by mass. , 10-95% by mass is more preferable, and 15-90% by mass is particularly preferable.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-4) is preferably 5 to 99% by mass. , 10-95% by mass is more preferable, and 15-90% by mass is particularly preferable.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive resin (I-1a) to the total content of all the components other than the solvent (that is, the first pressure-sensitive adhesive in the first pressure-sensitive adhesive layer). The ratio of the content of the adhesive resin (I-1a) to the total mass of the agent layer) is preferably 50 to 100% by mass, and may be, for example, 65 to 99% by mass, 80 to 98%. It may be% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a) in addition to the structural unit derived from alkyl (meth) acrylate, the pressure-sensitive adhesive composition (I-) is used. 4) preferably further contains a cross-linking agent.

The cross-linking agent, for example, reacts with the functional group to cross-link the adhesive resins (I-1a) with each other.
Examples of the cross-linking agent include tolylene diisocyanate (TDI) -based, hexamethylene diisocyanate (HDI) -based, xylylene diisocyanate (XDI) -based, and isocyanate-based cross-linking agents such as adducts of these diisocyanates (that is, cross-linking having an isocyanate group). Agent); Organic polyisocyanate-based cross-linking agent, epoxy-based cross-linking agent such as ethylene glycol glycidyl ether (that is, cross-linking agent having a glycidyl group); hexa [1- (2-methyl) -aziridinyl] triphosphatriazine and the like Aziridine-based cross-linking agent (that is, a cross-linking agent having an aziridinyl group); a metal chelate-based cross-linking agent such as an aluminum chelate (that is, a cross-linking agent having a metal chelate structure); Agent) and the like.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive force of the pressure-sensitive adhesive layer and being easily available.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane- 4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; tri Compounds in which any one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxyl groups of a polyol such as methylolpropane; lysine diisocyanate and the like can be mentioned.

The cross-linking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antioxidants, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).
The reaction retarder means, for example, that an unintended cross-linking reaction occurs in the pressure-sensitive adhesive composition (I-4) being stored due to the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-4). It suppresses the progress. Examples of the reaction retarder include those that form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

The other additives contained in the pressure-sensitive adhesive composition (I-4) may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof can be arbitrarily selected.

When other additives are used, the content of the other additives in the pressure-sensitive adhesive composition (I-4) is not particularly limited and may be appropriately selected depending on the type thereof.

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent. Since the pressure-sensitive adhesive composition (I-4) contains a solvent, the suitability for coating on the surface to be coated is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (for example, carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane and n-. Examples thereof include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

As the solvent, for example, the one used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-4) without being removed from the adhesive resin (I-1a). However, the same or different type of solvent as that used in the production of the pressure-sensitive adhesive resin (I-1a) may be added separately during the production of the pressure-sensitive adhesive composition (I-4).

The solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When a solvent is used, the content of the solvent in the pressure-sensitive adhesive composition (I-4) is not particularly limited and may be appropriately adjusted.

[Manufacturing method of adhesive composition]
The pressure-sensitive adhesive composition can be obtained by blending the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition, such as components other than the pressure-sensitive adhesive.
The order of addition of each component at the time of blending is not particularly limited, and two or more components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

(Second support sheet)
<Heat shrinkable base film>
In the film-like fired material with a support sheet of the present embodiment, the second support sheet 2 has a heat-shrinkable base film 7.

The shrinkage rate of the heat-shrinkable base film is preferably 10 to 90%, more preferably 20 to 80%. Here, the shrinkage rate is calculated based on the above mathematical formula.

Various heat-shrinkable base films as described above have been conventionally known, but in the present invention, any film that does not generally have an adverse effect such as ion contamination on the object to be cut is used. Can be used. Specifically, biaxially stretched films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, nylon, urethane, polyvinylidene chloride, and polyvinyl chloride can be exemplified.

The thickness of the heat-shrinkable base film as described above is preferably 5 to 300 μm, more preferably 10 to 200 μm.

As the heat-shrinkable base film, a stretched film such as a uniaxially stretched film or a biaxially stretched film can be used, but from the viewpoint of peelability, a biaxially stretched film is preferably used. Examples of the biaxially stretched film include stretched polyethylene, stretched polypropylene, stretched polyethylene terephthalate, and the like.

The base material of the heat-shrinkable base film may be one made of the above-mentioned heat-shrinkable film single layer, or may be a base material made of a plurality of layers. That is, it may be a combination of one or more types of heat-shrinkable base film, or a combination of the heat-shrinkable base film and the non-heat-shrinkable base film. Good.

The difference between the heat-shrinkable base film and the non-heat-shrinkable base film used in the present invention is that the shrinkage rate is different. For example, when producing a polyethylene film, it is possible to produce two types of polyethylene films having different shrinkage rates by appropriately setting the production conditions and the like.

<Second adhesive layer>
The second pressure-sensitive adhesive layer 8 is in the form of a sheet or a film, and can contain a pressure-sensitive adhesive.
The second support sheet 2 has an adhesive portion at least on the outer peripheral portion thereof. The adhesive portion has a function of temporarily fixing the ring frame 5 on the outer peripheral portion of the film-shaped fired material 100a with a support sheet, and it is preferable that the ring frame 5 can be peeled off after a required step. Therefore, as the second pressure-sensitive adhesive layer 8, a weakly adhesive one may be used, or an energy ray-curable one whose adhesive strength is reduced by energy ray irradiation may be used. The second pressure-sensitive adhesive layer may be energy ray-curable or non-energy ray-curable.

As shown in FIG. 2, the second support sheet 2 has a second pressure-sensitive adhesive layer 8 on the entire upper surface of the heat-shrinkable base film 7. As the second pressure-sensitive adhesive layer 8, a weak adhesive layer may be used or an energy ray-curable pressure-sensitive adhesive may be used as described above.

As the weakly adhesive pressure-sensitive adhesive, acrylic-based and silicone-based adhesives are preferably used.

In the support sheet having the configuration shown in FIG. 2, a second pressure-sensitive adhesive layer 8 of the heat-shrinkable base film 7 is provided in order to strengthen the adhesion between the heat-shrinkable base film 7 and the second pressure-sensitive adhesive layer 8. If desired, the surface to be subjected to unevenness treatment such as sandblasting or solvent treatment, or oxidation treatment such as corona discharge treatment, electron beam irradiation, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromium acid treatment, hot air treatment, etc. Can be applied. In addition, primer treatment can be applied.

The thickness of the second pressure-sensitive adhesive layer is not particularly limited, but is preferably 2 to 50 μm, particularly preferably 3 to 20 μm.

The second pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. When the second pressure-sensitive adhesive layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

<Adhesive composition>
The second pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target portion by applying the pressure-sensitive adhesive composition to the surface to be formed of the second pressure-sensitive adhesive layer and drying it if necessary. A more specific method for forming the second pressure-sensitive adhesive layer is the same as the method for forming the first pressure-sensitive adhesive layer described above. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer.

The coating and drying conditions of the pressure-sensitive adhesive composition in the second pressure-sensitive adhesive layer are the same as those in the pressure-sensitive adhesive composition in the first pressure-sensitive adhesive layer.

When the second pressure-sensitive adhesive layer 8 is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy-ray-curable pressure-sensitive adhesive composition is, for example, non-energy ray-curable. A pressure-sensitive adhesive composition (I-1) containing a sex-sensitive adhesive resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound. ); Energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter, "adhesive resin (I-)". 2a) ”)-containing pressure-sensitive adhesive composition (I-2); a pressure-sensitive adhesive composition (I-2) containing the pressure-sensitive resin (I-2a) and an energy ray-curable compound. -3) and the like.

When the second pressure-sensitive adhesive layer 8 is non-energy ray-curable, the non-energy ray-curable pressure-sensitive adhesive composition includes, for example, the pressure-sensitive adhesive composition containing the pressure-sensitive adhesive resin (I-1a). I-4) and the like can be mentioned.

Among the pressure-sensitive adhesive compositions (I-1) to (I-4) shown above, in order to enable more stable pick-up of the diced chips with a film-like firing material, the pressure-sensitive adhesive composition ( I-2) is preferable.

As the pressure-sensitive adhesive composition used for the second pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition (I-1) may be used, but as described above, it is more preferable to use the pressure-sensitive adhesive composition (I-2). The reason is that the pressure-sensitive adhesive composition (I-2) can exhibit energy ray-curable properties without using an energy ray-curable compound, and even a pressure-sensitive adhesive resin having low compatibility with the energy ray-curable compound. , It can be used without problems.
For example, in the pressure-sensitive adhesive composition (I-1), a highly polar pressure-sensitive adhesive resin may be selected in order to enhance compatibility with an energy ray-curable compound. However, with a highly polar adhesive resin, the adhesive strength tends to increase with time after application.
An adhesive resin containing a structural unit derived from a (meth) acrylate having 8 to 18 carbon atoms in the side chain alkoxy group is unlikely to increase in adhesive strength with time after application, but is different from an energy ray-curable compound. The compatibility may be low. However, when the adhesive resin is contained in the adhesive composition (I-2) and has an energy ray-polymerizable unsaturated group in its side chain, the problem of compatibility with the energy ray-curable compound is considered. It is possible to achieve both energy ray curability and reduction of adhesive strength at a high level without doing so.

When the second pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive composition (I-2) contains a pressure-sensitive resin, and the pressure-sensitive adhesive resin is the same. An example thereof has an energy ray-polymerizable unsaturated group in the side chain.

The pressure-sensitive adhesive layer contains a pressure-sensitive resin, the pressure-sensitive adhesive resin has an energy ray-polymerizable unsaturated group in its side chain, and the pressure-sensitive adhesive resin has the number of carbon atoms of the alkoxy group in the side chain. Examples include those containing structural units derived from 8 to 18 (meth) acrylates.

<Adhesive composition (I-1)>
As described above, the pressure-sensitive adhesive composition (I-1) contains the non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.

The adhesive resin (I-1a) preferably contains a structural unit derived from an alkyl (meth) acrylate among the (meth) acrylate compounds, and the side chain alkoxy group has 8 to 18 carbon atoms (meth). ) It is preferable to contain a structural unit derived from an acrylate, and more preferably to contain a structural unit derived from an alkyl (meth) acrylate having 8 to 18 carbon atoms in the alkoxy group of the side chain. The alkoxy group of the side chain preferably has 8 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms. The alkoxy group of the side chain may be linear or branched. The adhesive resin contains a structural unit derived from (meth) acrylate having 8 to 18 carbon atoms in the alkoxy group of the side chain, so that the adhesive resin adheres at the interface between the second pressure-sensitive adhesive layer and the film-like fired material. It is possible to reduce the force and pick up the die-dipped film-shaped chip with firing material more stably.

In the adhesive resin constituting the pressure-sensitive adhesive layer, the content of the structural unit derived from the (meth) acrylic acid ester having 8 to 18 carbon atoms in the alkoxy group of the side chain is the total mass (100% by mass) of the structural unit. On the other hand, it is preferably 50 to 100% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 90% by mass.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group may be a starting point of cross-linking by reacting with a cross-linking agent described later, or the functional group may react with an unsaturated group in an unsaturated group-containing compound described later. Then, there is one that enables the introduction of an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohols (ie, unsaturated alcohols having no (meth) acryloyl skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (that is, monocarboxylic acids having ethylenically unsaturated bonds); fumaric acid, itaconic acid, and maleic acid. , Ethylunsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate. Examples include esters.

From the viewpoint of further reducing the adhesive force of the adhesive resin with the film-like fired material containing the sintered metal particles, (meth) with respect to the total mass (100% by mass) of the constituent units of the adhesive resin. The content of the constituent unit derived from acrylic acid is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, and derived from (meth) acrylic acid. It is particularly preferable that the constituent units are substantially not contained.

As the functional group-containing monomer, a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.
As the hydroxyl group-containing monomer, hydroxyalkyl (meth) acrylate is preferable.

The functional group-containing monomer constituting the acrylic polymer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, based on the total amount of the structural units. It is particularly preferably 3 to 30% by mass.

The acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1a).
On the other hand, a product obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) has the above-mentioned energy ray-curable adhesiveness. It can be used as a resin (I-2a).

The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the pressure-sensitive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 5 to 99% by mass. , 10-95% by mass is more preferable, and 15-90% by mass is particularly preferable.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray-curable compounds, examples of the monomer include trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4. Polyvalent (meth) acrylates such as −butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.
The energy ray-curable compound has a relatively large molecular weight, and urethane (meth) acrylate and urethane (meth) acrylate oligomer are preferable in that the storage elastic modulus of the pressure-sensitive adhesive layer is unlikely to be lowered.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass. It is more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from alkyl (meth) acrylate is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I-) is used. 1) preferably further contains a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-1) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-4).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The cross-linking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When a cross-linking agent is used, the content of the cross-linking agent in the pressure-sensitive adhesive composition (I-1) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-4).

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) is 0.01 to 20 mass by mass with respect to 100 parts by mass of the content of the energy ray-curable compound. The amount is preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive in the pressure-sensitive adhesive composition (I-1) include the same as the other additives in the pressure-sensitive adhesive composition (I-4).
The other additives contained in the pressure-sensitive adhesive composition (I-1) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

When other additives are used, the content of the other additives in the pressure-sensitive adhesive composition (I-1) is not particularly limited and may be appropriately selected depending on the type thereof.

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-4).
Examples of the solvent in the pressure-sensitive adhesive composition (I-1) include the same solvent as in the pressure-sensitive adhesive composition (I-4).
The solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
When a solvent is used, the content of the solvent in the pressure-sensitive adhesive composition (I-1) is not particularly limited and may be appropriately adjusted.

<Adhesive composition (I-2)>
As described above, the pressure-sensitive adhesive composition (I-2) is an energy-ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.

[Adhesive resin (I-2a)]
The adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.

In addition to the energy ray-polymerizable unsaturated group, the unsaturated group-containing compound can further bind to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (also known as an ethenyl group), an allyl group (also known as a 2-propenyl group), and the like, and a (meth) acryloyl group is preferable. ..
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-2), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-2) is preferably 5 to 99% by mass. , 10-95% by mass is more preferable, and 10-90% by mass is particularly preferable.

In the pressure-sensitive adhesive composition (I-2), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total content of all the components other than the solvent (that is, the second pressure-sensitive adhesive in the second pressure-sensitive adhesive layer). The ratio of the content of the adhesive resin (I-1a) to the total mass of the agent layer) is preferably 50 to 100% by mass, and may be, for example, 65 to 99% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, the pressure-sensitive adhesive composition ( I-2) may further contain a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-4).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When a cross-linking agent is used, the content of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive resin (I-2a). It is preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 3 parts by mass.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-4).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) is 0.01 to 100 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). The amount is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same as the other additives in the pressure-sensitive adhesive composition (I-4).
The other additives contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When other additives are used, the content of the other additives in the pressure-sensitive adhesive composition (I-2) is not particularly limited and may be appropriately selected depending on the type thereof.

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-4).
Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-4).
The solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected.
When a solvent is used, the content of the solvent in the pressure-sensitive adhesive composition (I-2) is not particularly limited and may be appropriately adjusted.

<Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive resin (I-2a) and an energy ray-curable compound.

In the pressure-sensitive adhesive composition (I-3), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-3) is preferably 5 to 99% by mass. , 10-95% by mass is more preferable, and 15-90% by mass is particularly preferable.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition. Examples thereof include the same energy ray-curable compounds contained in the substance (I-1).
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-4).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) is 100 parts by mass of the total content of the pressure-sensitive resin (I-2a) and the energy ray-curable compound. On the other hand, it is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive include the same as the other additive in the pressure-sensitive adhesive composition (I-4).
The other additives contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

When other additives are used, the content of the other additives in the pressure-sensitive adhesive composition (I-3) is not particularly limited and may be appropriately selected depending on the type thereof.

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-4).
Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-4).
The solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
When a solvent is used, the content of the solvent in the pressure-sensitive adhesive composition (I-3) is not particularly limited and may be appropriately adjusted.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)>
Up to this point, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described, but those described as the components contained therein have been described. General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to in the present specification as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)") However, it can be used in the same way.

Examples of the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions as well as energy-ray-curable pressure-sensitive adhesive compositions.
Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. The pressure-sensitive adhesive composition (I-4) containing a sex-sensitive pressure-sensitive resin (I-1a) can be mentioned, and those containing an acrylic resin are preferable.

[Manufacturing method of adhesive composition]
The pressure-sensitive adhesive compositions (I-1) to (I-3) can be produced by the same method as the pressure-sensitive adhesive composition (I-4).

[Manufacturing method of film-like firing material with support sheet]
The film-like fired material with a support sheet of the present embodiment can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship.
For example, the second pressure-sensitive adhesive on the heat-shrinkable base film on the first pressure-sensitive adhesive layer of the first support sheet in which the first pressure-sensitive adhesive layer is laminated on the non-heat-shrinkable base film. When laminating the second support sheet on which the layers are laminated, first, a pressure-sensitive adhesive composition containing a component and a solvent for forming the first pressure-sensitive adhesive layer is applied onto the release film. A first pressure-sensitive adhesive layer is formed in advance on the release film by drying it as necessary and volatilizing the solvent to form a film, and the first pressure-sensitive adhesive layer that has been formed is combined with the release film. The exposed surface on the side opposite to the contacting side is bonded to the surface of the non-heat shrinkable base film to produce a first support sheet with a release film. Similarly, a pressure-sensitive adhesive composition containing a component and a solvent for forming a second pressure-sensitive adhesive layer is applied onto the release film, and if necessary, dried to volatilize the solvent to form a film. Then, a second pressure-sensitive adhesive layer is formed on the release film in advance, and the exposed surface of the formed second pressure-sensitive adhesive layer on the side opposite to the side in contact with the release film is heat-shrinked. A second support sheet with a release film is manufactured by laminating with the surface of the sex base film. Next, the release film on the first pressure-sensitive adhesive layer of the first support sheet is removed, and the first pressure-sensitive adhesive layer is attached onto the heat-shrinkable base film of the second support sheet. The release film of the second support sheet may be removed if necessary after the laminated structure is formed.

Next, the second adhesion on the heat-shrinkable base film is placed on the first pressure-sensitive adhesive layer of the first support sheet in which the first pressure-sensitive adhesive layer is laminated on the non-heat-shrinkable base film. A support sheet formed by laminating the heat-shrinkable base film of the second support sheet on which the agent layer is laminated, and further laminating a film-like fired material on the second pressure-sensitive adhesive layer of the second support sheet. Attached film-like firing material (The first support sheet is a laminate of a non-heat-shrinkable base film and a first pressure-sensitive adhesive layer, and the second support sheet is a heat-shrinkable base film and a second pressure-sensitive adhesive. In the case of producing a film-like fired material with a support sheet, which is a laminate of layers, first, a first pressure-sensitive adhesive layer and a heat-shrinkable base material are placed on a non-heat-shrinkable base material film by the above method. The film and the second pressure-sensitive adhesive layer are laminated in this order. Next, separately, a baking material composition containing a component and a solvent for forming a film-like baking material is applied or printed on a release film, and if necessary, dried to volatilize the solvent to form a film. As a result, a film-like firing material is formed on the release film, and the exposed surface of the film-like firing material is attached to the exposed surface of the second pressure-sensitive adhesive layer already laminated on the heat-shrinkable base film. At the same time, by laminating the film-shaped firing material on the second pressure-sensitive adhesive layer, a film-shaped firing material with a support sheet can be obtained. When forming a film-like fired material on a release film, the fired material composition is preferably coated or printed on the peeled surface of the release film, and the release film can be removed as necessary after forming the laminated structure. Just do it.

As described above, all the layers other than the non-heat-shrinkable base film and the heat-shrinkable base film constituting the film-like firing material with the support sheet are formed in advance on the release film, and the target layer is formed. Since it can be laminated by a method of laminating it on the surface, a film-like fired material with a support sheet may be produced by appropriately selecting a layer that employs such a process, if necessary.

The film-like fired material with a support sheet may be stored in a state where a release film is attached to the surface of the outermost layer opposite to the first support sheet after all the necessary layers are provided.

≪Roll body≫
As one embodiment of the present invention, the film-shaped firing material with a support sheet is laminated on a long release film with the film-shaped firing material inside.
Provided is a roll body in which the release film and the film-like firing material with a support sheet are rolled.

FIG. 5 is a cross-sectional view schematically showing a roll body according to an embodiment of the present invention, showing a state in which the roll winding is unwound and a part thereof is unfolded. In the roll body 110, two or more units of the film-shaped firing material 100 with a support sheet processed into a predetermined shape are laminated on the release film 15 with the film-shaped firing material inside. The release film 15 and the film-shaped firing material 100 with a support sheet are rolled so that the side on which the film-shaped firing material 100 with a support sheet is laminated faces the center side. The roll winding direction is the longitudinal direction of the elongated release film 15.

One unit of the film-shaped firing material with a support sheet may be a portion of the film-shaped firing material with a support sheet used for attaching one or one object to be attached, and the unit P in FIG. 4 may be used. It can be a included part. In FIG. 4, one film-like firing material 1 is included in each unit P, and two or more units P are continuously arranged at predetermined intervals. The film-like firing materials with support sheets included in each unit P may be processed into the same shape. A preferable shape of the film-shaped firing material with a support sheet is that a circular support sheet and a circular film-shaped firing material having a diameter smaller than that of the support sheet are laminated concentrically.

Since the film-like firing material 1 can be easily attached to a semiconductor wafer or the like (object to be attached) and has adhesiveness, the film-like firing material 1 is sandwiched between the release film 15 having poor adhesion and the support sheet 2. It is suitable for storage as a roll because of the structure.
The roll body is also suitable as a distribution form for a film-shaped fired material with a support sheet.

The roll body can be manufactured by laminating the film-shaped firing material with a support sheet and the release film so as to have a corresponding positional relationship.

≪Laminated body≫
As one embodiment of the present invention, there is provided a laminated body in which the film-shaped firing material with a support sheet and a wafer are attached, and the support sheet, the film-shaped firing material, and the wafer are laminated in this order.
The laminate can be used as an intermediate in the manufacturing method of the apparatus described later.

FIG. 6 is a cross-sectional view schematically showing a laminated body according to an embodiment of the present invention. In the laminated body 120, the film-shaped firing material 100 with a support sheet and the semiconductor wafer 18 are laminated, and the first support sheet 6, the second support sheet 2, the film-shaped firing material 1, and the semiconductor wafer 18 are laminated in this order. It is. The semiconductor wafer 18 may be provided in direct contact with the film-like firing material 1.

The semiconductor wafer may be a silicon wafer or a silicon carbide wafer, or may be a compound semiconductor wafer such as gallium arsenide or arsenide. A circuit may be formed on the surface of the semiconductor wafer. The circuit can be formed on the wafer surface by various methods including a conventionally used method such as an etching method and a lift-off method. The opposite surface (back surface) of the circuit surface of the semiconductor wafer may be ground by a known means using a grinder or the like. At the time of backside grinding, an adhesive sheet called a surface protection sheet can be attached to the circuit surface in order to protect the circuit on the surface. In the back surface grinding, the circuit surface side (that is, the surface protection sheet side) of the wafer can be fixed with a chuck table or the like, and the back surface side on which the circuit is not formed can be ground with a grinder. The thickness of the wafer after grinding is not particularly limited, but is usually about 20 to 500 μm. Then, if necessary, the crushed layer generated during backside grinding is removed. The crushed layer can be removed by chemical etching, plasma etching, or the like. After grinding, a metal film may be provided on the back surface, and the metal film may be a single film or a plurality of films. Various methods such as electrolytic or electroless plating and sputtering can be used for forming the metal film.

The shape of the work (wafer, etc.) to be attached is usually circular, and therefore, the shapes of the film-shaped fired material 1, the first support sheet 6, and the second support sheet 2 are also circular. Is preferable.

In the laminate 120, the diameter of the film-like firing material 1 is preferably the same as the diameter of the semiconductor wafer 18 or larger than the diameter of the semiconductor wafer 18.
More specifically, the diameter difference between the film-shaped firing material and the wafer (diameter of the film-shaped firing material-diameter of the wafer) is preferably 0 to 20 mm, more preferably 1 to 15 mm. When the diameter difference is equal to or greater than the lower limit, the effect of suppressing chip skipping is excellent. When the above diameter difference is not more than the above upper limit value, an excellent wafer contamination prevention effect is exhibited.

In the laminated body 120, the diameter of the second support sheet 2 is preferably the same as the diameter of the film-shaped firing material 1 or larger than the diameter of the film-shaped firing material 1. Further, it is preferable that the diameter of the first support sheet 6 is the same as the diameter of the second support sheet 2 or larger than the diameter of the second support sheet 2.

The laminated body can be manufactured by laminating the film-shaped firing material with a support sheet and the wafer so as to have a corresponding positional relationship.

≪Manufacturing method of equipment≫
Next, a method of using the film-shaped firing material with a support sheet of the present embodiment will be described by taking as an example a case where a semiconductor wafer is used as a wafer and the firing material is applied to the manufacture of a semiconductor device.

As one embodiment of the present invention, the method for manufacturing a semiconductor device using the film-shaped firing material with a support sheet is the method for manufacturing a semiconductor device using the film-shaped firing material with a support sheet according to the present invention. This is a method in which steps (1) to (5) are sequentially performed.

Step (1): A step of dying the semiconductor wafer (work) and the film-like firing material of the laminate.
Step (2): A step of heating the diced film-like firing material and shrinking the second support sheet.
Step (3): A step of peeling the diced film-shaped firing material from the second support sheet to obtain a chip with a film-shaped firing material.
Step (4): A step of attaching the film-shaped firing material of the chip with the film-shaped firing material to the surface of the substrate.
Step (5): A step of firing the film-shaped firing material of the chip with the film-shaped firing material and joining the chip and the substrate.

Hereinafter, steps (1) to (5) of the method for manufacturing a semiconductor device will be described with reference to FIGS. 7A and 7B.

・ Process (1)
In the step (1), as shown in FIG. 7A (a), the film-shaped firing material 1 of the film-shaped firing material with a support sheet is attached to the semiconductor wafer 18, and the support sheet 2, the film-shaped firing material 1, and the semiconductor are attached. A laminated body 120 in which wafers 18 are laminated in this order is used.

Next, dicing of the semiconductor wafer is performed. Dicing of the semiconductor wafer can be performed by a known method and is not particularly limited.
For example, dicing of a semiconductor wafer is performed by a method using a blade (that is, blade dicing), a method by laser irradiation (that is, laser dicing), a method by spraying water containing an abrasive (that is, water dicing), and the like. This can be done by cutting a semiconductor wafer.

Here, as shown in FIG. 7A (b), a case where the semiconductor wafer 18 and the film-like firing material 1 of the laminate 120 are diced from the side of the semiconductor wafer 18 by using a dicing blade is illustrated. In dicing, the semiconductor wafer 18 and the film-like firing material 1 are cut together by forming a notch C, and the semiconductor wafer is divided to form a semiconductor chip 19. The notch C preferably reaches the first pressure-sensitive adhesive layer 4, but does not have to reach the non-heat-shrinkable base film 3.

A semiconductor wafer having a circuit formed on its surface is fragmented (chip), and is particularly referred to as an element or a semiconductor element.

In dicing, the rotation speed of the dicing blade is preferably 1000 to 60,000 rpm, more preferably 2000 to 50000 rpm. The moving speed of the dicing blade is preferably 20 to 80 mm / s, more preferably 40 to 60 mm / s.
Further, when the dicing blade is operated, it is preferable to flow cutting water at an amount of, for example, about 0.5 to 1.5 L / min to the portion where the dicing is performed.

・ Process (2)
In the step (2), the diced film-like firing material is heated to shrink the second support sheet 2.
As shown in FIG. 7A (c), when the heat-shrinkable base film 7 of the second support sheet 2 is shrunk by heating the died film-like fired material, the second support sheet 2 is formed on the heat-shrinkable base film 7. Since the pressure-sensitive adhesive layer 8 of 2 is also deformed along with the shrinkage of the heat-shrinkable base film, the bonding area between the semiconductor chip 19 and the second pressure-sensitive adhesive layer 8 is reduced.

・ Process (3)
In the step (3), the diced film-shaped firing material 1 and the second support sheet 2 are peeled off to obtain a chip 130 with a film-shaped firing material.
As shown in FIG. 7B (d), the semiconductor chip 19 is attached to the laminated body 120 after the notch C is formed, together with the diced film-like firing material 1, by the pulling portion 71 of the second support sheet. It can be separated (picked up) from the second pressure-sensitive adhesive layer 8 to obtain a chip 130 with a film-like firing material.

Here, as one embodiment, a chip 130 with a film-shaped firing material including a semiconductor chip 19 and a film-shaped firing material 1 can be manufactured.

In the step (2), the second pressure-sensitive adhesive layer 8 formed on the heat-shrinkable base film 7 of the second support sheet 2 is deformed along with the shrinkage of the heat-shrinkable base film 7. Since the adhesive area between the semiconductor chip 19 and the second pressure-sensitive adhesive layer 8 is reduced, for example, as shown in FIG. 7B (d), only the pull-up portion 71 is used without using the push-up pin, and the arrow I indicates. The semiconductor chip 19 can be easily picked up by pulling it up in the indicated direction.

The method of pulling up the semiconductor chip 19 may be a known method, and examples thereof include a method of sucking and pulling up the surface of the semiconductor chip 19 with a vacuum collet.

When the second pressure-sensitive adhesive layer 8 has curability such as energy ray curability, it is necessary to perform after dying and before peeling (picking up) the film-like firing material 1 and the second support sheet 2. The second pressure-sensitive adhesive layer 8 can be cured by irradiation with energy rays or the like to reduce the adhesive strength of the second pressure-sensitive adhesive layer 8. As a result, during dicing, the high adhesive force prevents the chips from scattering, and at the time of picking up, the adhesive force decreases due to curing, and the film-like fired material 1 can be more easily peeled (picked up) from the second support sheet. it can.

According to the film-like firing material with a support sheet of the present embodiment, the heat-shrinkable base film is used for the second support sheet to heat the die-dated film-like firing material. The base film shrinks, the contact surface between the second support sheet and the film-like firing material can be reduced, and the died chips with the film-like firing material can be stably picked up.

Further, in the laminated body 120, since the diameter of the film-shaped firing material 1 is the same as the diameter of the semiconductor wafer 18 or larger than the diameter of the semiconductor wafer 18, chip skipping is effectively prevented.

・ Process (4)
Subsequently, in the step (4), as shown in FIG. 7B (e), the film-shaped firing material 1 of the chip 130 with the film-shaped firing material is attached to the surface of the substrate 9. As a result, the chip 19 is attached to the substrate 9 via the film-like firing material 1. The substrate 9 also includes a lead frame, a heat sink, and the like. According to the film-shaped firing material with a support sheet of the present embodiment, it is expected that the adhesive force is exhibited between the film-shaped firing material and the substrate. Even in a state where the chip and the substrate are temporarily fixed with the film-like firing material before firing, it is possible to prevent the chip position from shifting during transportation or the like.

・ Process (5)
Next, in the step (5), the film-shaped firing material is fired, and the chip 19 and the substrate 9 are sintered and joined (FIG. 7B (f)). The exposed surface of the film-shaped firing material 1 of the chip 130 with the film-shaped firing material is attached to the substrate 9, and the substrate 9 and the chip 19 can be sintered and joined via the film-shaped firing material 1. By firing, the sintered metal particles of the film-shaped fired material 1 are melted and bonded to each other to form a sintered body 11, and the chip 19 and the substrate 9 are sintered and joined to obtain a semiconductor device 140.

The heating temperature for firing the film-shaped firing material may be appropriately determined in consideration of the type of the film-shaped firing material, but is preferably 100 to 600 ° C, more preferably 150 to 550 ° C, and further preferably 250 to 500 ° C. preferable. The heating time may be appropriately determined in consideration of the type of film-like firing material and the like, but is preferably 5 seconds to 60 minutes, more preferably 5 seconds to 30 minutes, still more preferably 10 seconds to 10 minutes.

The film-like firing material may be fired under pressure by applying pressure to the film-like firing material. The pressurizing condition can be, for example, about 1 to 50 MPa.

In the above embodiment, the sintering and joining of the chip of the film-shaped firing material and the substrate thereof has been exemplified, but the target of the sintering and joining of the film-shaped firing material is not limited to the one exemplified above, and the film-shaped firing Sintered bonding is possible for various articles that have been sintered in contact with the material.

Further, in the above embodiment, the chip can be processed as a film-like firing material having the same shape as the chip by being individualized together with the semiconductor wafer by using a blade or the like, and the chip with the film-like firing material can be manufactured. it can. That is, in the chip with the film-shaped firing material, the size (area) of the contact surface of the film-shaped firing material and the contact surface of the chip are the same, but they may be different. For example, the substrate and the chip may be bonded to each other via the film-shaped firing material in a state where the contact surface of the film-shaped firing material is larger than the contact surface of the chip. Specifically, a film-shaped firing material having a desired size may be arranged on the substrate, and a chip having a smaller contact surface than the film-shaped firing material may be attached onto the film-shaped firing material.

Depending on the method for manufacturing the apparatus of the embodiment, the apparatus can be manufactured with high efficiency by using a film-like firing material with a support sheet having excellent dicing suitability.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Example 1]
<Manufacturing of the first support sheet>
(Manufacturing of Adhesive Composition A)
It contains an acrylic polymer (100 parts by mass, solid content) and a toluene isocyanate adduct of trimethylolpropane (“Coronate L” manufactured by Toso Co., Ltd.) (2.5 parts by mass (solid content)), and further serves as a solvent. A non-energy ray-curable pressure-sensitive adhesive composition A containing a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate and having a solid content concentration of 30% by mass was produced. The acrylic polymer is a copolymer having a weight average molecular weight of 800,000, which is obtained by copolymerizing butyl acrylate (BA) (91 parts by mass) and acrylic acid (AA) (9 parts by mass).

(Manufacturing of first support sheet)
A release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) obtained by peeling one side of a polyethylene terephthalate film by a silicone treatment was used, and the pressure-sensitive adhesive composition A obtained above was used on the peeled surface. Was applied and dried by heating at 120 ° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer. At this time, the pressure-sensitive adhesive composition was applied by setting the conditions so that the thickness of the pressure-sensitive adhesive layer was 10 μm. A first support sheet was obtained by laminating a polyethylene-methacrylic acid (EMAA) film having a thickness of 80 μm as a base material on the exposed surface of the pressure-sensitive adhesive layer.

<Manufacturing of second support sheet>
(Manufacturing of Adhesive Composition B)
Energy ray-curable acrylic polymer (100 parts by mass, solid content), trimylene isocyanate adduct of trimethylolpropane ("Coronate L" manufactured by Toso Co., Ltd.) (1 part by mass (solid content)), photopolymerization initiator Energy ray-curable pressure-sensitive adhesive composition B having a solid content concentration of 30% by mass, containing 2.5 parts by mass of (OMNIRAD184 manufactured by IGM Resins) and further containing a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate as a solvent. Manufactured. The acrylic polymer is a copolymer of 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass), and has a weight average molecular weight of 600,000. It is a coalescence and is formed by reacting 100 g of the copolymer with 21.5 g of methacryloyloxyethyl isocyanate.

(Manufacturing of second support sheet)
A release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate film was peeled by a silicone treatment was used, and the pressure-sensitive adhesive composition B obtained above was used on the peeled surface. Was applied and dried by heating at 100 ° C. for 2 minutes to form an energy ray-curable pressure-sensitive adhesive layer. At this time, the pressure-sensitive adhesive composition was applied by setting the conditions so that the thickness of the pressure-sensitive adhesive layer was 10 μm. A second support sheet was obtained by laminating a heat-shrinkable polyethylene terephthalate film (shrinkage rate: 50%) having a thickness of 50 μm on the exposed surface of the pressure-sensitive adhesive layer as a base material.

<Manufacturing of firing material composition>
The components used in the production of the calcined material composition are shown below. Here, metal particles having a particle diameter of 100 nm or less are referred to as “sinterable metal particles”.
(Sinterable metal particle inclusion paste material)
-Arconano silver paste ANP-4 (organic coated composite silver nanopaste, manufactured by Applied Nanoparticle Research Institute: alcohol derivative coated silver particles, silver particles with a metal content of 80% by mass or more and an average particle size of 100 nm or less (sinterable metal) Particles) 25% by mass or more)
(Binder component)
-Acrylic polymer 1 (2-ethylhexyl methacrylate polymer, mass average molecular weight 260,000, Tg: -10 ° C)
The Tg of the acrylic polymer 1 is a calculated value using the Fox formula.

A paste material containing sinterable metal particles of 86.8 parts by mass and a binder component of 13.2 parts by mass were mixed to obtain a fired material composition. Since the sinterable metal particle-encapsulating paste material is sold containing a high boiling point solvent and remains in the film-like baking material after coating or drying, it is a component of the sinterable metal particle-encapsulating paste material. Is described including these. Considering that the solvent in the binder component volatilizes during drying, it represents the mass part of the solid content excluding the solvent component.

<Manufacturing of film-like firing material>
By printing the firing material composition obtained above on one side of a 230 mm wide release film (thickness 38 μm, SP-PET381031, manufactured by Lintec Corporation) so that the coating diameter is 155 mm, and drying at 150 ° C. for 10 minutes. , A film-like firing material having a thickness of 40 μm was obtained.

<Manufacturing of film-like firing material with support sheet>
A film-like firing material printed in a circular shape with a diameter of 205 mm is attached to the pressure-sensitive adhesive layer surface of the second support sheet (after the release film is peeled off), and the second support sheet is used as a base material in a concentric shape with a diameter of 210 mm. A second support in which a circular film-like firing material and a release film are laminated on a second second support sheet that is cut from the side and has a second pressure-sensitive adhesive layer on a heat-shrinkable base film. A film-like firing material with a sheet was obtained.
The film-like firing material with the second support sheet is attached to the pressure-sensitive adhesive layer surface of the first support sheet (after the release film is peeled off), and the first support sheet is concentrically placed on the substrate side with a diameter of 270 mm. A second support sheet, a circular film-like firing material, and a release film were laminated on a first support sheet having a first pressure-sensitive adhesive layer on a non-heat-shrinkable base film. A film-like firing material with a support sheet was obtained.

Table 1 shows the configurations of the first support sheet and the second support sheet.

[Example 2]
As the base material of the second support sheet, a heat-shrinkable polyethylene film (shrinkage rate: 40%) having a thickness of 25 μm is used instead of the heat-shrinkable polyethylene terephthalate film (shrinkage rate: 50%) having a thickness of 50 μm. A film-like fired material with a support sheet of Example 2 was obtained in the same manner as in Example 1 above except for the above.

[Comparative Example 1]
A film-like firing material printed in a circular shape with a diameter of 205 mm is attached to the pressure-sensitive adhesive layer surface of the first support sheet (after the release film is peeled off), and the first support sheet is concentrically used as a base material with a diameter of 270 mm. Support of Comparative Example 1 in which a circular film-like fired material and a release film are laminated on a first support sheet which is cut from the film side and has a first pressure-sensitive adhesive layer on a non-heat-shrinkable base film. A film-like firing material with a sheet was obtained.

≪Pickup evaluation≫
The film-like fired material with a support sheet obtained in each of the above Examples and Comparative Examples has a diameter of 20 mm / s at a table temperature of 60 ° C. using a wafer attachment device RAD-2500 m / 12 (manufactured by Lintec Corporation). It was attached to the back surface of a silicon wafer having a thickness of 200 mm and 100 μm, stretched on a ring frame made of SUS, and the following dicing was performed.

Dicing was performed using a blade dicer DFD6362 (manufactured by Disco Corporation) under the following conditions.
・ Dicing conditions: Implemented so that each tip has a size of 5 mm × 5 mm ・ Blade thickness: 25 μm width (27HECC)
・ Blade rotation speed: 30,000 rpm
-Cut condition: Performed so that the first base film is cut to a depth of 20 μm from the side of the film-like fired material.-Cut speed: 30 mm / s
・ Cut range: Wafer diameter + 20 mmφ
・ Cutting water volume: 1.5L / min ・ Cutting water temperature: 24 ℃

The chip having a size of 5 mm × 5 mm obtained by the above dicing is heated on a heating table at 110 ° C. for 60 seconds, fixed to the adsorption table, and adsorbed from the chip surface using an adsorption collet, and the pickup speed is 5 mm / Under the condition of s, 5 chips were picked up in succession.
If you can pick up 5 chips without any problem, ○,
If the pick-up is not possible, or if the pick-up is possible but there is a problem that a part of the film-like firing material remains on the second support sheet, and only 4 to 3 chips can be picked up without any problem.
A case where the pick-up was not possible or the pick-up was possible but a part of the film-like fired material remained on the second support sheet occurred and only two chips or less could be picked up without any problem was determined as x.

The above evaluation results are shown in Table 1 below.

As shown in Table 1, the heat-shrinkable base material is placed on the first pressure-sensitive adhesive layer side of the first support sheet having the first pressure-sensitive adhesive layer on one surface of the non-heat-shrinkable base film. In the second support sheet having a film and the film-like fired materials with support sheets of Examples 1 and 2 in which the film-shaped fired materials were laminated in this order, pick-up defects were suppressed. On the other hand, the first support sheet having a first pressure-sensitive adhesive layer on one surface of a non-heat-shrinkable base film without having a second support sheet having a heat-shrinkable base film. The film-like firing material with a support sheet of Comparative Example 1 in which the film-like firing material was directly laminated on the pressure-sensitive adhesive layer side of No. 1 had a pick-up defect.

Each configuration and a combination thereof in each embodiment are examples, and the configurations can be added, omitted, replaced, and other changes are possible without departing from the spirit of the present invention. Moreover, the present invention is not limited to each embodiment, but is limited only to the scope of claims.

1 ... film-like fired material, 2 ... second support sheet, 3 ... non-heat shrinkable base film, 4 ... first pressure-sensitive adhesive layer, 5 ... ring frame, 6 ... first support sheet, 7 ... heat Shrinkable substrate film, 8 ... second pressure-sensitive adhesive layer, 9 ... substrate, 10 ... sintered metal particles, 11 ... sintered body, 15 ... release film, 18 ... wafer, 19 ... chip, 20 ... binder component , 71 ... Pulling part, 100 ... Film-like firing material with support sheet, 100a ... Film-like firing material with support sheet, 110 ... Roll body, 120 ... Laminated body, 130 ... Chip with film-like firing material, 140 ... Semiconductor device, P ... unit, C ... notch

Claims (11)

A second support sheet having a heat-shrinkable base film on the first pressure-sensitive adhesive layer side of the first support sheet having a first pressure-sensitive adhesive layer on one surface of the non-heat-shrinkable base film. , And a film-like firing material with a support sheet in which film-like firing materials are laminated in this order. The support according to claim 1, wherein the second support sheet includes a second pressure-sensitive adhesive layer, and the film-like firing material is laminated on the second pressure-sensitive adhesive layer side of the second support sheet. Film-like firing material with sheet. The film-like firing material with a support sheet according to claim 2, wherein the second pressure-sensitive adhesive layer is energy ray-curable. The film-like firing material with a support sheet according to claim 3, wherein the second pressure-sensitive adhesive layer contains a pressure-sensitive adhesive resin, and the pressure-sensitive adhesive resin has an energy ray-polymerizable unsaturated group in its side chain. The film-like firing material with a support sheet according to any one of claims 1 to 4, wherein the first pressure-sensitive adhesive layer is non-energy ray-curable. The diameter of the first support sheet is the same as the diameter of the second support sheet, or larger than the diameter of the second support sheet, and the diameter of the second support sheet is the diameter of the film-like fired material. The film-shaped firing material with a support sheet according to any one of claims 1 to 5, which has the same diameter or is larger than the diameter of the film-shaped firing material. The film-like firing material with a support sheet according to any one of claims 1 to 6, wherein the heat-shrinkable base film comprises at least one selected from the group consisting of stretched polyethylene, stretched polypropylene, and stretched polyethylene terephthalate. .. The film-like firing material with a support sheet according to any one of claims 1 to 7 is laminated on a long release film with the film-shaped firing material inside.
A roll body in which the release film and the film-like firing material with a support sheet are rolled. The film-like baking material with a support sheet according to any one of claims 1 to 7 and a wafer are attached to the first support sheet, the second support sheet, the film-like baking material, and the above. A laminate in which wafers are laminated in this order. The laminate according to claim 9, wherein the diameter of the film-like fired material is the same as the diameter of the wafer or larger than the diameter of the wafer. A method for manufacturing an apparatus in which the following steps (1) to (5) are sequentially performed:
Step (1): A step of dying the wafer and the film-like firing material of the laminate according to claim 9 or 10.
Step (2): A step of heating the diced film-like firing material and shrinking the second support sheet.
Step (3): A step of peeling the diced film-shaped firing material and the second support sheet to obtain a chip with a film-shaped firing material.
Step (4): A step of attaching the film-shaped firing material of the chip with the film-shaped firing material to the surface of the substrate.
Step (5): A step of firing the film-shaped firing material of the chip with the film-shaped firing material and joining the chip and the substrate.

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